A mould-resistant halogen-free low-smoke flame-retardant rubber sheath material and a preparation method thereof

Abstract

The application discloses a kind of mould-resistant type halogen-free low-smoke flame-retardant rubber sheath material and preparation method thereof, sheath material includes the following components: EVM 40-60 parts, EVA 40-60 parts, POE 2-10 parts, calcium carbonate 20-50 parts, aluminium hydroxide 30-60 parts, zinc borate 15-30 parts, polyetheramine modified polystyrene maleic anhydride 5-20 parts, fire-extinguishing capsule powder 2-10 parts, antifungal agent 2-10 parts, white carbon black 1-10 parts, microcrystalline wax 1-10 parts, antioxidant 1-6 parts, wear-resistant carbon black 1-5 parts, release agent 1-5 parts, coupling agent 0.5-3 parts, sulfur 0.1-2 parts, accelerator 1-10 parts.The EVA of the application is compounded with EVM, and is matched with EVM release agent, polyetheramine modified polystyrene maleic anhydride, fire-extinguishing capsule powder and the like, so that the rubber sheath material shows excellent tensile property, oil resistance, mould resistance, flame retardancy, ageing resistance and low-temperature resistance and the like.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of cables, and particularly relates to a mold-resistant halogen-free low-smoke flame-retardant rubber sheath material and a preparation method thereof. BACKGROUND

[0002] Traditional cable sheath materials, such as PVC, can produce a large amount of toxic smoke and hydrogen halide gas during a fire, which poses a serious threat to the safety of personnel. Therefore, it is particularly important to develop low-smoke halogen-free flame-retardant materials.

[0003] In addition, in specific use environments such as ships, offshore platforms, and hot and humid areas, the growth and reproduction of mold are particularly serious for cables. The growth of mold can cause the insulation performance of cables to decrease, and even cause short circuits and failures, which seriously affect the service life and safety of cables. Therefore, it is particularly important to develop mold-resistant low-smoke halogen-free flame-retardant materials.

[0004] It is worth mentioning that in specific environments such as wind turbines, the cables laid inside the wind turbine need to follow the blades to twist, which requires the cables to have excellent softness and resilience to avoid the cracking of the sheath. SUMMARY

[0005] To solve the technical problems existing in the prior art, the purpose of the present application is to provide a mold-resistant halogen-free low-smoke flame-retardant rubber sheath material and a preparation method thereof.

[0006] To achieve the above-mentioned purposes and achieve the above-mentioned technical effects, the technical solution adopted by the present application is as follows:

[0007] A mold-resistant halogen-free low-smoke flame-retardant rubber sheath material, by weight, comprises the following components:

[0008] EVM 40-60 parts

[0009] EVA 40-60 parts

[0010] POE 2-10 parts

[0011] Calcium carbonate 20-50 parts

[0012] Aluminum hydroxide 30-60 parts

[0013] Zinc borate 15-30 parts

[0014] Polyetheramine modified polystyrene maleic anhydride 5-20 parts

[0015] Fire-extinguishing capsule powder 2-10 parts

[0016] Mold inhibitor 2-10 parts

[0017] White carbon black 1-10 parts

[0018] Microcrystalline wax 1-10 parts

[0019] Antioxidant 1-6 parts

[0020] Wear-resistant carbon black 1-5 parts

[0021] Release agent 1-5 parts

[0022] Coupling agent 0.5-3 parts

[0023] Sulfur 0.1-2 parts

[0024] Accelerator 1-10 parts.

