A sulfur-free environment-friendly automobile wire harness protective sleeve processing material and a preparation method thereof

Abstract

The application discloses a sulfur-free environment-friendly automobile wire harness protection sleeve processing material and a preparation method thereof, and relates to the technical field of rubber product processing, which is prepared from the following raw materials in parts by weight: 100-150 parts of ethylene-propylene-diene rubber, 70-110 parts of reinforcing agent, 20-40 parts of filling agent, 50-90 parts of softening agent, 3-10 parts of zinc oxide, 1-5 parts of stearic acid, 1-5 parts of activated dispersing agent, 1-5 parts of vulcanizing agent and 2-8 parts of accelerator; the sulfur-free environment-friendly automobile wire harness protection sleeve processing material can be used in the full-automatic production of automobile headlamp wire harness protection sleeves, has good environmental protection, meets the ROHS 2.0 instruction and the REACH regulation, and does not contain free sulfur and cannot corrode surrounding products.

Description

Technical fields:

[0001] This invention relates to the field of rubber product processing technology, specifically to a sulfur-free, environmentally friendly automotive wiring harness protective sleeve processing material and its preparation method. Background technology:

[0002] Automotive wiring harnesses are the core of a vehicle's electrical network; without them, there is no automotive electrical system. A wiring harness is an assembly consisting of copper-formed contact terminals (connectors) crimped to wires and cables, then covered with a molded insulator or an outer metal shell, and bundled together to form a connected circuit. Automotive wiring harnesses are mostly protected by perforated corrugated tubing, braided tubing, or spiral tubing; the material and structure of the protective sleeve directly affect the reliability of the automotive wiring harness.

[0003] Currently, the impact resistance, flame retardancy, and heat resistance of automotive wiring harness protective sleeves generally meet application requirements, but their environmental friendliness still needs improvement. Free sulfur refers to unbonded sulfur in the vulcanized rubber or compound; its presence can corrode metals. Furthermore, the presence of harmful chemicals affects the safety of automotive wiring harness protective sleeves and their environmental pollution after disposal. Summary of the Invention:

[0004] The technical problem to be solved by the present invention is to provide a processing material for automotive wiring harness protective sleeves. This processing material is environmentally friendly, does not contain free sulfur, and its preparation method is characterized by simple operation, simple equipment, high production efficiency, and stable product quality.

[0005] The technical problem to be solved by this invention is achieved by the following technical solution:

[0006] One objective of this invention is to provide a sulfur-free, environmentally friendly automotive wiring harness protective sleeve processing material, which is processed from the following raw materials in parts by weight:

[0007]

[0008]

[0009] Ethylene propylene diene monomer (EPDM) rubber is a terpolymer of ethylene, propylene, and non-conjugated olefins. Due to its high main chain saturation, it possesses superior resistance to oxidation, ozone, and chemical attack. It also exhibits excellent vulcanization properties, allowing for various methods such as sulfur vulcanization and peroxide vulcanization. Furthermore, EPDM has the lowest specific gravity of all rubbers, enabling it to be filled with large quantities of various fillers and oils, thus facilitating the production of low-cost rubber products.

[0010] Preferably, the reinforcing agent is carbon black. EPDM is a non-crystalline rubber with inherently low mechanical strength, requiring reinforcing agents for improvement. Carbon black is the preferred choice due to its high abrasion resistance, semi-reinforcing properties, and fast extrusion characteristics.

[0011] Preferably, the filler is one or more of calcined clay, calcium carbonate, and talc. Other fillers commonly used in the art may also be used. The filler has virtually no reinforcing effect, but its extensive use in EPDM can reduce costs.

[0012] Preferably, the softener is paraffin oil. Aromatic oils and naphthenic oils may also be used. The softener can improve the processing properties of the rubber to some extent.

[0013] The present invention also modifies the paraffin oil and uses the resulting modified paraffin oil as a softener, which can improve the processing performance of rubber and significantly improve the physical and mechanical properties of rubber.

[0014] Preferably, the softener is modified paraffin oil, which is prepared by adding paraffin oil, N-allyl isopropylamine, acryloyloxypropyltrimethoxysilane and an azo initiator to a reaction vessel, heating to carry out a copolymerization reaction, and obtaining modified paraffin oil.

