Mould-resistant halogen-free low-smoke flame-retardant rubber sheath material and preparation method thereof

Abstract

The invention discloses a mould-resistant halogen-free low-smoke flame-retardant rubber sheath material and a preparation method thereof. The sheath material comprises the following components: 40-60 parts of EVM, 40-60 parts of EVA, 2-10 parts of POE, 20-50 parts of calcium carbonate, 30-60 parts of aluminum hydroxide, 15-30 parts of zinc borate, 5-20 parts of polyether amine modified polystyrene maleic anhydride, 2-10 parts of fire extinguishing capsule powder, 2-10 parts of a mildew inhibitor, 1-10 parts of white carbon black, 1-10 parts of microcrystalline wax, 1-6 parts of an anti-aging agent, 1-5 parts of wear-resistant carbon black, 1-5 parts of a release agent, 0.5-3 parts of a coupling agent, 0.1-2 parts of sulfur and 1-10 parts of an accelerant. The EVA and the EVM are compounded, and the EVM release agent, the polyether amine modified polystyrene maleic anhydride, the fire extinguishing capsule powder and the like are matched, so that the rubber sheath material has excellent tensile property, oil resistance, mold resistance, flame retardance, aging resistance, low temperature resistance and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of cables, and in particular relates to a mildew-resistant halogen-free low-smoke flame-retardant rubber sheath material and a preparation method thereof. Background Art

[0002] Traditional cable sheath materials, such as PVC, will produce a large amount of toxic smoke and hydrogen halide gas in the event of a fire, posing 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 certain use environments, such as ships, offshore platforms, and hot and humid areas, the growth and reproduction of mold is particularly harmful to cables. The growth of mold can cause the insulation performance of cables to deteriorate, and even cause short circuits and failures, seriously affecting 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 certain environments, such as wind turbines, the cables laid inside the wind turbine need to twist with the blades, which requires the cables to have excellent flexibility and resilience to avoid cracking of the sheath. Summary of the invention

[0005] In order to solve the technical problems existing in the prior art, the object of the present invention is to provide a mildew-resistant halogen-free low-smoke flame-retardant rubber sheath material and a preparation method thereof.

[0006] In order to achieve the above purpose and the above technical effect, the technical solution adopted by the present invention is:

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

[0008] EVM 40-60 copies

[0009] EVA 40-60 parts

[0010] POE 2-10 copies

[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 portions

[0016] 2-10 parts of mildew inhibitor

[0017] 1-10 parts of white carbon black

[0018] Microcrystalline wax 1-10 parts

[0019] Anti-aging agent 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] Furthermore, the mildew-resistant halogen-free low-smoke flame-retardant rubber sheath material comprises the following components by weight:

[0026] EVM 50 copies

[0027] EVA 50 parts

[0028] POE 5 copies

[0029] Calcium carbonate 35 parts

[0030] Aluminium hydroxide 55 parts

[0031] 24 parts of zinc borate

[0032] Polyetheramine modified polystyrene maleic anhydride 15 parts

[0033] Fire extinguishing capsule powder 5 portions

[0034] 5 parts of mildew inhibitor

[0035] 6 parts of white carbon black

[0036] 5 parts microcrystalline wax

[0037] 3 parts of antioxidant

[0038] 2 parts of wear-resistant carbon black

[0039] 1.5 parts of release agent

[0040] 1.2 parts of coupling agent

[0041] 1 part sulfur

[0042] 4 parts of accelerator.

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

[0044] Furthermore, the mildew inhibitor is a mixture of dichlorophenol and 2-butyl-1,2-benzisothiazolin-3-one in a mass ratio of 2:1, and the antioxidant is antioxidant XH-3.

[0045] Furthermore, the wear-resistant carbon black adopts high wear-resistant carbon black N330.

[0046] Furthermore, the release agent is an EVM release agent.

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

[0048] Furthermore, the accelerator is TAC.

[0049] The present invention also discloses a method for preparing a mildew-resistant halogen-free, low-smoke, flame-retardant rubber sheath material, comprising the following steps:

[0050] 1) Mix EVM, EVA and POE evenly in an internal mixer;

[0051] 2) adding calcium carbonate, aluminum hydroxide, white carbon black, zinc borate, polyetheramine-modified polystyrene maleic anhydride, fire extinguishing capsule powder, mildew inhibitor, microcrystalline wax, antioxidant, wear-resistant carbon black, release agent, coupling agent to the mixture obtained in step 1), and continuing to mix for 4-5 minutes until the mixture is evenly mixed;

[0052] 3) adding sulfur as a vulcanizing agent and an accelerator to the mixture obtained in step 2), and continuing to mix for 1-5 minutes. After mixing evenly, the mixed rubber material is discharged;

[0053] 4) The mixed rubber material obtained in step 3) is thinned on an open mill for 2-3 times, and the rubber is swung for 2-3 times, and then is passed through a three-roll calender to form a sheet, and then talcum powder is passed to obtain the desired mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material.