[0025] Further, the mold-resistant halogen-free low-smoke flame-retardant rubber sheath material includes the following components by weight parts:

[0026] EVM 50 parts

[0027] EVA 50 parts

[0028] POE 5 parts

[0029] Calcium carbonate 35 parts

[0030] Aluminum hydroxide 55 parts

[0031] Zinc borate 24 parts

[0032] Polyetheramine modified polystyrene maleic anhydride 15 parts

[0033] Fire extinguishing capsule powder 5 parts

[0034] Mold inhibitor 5 parts

[0035] White carbon black 6 parts

[0036] Microcrystalline wax 5 parts

[0037] Antioxidant 3 parts

[0038] Wear-resistant carbon black 2 parts

[0039] Release agent 1.5 parts

[0040] Coupling agent 1.2 parts

[0041] Sulfur 1 part

[0042] Accelerator 4 parts.

[0043] Further, the mass ratio of EVM to EVA is 1:1, EVM uses ethylene-vinyl acetate 500HV, EVA uses maleic anhydride grafted EVA 40LW, and the grafting rate is 3-5%.

[0044] Further, the antifungal agent is a mixture of diclofenac and 2-butyl-1,2-benzisothiazoline-3-ketone with a mass ratio of 2:1, and the anti-aging agent is anti-aging agent XH-3.

[0045] Further, the wear-resistant carbon black is high-wear-resistant carbon black N330.

[0046] Further, the release agent is EVM release agent.

[0047] Further, the coupling agent is coupling agent A-172.

[0048] Further, the accelerator is accelerator TAC.

[0049] The application also discloses a preparation method of the mold-resistant halogen-free low-smoke flame-retardant rubber sheath material.

[0050] 1) uniformly mix EVM, EVA and POE in a mixer;

[0051] 2) add calcium carbonate, aluminum hydroxide, white carbon black, zinc borate, polyether amine modified polystyrene maleic anhydride, fire extinguishing capsule powder, an antifungal agent, microcrystalline wax, an anti-aging agent, wear-resistant carbon black, a release agent and a coupling agent into the mixture obtained in step 1) and continue to mix for 4-5 min until uniform;

[0052] 3) add vulcanizing agent sulfur and an accelerator into the mixture obtained in step 2) and continue to mix for 1-5 min until uniform, and then discharge the mixed rubber compound;

[0053] 4) pass the mixed rubber compound obtained in step 3) through a two-roller mill for 2-3 times and lay rubber for 2-3 times, and then pass through a three-roller calender to open the strip and obtain the mold-resistant halogen-free low-smoke flame-retardant rubber sheath material.

[0054] Further, in step 1), the mixing conditions are 85-95 DEG C and mixing for 2-3 min.

[0055] Compared with the prior art, the application has the following beneficial effects:

[0056] The application discloses a kind of mould-resistant type halogen-free low smoke flame-retardant rubber sheath material and preparation method thereof, EVA is used with EVM, EVM release agent, polyetheramine modified polystyrene maleic anhydride, fire-extinguishing capsule powder and other components are matched simultaneously, so that rubber sheath material shows excellent compatibility, tensile property, good resilience, excellent oil resistance, mould resistance, flame retardancy, ageing resistance and low temperature resistance, with good low smoke halogen-free characteristics, can reduce the emission of harmful gases when burning, can also provide good protection when fire occurs, ensure personnel safety, high resilience ensures that it can be used in fan cable, can avoid the situation that sheath cracks, and also solve the problem of existing sheath material in preparation process. DETAILED DESCRIPTION

[0057] The application will be described in detail below, so that the advantages and characteristics of the application can be more easily understood by those skilled in the art, so as to make the protection scope of the application more clear and definite.

[0058] The following gives a brief summary of one or more aspects to provide a basic understanding of these aspects. This summary is not an exhaustive overview of all contemplated aspects, and neither is it intended to identify key or essential elements of all aspects nor to delineate the scope of any or all aspects. Its sole purpose is to present some concepts of one or more aspects in a simplified form as a prelude to the more detailed description to be given later.

[0059] Noun explanation:

[0060] EVM: ethylene-vinyl acetate rubber;

[0061] EVA: maleic anhydride grafted ethylene-vinyl acetate copolymer;

[0062] POE: polyolefin elastomer.