[0015] In-situ generation of binary copolymers with unique molecular and spatial structures within paraffin oil achieves modification of the oil. Since paraffin oil is used in large quantities, its modified form can optimize the physical and mechanical properties of rubber.

[0016] More preferably, the molar ratio of N-allyl isopropylamine to acryloyloxypropyltrimethoxysilane is (2-3):1; and the total mass of N-allyl isopropylamine and acryloyloxypropyltrimethoxysilane is 20-30% of the mass of paraffin oil.

[0017] Zinc oxide can improve crosslinking activity, increase crosslinking density, and enhance the heat resistance and dynamic fatigue properties of rubber.

[0018] Stearic acid can not only improve the processing performance of rubber compounds and promote the dispersion of raw materials, but also increase the crosslinking density of sulfur vulcanization.

[0019] Preferably, the activating dispersant is polyethylene glycol (PEG). When a large amount of filler is added to rubber, an activating dispersant is needed to promote the uniform dispersion of the filler in the rubber.

[0020] Preferably, the vulcanizing agent is pre-dispersed sulfur. Using a sulfur vulcanization system results in a fast vulcanization rate, good physical properties, easy trimming, and lower cost.

[0021] Preferably, the accelerator is EG3T-75GE. The function of the accelerator is to shorten the vulcanization time, lower the vulcanization temperature, reduce the amount of vulcanizing agent used, and improve the physical and mechanical properties of the rubber.

[0022] The second objective of this invention is to provide a method for preparing a sulfur-free, environmentally friendly automotive wiring harness protective sleeve material, comprising the following steps:

[0023] (1) First stage of mixing: EPDM rubber is put into a mixer for mixing, then zinc oxide, stearic acid and activating dispersant are added for mixing, then reinforcing agent, filler and softener are added for mixing. When the temperature of the mixer reaches 130°C, the material is fed out and then sheeted out of the open mill and left to stand for a period of time.

[0024] (2) Two-stage mixing: After the rubber compound has been left to stand, it is put into an internal mixer, then vulcanizing agent and accelerator are added and mixed. The mixture is then fed into a two-roll mill to form sheets, which are then cooled and packaged.

[0025] The beneficial effects of this invention are:

[0026] 1. The method for preparing sulfur-free environmentally friendly automotive wiring harness protective sleeve processing material provided by the present invention has the characteristics of simple operation, simple equipment, high production efficiency, and stable product quality, thereby reducing production costs and improving economic benefits.

[0027] 2. The sulfur-free environmentally friendly automotive wiring harness protective sleeve processing material provided by this invention can be used for the fully automated production of automotive headlight wiring harness protective sleeves. It has good environmental performance, complies with the EU RoHS 2.0 directive and REACH regulations, and does not contain free sulfur, so it will not corrode surrounding products, greatly improving the environmental protection and safety of automotive wiring harness protective sleeves. Detailed implementation method:

[0028] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below with reference to specific embodiments.

[0029] The following examples and comparative examples illustrate the sources of raw materials:

[0030] Carbon black N550 is sourced from Longxing Chemical Co., Ltd.

[0031] The calcined clay comes from Shanxi Jinyu Kelin Technology Co., Ltd.;

[0032] The paraffin oil is sourced from Shanghai Haide Lubricating Oil Co., Ltd.

[0033] The zinc oxide comes from Jinhua Zinc Oxide Plant in Hanshan County, Anhui Province;

[0034] Stearic acid is sourced from Hangzhou Oil & Fat Chemical Co., Ltd.

[0035] PEG4000 is sourced from Lotte in South Korea;

[0036] Predispersed sulfur S-80H is sourced from Sichuan Antai Rubber Technology Co., Ltd.

[0037] The accelerator EG3T-75GE is sourced from Taiwan Science & Trade Corporation.