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

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

[0056] The invention discloses a mildew-resistant halogen-free, low-smoke, flame-retardant rubber sheath material and a preparation method thereof. EVA and EVM are compounded for use, and are matched with an EVM release agent, polyetheramine-modified polystyrene maleic anhydride, fire-extinguishing capsule powder and other components, so that the rubber sheath material exhibits excellent compatibility, tensile properties, good resilience, excellent oil resistance, mildew resistance, flame retardancy, aging resistance and low-temperature resistance, and has good low-smoke and halogen-free properties, can reduce the emission of harmful gases during combustion, and can also provide good protection when a fire occurs to ensure personnel safety. The high resilience ensures that it can be used in fan cables to avoid the cracking of the sheath, and also solves the problem of sticking to the roller during the preparation process of the existing sheath material. DETAILED DESCRIPTION

[0057] The present invention is described in detail below so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making a clearer and more definite definition of the protection scope of the present invention.

[0058] A brief summary of one or more aspects is given below to provide a basic understanding of these aspects. This summary is not an exhaustive overview of all conceived aspects, and is neither intended to identify the key or critical elements of all aspects nor to define the scope of any or all aspects. Its only purpose is to give some concepts of one or more aspects in a simplified form as a prelude to a more detailed description that will be given later.

[0059] Glossary:

[0060] EVM: ethylene vinyl acetate rubber;

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

[0062] POE: Polyolefin elastomer.

[0063] The present invention discloses a mildew-resistant halogen-free low-smoke flame-retardant rubber sheath material, which comprises the following components by weight:

[0064] EVM 40-60 copies

[0065] EVA 40-60 parts

[0066] POE 2-10 copies

[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 portions

[0072] 2-10 parts of mildew inhibitor

[0073] 1-10 parts of white carbon black

[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] Accelerator 1-10 parts.

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

[0082] In some embodiments, the EVM uses EVM 500HV.

[0083] In some embodiments, the EVA is EVA 40LW grafted with maleic anhydride, and the grafting rate is 3-5%.

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

[0085] In some embodiments, the antioxidant is antioxidant XH-3.

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

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

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

[0089] In some embodiments, the accelerator is TAC.

[0090] The present invention also discloses a method for preparing a mildew-resistant halogen-free, low-smoke, flame-retardant rubber sheath material, comprising the following steps:

[0091] 1) Mix EVM, EVA and POE evenly in an internal mixer at 85-95°C for 2-3 minutes;

[0092] 2) adding calcium carbonate, aluminum hydroxide, white carbon black, zinc borate, polyetheramine-modified polystyrene maleic anhydride, fire extinguishing capsule powder, mildew inhibitor, microcrystalline wax, antioxidant, wear-resistant carbon black, release agent, coupling agent to the mixture obtained in step 1), and continuing to mix for 4-5 minutes until the mixture is evenly mixed;

[0093] 3) adding sulfur as a vulcanizing agent and an accelerator to the mixture obtained in step 2), and continuing to mix for 1-5 minutes. After mixing evenly, the mixed rubber material is discharged;

[0094] 4) The mixed rubber material obtained in step 3) is thinned on an open mill for 2-3 times, and the rubber is swung for 2-3 times, and then is passed through a three-roll calender to form a sheet, and then talcum powder is passed to obtain the desired mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material.

[0095] Example 1

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

[0097] EVM 50 copies

[0098] EVA 50 parts

[0099] POE 5 copies

[0100] Calcium carbonate 35 parts

[0101] Aluminium hydroxide 55 parts

[0102] 24 parts of zinc borate

[0103] Polyetheramine modified polystyrene maleic anhydride 15 parts

[0104] Fire extinguishing capsule powder 5 portions

[0105] 5 parts of mildew inhibitor

[0106] 6 parts of white carbon black

[0107] 5 parts microcrystalline wax

[0108] Anti-aging agent XH-3 3 parts

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

[0110] 1.5 parts of EVM release agent

[0111] Coupling agent A-172 1.2 parts

[0112] 1 part sulfur

[0113] Accelerator TAC 4 parts.