[0063] The application discloses a kind of mould-resistant type halogen-free low smoke flame-retardant rubber sheath material, by weight fraction, including the following components:

[0064] EVM 40-60 parts

[0065] EVA 40-60 parts

[0066] POE 2-10 parts

[0067] Calcium carbonate 20-50 parts

[0068] Aluminum hydroxide 30-60 parts

[0069] Zinc borate 15-30 parts

[0070] Polyetheramine modified polystyrene maleic anhydride 5-20 parts

[0071] Fire extinguishing capsule powder 2-10 parts

[0072] Mold inhibitor 2-10 parts

[0073] White carbon black 1-10 parts

[0074] Microcrystalline wax 1-10 parts

[0075] Anti-aging agent 1-6 parts

[0076] Wear-resistant carbon black 1-5 parts

[0077] Release agent 1-5 parts

[0078] Coupling agent 0.5-3 parts

[0079] Sulfur 0.1-2 parts

[0080] Promoter 1-10 parts.

[0081] In the present application, the mass ratio of EVM to EVA is 1:1.

[0082] In some embodiments, EVM adopts ethylene-vinyl acetate copolymer 500HV.

[0083] In some embodiments, EVA adopts maleic anhydride grafted EVA 40LW with a grafting rate of 3-5%.

[0084] In some embodiments, the mold inhibitor is a mixture of dichlorophen and 2-butyl-1,2-benzisothiazolin-3-one in a mass ratio of 2:1.

[0085] In some embodiments, the anti-aging agent adopts anti-aging agent XH-3.

[0086] In some embodiments, the wear-resistant carbon black adopts high-wear-resistant carbon black N330.

[0087] In some embodiments, the release agent adopts EVM release agent.

[0088] In some embodiments, the coupling agent adopts coupling agent A-172.

[0089] In some embodiments, the promoter adopts promoter TAC.

[0090] The present application also discloses a preparation method of a mold-resistant halogen-free low-smoke flame-retardant rubber sheath material, comprising the following steps:

[0091] 1) uniformly mix EVM, EVA and POE in a mixer, and the mixing conditions are: 85-95℃, mixing for 2-3min;

[0092] 2) To the mixture obtained in step 1), calcium carbonate, aluminum hydroxide, white carbon black, zinc borate, polyether amine modified polystyrene maleic anhydride, fire extinguishing capsule powder, mildew inhibitor, microcrystalline wax, antioxidant, wear-resistant carbon black, release agent, coupling agent were added, and mixing was continued for 4-5 min, and the mixing was uniform;

[0093] 3) To the mixture obtained in step 2), vulcanizing agent sulfur and accelerator were added, and mixing was continued for 1-5 min, and after the mixing was uniform, the mixed rubber was discharged;

[0094] 4) The mixed rubber obtained in step 3) was passed through a mill on a mill 2-3 times, and the rubber was laid 2-3 times, and then the sheet was cut out by a three-roll calender, and the desired mold-resistant halogen-free low-smoke flame-retardant rubber sheath material was obtained after passing through talcum powder.

[0095] Example 1

[0096] A mold-resistant halogen-free low-smoke flame-retardant rubber sheath material, by weight fraction, includes the following components:

[0097] EVM 50 parts

[0098] EVA 50 parts

[0099] POE 5 parts

[0100] Calcium carbonate 35 parts

[0101] Aluminum hydroxide 55 parts

[0102] Zinc borate 24 parts

[0103] Polyether amine modified polystyrene maleic anhydride 15 parts

[0104] Fire extinguishing capsule powder 5 parts

[0105] Mildew inhibitor 5 parts

[0106] White carbon black 6 parts

[0107] Microcrystalline wax 5 parts

[0108] Antioxidant XH-3 3 parts

[0109] High wear-resistant carbon black N330 2 parts

[0110] EVM release agent 1.5 parts

[0111] Coupling agent A-172 1.2 parts

[0112] Sulfur 1 part

[0113] Accelerator TAC 4 parts.