[0114] EVA: EVA 40LW (maleic anhydride grafted, grafting rate 3%), from Shanghai Xuerkai New Materials Co., Ltd. EVA has excellent softness and thermal stability, will not release harmful substances when burned, and has excellent environmental performance, but poor durability. Through maleic anhydride grafting treatment, through chemical reaction, a strong polar side group is introduced into the molecular chain of EVA to form a grafted copolymer, giving EVA new properties, improving compatibility with non-polar materials, enhancing adhesion, and improving processing performance. When used in cable materials, it can improve the flame retardant properties of the cable.

[0115] EVM: EVM 500HV, from Shanghai Tianliu Cable Materials Co., Ltd.

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

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

[0118] The mildew inhibitor is a mixture of dichlorophenol and 2-butyl-1,2-benzisothiazolin-3-one in a mass ratio of 2:1, which improves the mildew resistance of the sheath material.

[0119] Calcium carbonate and aluminum hydroxide are compounded, and the two have an endothermic effect when they decompose, which can limit the temperature from continuing to rise and achieve a flame retardant effect. The compound fire extinguishing capsule powder is sensitive to temperature and begins to release after being affected by temperature, which can prevent the spread of flames.

[0120] Polyetheramine-modified polystyrene maleic anhydride has polystyrene maleic anhydride as the main chain and polyetheramine as the side chain. Polystyrene maleic anhydride is modified by polyetheramine to improve the water solubility and thermal stability of polystyrene maleic anhydride, and also plays a role in stabilizing dispersion to achieve compatibility of various components.

[0121] The main component of white carbon black is silicon dioxide. When silicon compounds burn, they produce non-combustible carbon-containing compounds to form a glassy non-polar carbonized layer, which can act as a heat-insulating and oxygen-blocking layer, thereby inhibiting combustion.

[0122] Sulfur is compounded with accelerator TAC, with high accelerator and low sulfur. The cross-linking structure of the positive vulcanization is mainly single sulfur bond, and there is no vulcanization reversion phenomenon after persulfurization. The resulting material has excellent heat resistance.

[0123] A method for preparing a mildew-resistant halogen-free, low-smoke, flame-retardant rubber sheath material comprises the following steps:

[0124] 1) EVM, EVA and POE were mixed evenly in an internal mixer at 85°C for 3 minutes;

[0125] 2) Add calcium carbonate, aluminum hydroxide, white carbon black, zinc borate, polyetheramine modified polystyrene maleic anhydride, fire extinguishing capsule powder, mildew inhibitor, 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 mixing for 5 minutes until the mixture is evenly mixed;

[0126] 3) adding sulfur as a vulcanizing agent and TAC as an accelerator to the mixture obtained in step 2), and continuing to mix for 3 minutes. After mixing evenly, the mixed rubber material is discharged;

[0127] 4) The mixed rubber material obtained in step 3) is thinned on an open mill for 3 times, and the rubber is swung for 3 times, and then is passed through a three-roll calender to form a sheet, and then talcum powder is passed to obtain the desired mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material.

[0128] Example 2

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

[0130] EVM 40 copies

[0131] EVA 40 parts

[0132] POE 10

[0133] Calcium carbonate 50 parts

[0134] 60 parts of aluminum hydroxide

[0135] 30 parts of zinc borate

[0136] Polyetheramine modified polystyrene maleic anhydride 20 parts

[0137] Fire extinguishing capsule powder 10 portions

[0138] 10 parts of mildew inhibitor

[0139] 10 parts of white carbon black

[0140] 10 parts microcrystalline wax

[0141] Anti-aging agent 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] 2 parts sulfur

[0146] Accelerator TAC 10 parts.

[0147] EVM uses Yihuaping 500HV.

[0148] The EVA used was EVA 40LW grafted with maleic anhydride, and the grafting rate was 4%.

[0149] The mildew inhibitor is a mixture of dichlorophenol and 2-butyl-1,2-benzisothiazolin-3-one in a mass ratio of 2:1.

[0150] A method for preparing a mildew-resistant halogen-free, low-smoke, flame-retardant rubber sheath material comprises the following steps:

[0151] 1) EVM, EVA and POE were mixed evenly in an internal mixer at 95°C for 2 min;

[0152] 2) adding calcium carbonate, aluminum hydroxide, white carbon black, zinc borate, polyetheramine-modified polystyrene maleic anhydride, fire extinguishing capsule powder, mildew inhibitor, microcrystalline wax, antioxidant, wear-resistant carbon black, release agent, coupling agent to the mixture obtained in step 1), and continuing to mix for 5 minutes until the mixture is evenly mixed;

[0153] 3) adding sulfur as a vulcanizing agent and an accelerator to the mixture obtained in step 2), and continuing to mix for 5 minutes. After mixing evenly, the mixed rubber material is discharged;

[0154] 4) The mixed rubber material obtained in step 3) is thinned twice on an open mill, and the rubber is swung twice, and then is passed through a three-roll calender to form a sheet, and then talcum powder is passed to obtain the desired mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material.