[0114] EVA: EVA 40LW (maleic anhydride grafting, grafting rate is 3%), from Shanghai Xukai New Material Co., Ltd. EVA has excellent softness, thermal stability, and does not release harmful substances during combustion, and has excellent environmental performance, but has poor durability. By maleic anhydride grafting treatment, by chemical reaction, strong polar side groups are introduced into the molecular chain of EVA to form a graft copolymer, which gives EVA new properties, improves compatibility with non-polar materials, enhances adhesion, and improves processing performance. When used in cable materials, it can improve the flame retardant performance of the cable.

[0115] EVM: Ethylene-vinyl acetate copolymer 500HV, from Shanghai Tianlu Cable Material Co., Ltd.

[0116] EVA and EVM are compounded. Compared with EVA, EVM has excellent high temperature resistance, oil resistance, aging resistance and flame retardant performance, low smoke emission, toxicity and corrosiveness of smoke, and can maintain good elasticity under high temperature and high load. EVA and EVM compound not only shows excellent tensile properties, good resilience, but also has excellent oil resistance. However, due to the high elasticity and high temperature resistance of EVM, the processing difficulty is relatively large, and it is easy to stick to the roller during the production of the film. The higher the processing temperature, the stronger the adhesion. Therefore, EVM release agent is used to solve the above problems. The test proves that the sheath material of the embodiment has qualified performance, simple preparation process and strong operability.

[0117] EVM release agent: from Wuxi Norman Polymer Material Co., Ltd.

[0118] The mildew-proof agent is a mixture of dichlorophen and 2-butyl-1,2-benzisothiazolin-3-one in a mass ratio of 2:1 to improve the mildew resistance of the sheath material.

[0119] Calcium carbonate and aluminum hydroxide are compounded. When they decompose, they have endothermic effect, which can limit the continuous rise of temperature to achieve flame retardant effect. Compound fire extinguishing capsule powder, fire extinguishing capsule powder is sensitive to temperature and starts to release after being affected by temperature, which can prevent the spread of fire.

[0120] Polyetheramine modified polystyrene maleic anhydride uses polystyrene maleic anhydride as main chain and polyetheramine as side chain. By modifying polystyrene maleic anhydride with polyetheramine, the water solubility and thermal stability of polystyrene maleic anhydride are improved, and the dispersion is stabilized, realizing the compatibility of each component.

[0121] The main component of white carbon black is silicon dioxide. When silicon compounds burn, non-combustible carbon-containing compounds form a glassy non-polar carbon layer, which can play a role in heat insulation and oxygen resistance, and inhibit combustion.

[0122] Sulfur and accelerator TAC compound, high promotion low sulfur compound, crosslinked structure of positive sulfurization is mainly single sulfur bond, over sulfurization does not appear vulcanization back to the original phenomenon, thus the material has excellent heat resistance.

[0123] A preparation method of a mold-resistant halogen-free low-smoke flame-retardant rubber sheath material, comprising the following steps:

[0124] 1) uniformly mix EVM, EVA and POE in a mixer, and the mixing conditions are: 85 DEG C, mixing for 3 min;

[0125] 2) add calcium carbonate, aluminum hydroxide, white carbon black, zinc borate, polyether amine modified polystyrene maleic anhydride, fire extinguishing capsule powder, mildew-proof agent, microcrystalline wax, antioxidant XH-3, high wear-resistant carbon black N330, EVM release agent, coupling agent A-172 to the mixture obtained in step 1), and continue to mix for 5 min;

[0126] 3) add sulfur and accelerator TAC to the mixture obtained in step 2), and continue to mix for 3 min, and then discharge the mixed rubber after uniform mixing;

[0127] 4) thin pass the mixed rubber obtained in step 3) on an open mill for 3 times, and lay rubber for 3 times, and then pass through a three-roll calender to open the strip and obtain the desired mold-resistant halogen-free low-smoke flame-retardant rubber sheath material.