[0155] The rest is the same as in Example 1.

[0156] The difference between Example 1 and Comparative Examples 1-3 is only the different formula composition of the sheath material. The difference between Example 1 and Comparative Examples 1-3 is only the formula composition of the rubber sheath material, see Table 1.

[0157] Table 1

[0158]

[0159]

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

[0161] Table 2

[0162]

[0163] Table 3

[0164]

[0165]

[0166] It can be seen from Tables 1-3 that the rubber sheath material of this embodiment exhibits excellent tensile properties, low smoke and halogen-free properties, flame retardant properties, aging resistance, low temperature resistance, salt spray resistance, and mildew resistance. It also solves the problem of roller sticking during the preparation process of existing sheath materials, and is easy to process and has high operability.

[0167] Parts or structures not specifically described in the present invention may adopt existing technologies or existing products and will not be described in detail here.

[0168] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material, characterized in that: By weight, it includes the following components: EVM 40-60 copies EVA 40-60 parts POE 2-10 copies Calcium carbonate 20-50 parts Aluminum hydroxide 30-60 parts Zinc borate 15-30 parts Polyetheramine modified polystyrene maleic anhydride 5-20 parts Fire extinguishing capsule powder 2-10 portions 2-10 parts of mildew inhibitor 1-10 parts of white carbon black Microcrystalline wax 1-10 parts Anti-aging agent 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.

2. The mildew-resistant halogen-free low-smoke flame-retardant rubber sheath material according to claim 1, characterized in that: The mildew-resistant halogen-free low-smoke flame-retardant rubber sheath material comprises the following components by weight: EVM 50 copies EVA 50 parts POE 5 copies Calcium carbonate 35 parts Aluminium hydroxide 55 parts 24 parts of zinc borate Polyetheramine modified polystyrene maleic anhydride 15 parts Fire extinguishing capsule powder 5 portions 5 parts of mildew inhibitor 6 parts of white carbon black 5 parts microcrystalline wax 3 parts of antioxidant 2 parts of wear-resistant carbon black 1.5 parts of release agent 1.2 parts of coupling agent 1 part sulfur 4 parts of accelerator.

3. The mildew-resistant halogen-free low-smoke flame-retardant rubber sheath material according to claim 1, characterized in that: The mass ratio of EVM to EVA is 1:1, EVM adopts EVA 500HV, and EVA adopts EVA 40LW grafted with maleic anhydride, with a grafting rate of 3-5%.

4. The mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material according to claim 1, characterized in that: The mildew inhibitor is a mixture of dichlorophenol and 2-butyl-1,2-benzisothiazolin-3-one in a mass ratio of 2:1, and the antioxidant is antioxidant XH-3.

5. The mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material according to claim 1, characterized in that: The wear-resistant carbon black adopts high wear-resistant carbon black N330.

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

7. The mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material according to claim 1, characterized in that: The coupling agent is coupling agent A-172.

8. The mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material according to claim 1, characterized in that: The accelerator used is accelerator TAC.

9. A method for preparing a mildew-resistant halogen-free low-smoke flame-retardant rubber sheath material, characterized in that: The following steps are involved: 1) Mix EVM, EVA and POE evenly in an internal mixer; 2) adding calcium carbonate, aluminum hydroxide, white carbon black, zinc borate, polyetheramine-modified polystyrene maleic anhydride, fire extinguishing capsule powder, mildew inhibitor, microcrystalline wax, antioxidant, wear-resistant carbon black, release agent, coupling agent to the mixture obtained in step 1), and continuing to mix for 4-5 minutes until the mixture is evenly mixed; 3) adding sulfur as a vulcanizing agent and an accelerator to the mixture obtained in step 2), and continuing to mix for 1-5 minutes. After mixing evenly, the mixed rubber material is discharged; 4) The mixed rubber material obtained in step 3) is thinned on an open mill for 2-3 times, and the rubber is swung for 2-3 times, and then is passed through a three-roll calender to form a sheet, and then talcum powder is passed to obtain the desired mildew-resistant, halogen-free, low-smoke, flame-retardant rubber sheath material.

10. The method for preparing a mildew-resistant halogen-free low-smoke flame-retardant rubber sheath material according to claim 9, characterized in that: In step 1), the mixing conditions are: 85-95° C., and mixing for 2-3 min.

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