[0128] Example 2

[0129] A mold-resistant halogen-free low-smoke flame-retardant rubber sheath material, comprising the following components in parts by weight:

[0130] EVM 40 parts

[0131] EVA 40 parts

[0132] POE 10 parts

[0133] Calcium carbonate 50 parts

[0134] Aluminum hydroxide 60 parts

[0135] Zinc borate 30 parts

[0136] Polyether amine modified polystyrene maleic anhydride 20 parts

[0137] Fire extinguishing capsule powder 10 parts

[0138] Mildew-proof agent 10 parts

[0139] White carbon black 10 parts

[0140] Microcrystalline wax 10 parts

[0141] Antioxidant XH-3 6 parts

[0142] High wear resistant carbon black N330 5 parts

[0143] EVM release agent 5 parts

[0144] Coupling agent A-172 3 parts

[0145] Sulfur 2 parts

[0146] Accelerator TAC 10 parts.

[0147] EVM uses ethylated vegetable oil 500HV.

[0148] EVA uses maleic anhydride grafted EVA 40LW, grafting rate is 4%.

[0149] Mildewcide is a mixture of dichlorophen and 2-butyl-1,2-benzisothiazolin-3-ketone in a mass ratio of 2:1.

[0150] A kind of preparation method of halogen-free low smoke flame-retardant rubber sheath material resistant to mildew, comprising the following steps:

[0151] 1) EVM, EVA, POE are uniformly mixed in an internal mixer, and the mixing conditions are: 95 DEG C, mixing for 2 min;

[0152] 2) calcium carbonate, aluminum hydroxide, white carbon black, zinc borate, polyether amine modified polystyrene maleic anhydride, fire extinguishing capsule powder, mildewcide, microcrystalline wax, antioxidant, wear-resistant carbon black, release agent, coupling agent are added to the mixture obtained in step 1), and continue to mix for 5 min, and mix uniformly;

[0153] 3) sulfur and accelerator are added to the mixture obtained in step 2), and continue to mix for 5 min, and the mixed rubber is discharged after mixing uniformly;

[0154] 4) the mixing rubber obtained in step 3) is thin passed twice on the open mill, and laid twice at the same time, and then opened and sheeted by three roll calender, and the desired halogen-free low smoke flame-retardant rubber sheath material resistant to mildew is obtained after passing through talcum powder.

[0155] The rest is the same as example 1.

[0156] The difference between example 1 and comparative examples 1-3 is only that the formula composition of the sheath material is different, and the difference between example 1 and comparative examples 1-3 is only that the formula composition of the rubber sheath material is shown in table 1.

[0157] Table 1

[0158]

[0159]

[0160] The rubber sheath material obtained in Example 1 and Comparative Examples 1-3 is subjected to mechanical property testing, and the testing items and testing standards are shown in Table 2, and the testing results are shown in Table 3.

[0161] Table 2

[0162]

[0163] Table 3

[0164]

[0165]

[0166] As can be seen from Tables 1-3, the rubber sheath material of the present embodiment exhibits excellent tensile properties, low smoke halogen-free properties, flame retardant properties, aging resistance, low temperature resistance, salt mist resistance, and mold resistance, and also solves the problem of roller sticking in the preparation process of the existing sheath material, and is convenient to process and has high operability.

[0167] Parts or structures not specifically described in the present application can be adopted in the prior art or existing products, and will not be described here.

[0168] The above is only an embodiment of the present application, and does not limit the patent scope of the present application, and any equivalent structure or equivalent process transformation using the content of the present application specification, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A mold-resistant, halogen-free, low smoke, flame-retardant rubber jacketing material, characterized in that, By weight parts, including the following components: EVM 40-60 parts EVA 40-60 parts POE 2-10 parts Calcium carbonate 20-50 parts Aluminum hydroxide 30-60 parts Zinc borate 15-30 parts Polyether amine modified polystyrene maleic anhydride 5-20 parts Fire extinguishing capsule powder 2-10 parts Mildew-proof agent 2-10 parts White carbon black 1-10 parts Microcrystalline wax 1-10 parts Antioxidant 1-6 parts Wear-resistant carbon black 1-5 parts Release agent 1-5 parts Coupling agent 0.5-3 parts Sulfur 0.1-2 parts Promoter 1-10 parts The mass ratio of EVM to EVA is 1:1, EVM uses ethylene-vinyl acetate copolymer 500HV, EVA uses maleic anhydride grafted EVA 40LW, the grafting rate is 3-5%; The mildew-proof agent is a mixture of dichlorophen and 2-butyl-1,2-benzisothiazolin-3-one in a mass ratio of 2:1; Calcium carbonate and aluminum hydroxide are compounded, which has an endothermic effect when decomposed, limiting the temperature from rising continuously to achieve the effect of flame retardation, and fire extinguishing capsule powder is compounded, which is sensitive to temperature and starts to release after being affected by temperature, preventing the spread of fire.

2. A mould resistant, halogen-free, low smoke, flame retardant rubber jacketing material according to claim 1, characterised in that, By weight parts, the mildew-resistant halogen-free low-smoke flame-retardant rubber sheath material includes the following components: EVM 50 parts EVA 50 parts POE 5 parts Calcium carbonate 35 parts Aluminum hydroxide 55 parts Zinc borate 24 parts Polyether amine modified polystyrene maleic anhydride 15 parts Fire extinguishing capsule powder 5 parts Mildew-proof agent 5 parts White carbon black 6 parts Microcrystalline wax 5 parts Antioxidant 3 parts Wear-resistant carbon black 2 parts Release agent 1.5 parts Coupling agent 1.2 parts Sulfur 1 part Promoter 4 parts.

3. A mould resistant, halogen-free, low smoke, flame retardant rubber jacketing material as claimed in claim 1, wherein, the said jacketing material is a blend of chlorosulphonated polyolefin and chlorinated polyethylene. 5 The antioxidant uses antioxidant XH-3.

4. A mould resistant, halogen-free, low smoke, flame retardant rubber jacketing material as claimed in claim 1, wherein, ###0002### The wear-resistant carbon black uses high-wear-resistant carbon black N330.

5. The mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material according to claim 1, characterized in that, The release agent uses EVM release agent.

6. A mould resistant, halogen-free, low smoke, flame retardant rubber jacketing material as claimed in claim 1, wherein, ###0001### The coupling agent uses coupling agent A-172.

7. The mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material according to claim 1, characterized in that, The promoter uses promoter TAC.

8. A process for the preparation of a mould resistant, halogen-free, low smoke, flame retardant rubber jacketing material as claimed in claim 1, characterized in that, The steps include: 1) Mix EVM, EVA and POE uniformly in a mixer; 2) Add calcium carbonate, aluminum hydroxide, white carbon black, zinc borate, polyether amine modified polystyrene maleic anhydride, fire extinguishing capsule powder, mildew-proof agent, microcrystalline wax, antioxidant, wear-resistant carbon black, release agent and coupling agent to the mixture obtained in step 1) and continue mixing for 4-5 min until uniform; 3) Add vulcanizing agent sulfur and promoter to the mixture obtained in step 2) and continue mixing for 1-5 min until uniform, then discharge the mixed rubber; 4) Thin pass the mixed rubber obtained in step 3) on an open mill for 2-3 times, lay rubber for 2-3 times, then pass through a three-roll calender to open strips and sheets, and pass through talcum powder to obtain the desired mildew-resistant halogen-free low-smoke flame-retardant rubber sheath material.

9. A process for the preparation of a moulding compound according to claim 8, characterized in that In step 1), the mixing conditions are: 85-95℃, mixing for 2-3 min.

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