[0038] Example 1

[0039] 1. Raw material formula for automotive wiring harness protective sleeve processing materials:

[0040] raw material weight EPDM rubber 125 Carbon Black N550 90 Calcination of clay 30 paraffin oil 70 Zinc oxide 5 stearic acid 1 PEG4000 2 Predispersed Sulfur S-80H 1.5 Accelerator EG3T-75GE 4

[0041] 2. Prepare the automotive wiring harness protective sleeve processing material according to the above formula, including the following steps:

[0042] (1) First stage of mixing: EPDM rubber is put into the internal mixer and mixed for 60s, then zinc oxide, stearic acid and activating dispersant are added and mixed for 30s, then reinforcing agent, filler and softener are added and mixed. When the internal mixer temperature reaches 130℃, the material is fed out and sheeted out of the open mill and left to stand for 24h.

[0043] (2) Two-stage mixing: After the rubber compound has been left to stand, it is put into the internal mixer, then vulcanizing agent and accelerator are added and mixed for 3 minutes. The mixture is then fed into the open mill and sheeted out after 120 seconds. It is then cooled and packaged.

[0044] Example 2

[0045] 1. Raw material formula for automotive wiring harness protective sleeve processing materials:

[0046] raw material weight EPDM rubber 120 Carbon Black N550 80 Calcination of clay 20 paraffin oil 60 Zinc oxide 5 stearic acid 2 PEG4000 2 Predispersed Sulfur S-80H 2 Accelerator EG3T-75GE 4

[0047] 2. Prepare the automotive wiring harness protective sleeve processing material according to the above formula, including the following steps:

[0048] (1) First stage of mixing: EPDM rubber is put into the internal mixer and mixed for 60s, then zinc oxide, stearic acid and activating dispersant are added and mixed for 30s, then reinforcing agent, filler and softener are added and mixed. When the internal mixer temperature reaches 130℃, the material is fed out and sheeted out of the open mill and left to stand for 24h.

[0049] (2) Two-stage mixing: After the rubber compound has been left to stand, it is put into the internal mixer, then vulcanizing agent and accelerator are added and mixed for 3 minutes. The mixture is then fed into the open mill and sheeted out after 120 seconds. It is then cooled and packaged.

[0050] Example 3

[0051] 1. Raw material formula for automotive wiring harness protective sleeve processing materials:

[0052] raw material weight EPDM rubber 115 Carbon Black N550 80 Calcination of clay 20 paraffin oil 50 Zinc oxide 4 stearic acid 1 PEG4000 2 Predispersed Sulfur S-80H 1.5 Accelerator EG3T-75GE 3.5

[0053] 2. Prepare the automotive wiring harness protective sleeve processing material according to the above formula, including the following steps:

[0054] (1) First stage of mixing: EPDM rubber is put into the internal mixer and mixed for 60s, then zinc oxide, stearic acid and activating dispersant are added and mixed for 30s, then reinforcing agent, filler and softener are added and mixed. When the internal mixer temperature reaches 130℃, the material is fed out and sheeted out of the open mill and left to stand for 24h.

[0055] (2) Two-stage mixing: After the rubber compound has been left to stand, it is put into the internal mixer, then vulcanizing agent and accelerator are added and mixed for 3 minutes. The mixture is then fed into the open mill and sheeted out after 120 seconds. It is then cooled and packaged.

[0056] Example 4

[0057] 1. Raw material formula for automotive wiring harness protective sleeve processing materials:

[0058] raw material weight EPDM rubber 120 Carbon Black N550 80 Calcination of clay 25 paraffin oil 60 Zinc oxide 4 stearic acid 1 PEG4000 2 Predispersed Sulfur S-80H 1.5 Accelerator EG3T-75GE 4

[0059] 2. Prepare the automotive wiring harness protective sleeve processing material according to the above formula, including the following steps:

[0060] (1) First stage of mixing: EPDM rubber is put into the internal mixer and mixed for 60s, then zinc oxide, stearic acid and activating dispersant are added and mixed for 30s, then reinforcing agent, filler and softener are added and mixed. When the internal mixer temperature reaches 130℃, the material is fed out and sheeted out of the open mill and left to stand for 24h.

[0061] (2) Two-stage mixing: After the rubber compound has been left to stand, it is put into the internal mixer, then vulcanizing agent and accelerator are added and mixed for 3 minutes. The mixture is then fed into the open mill and sheeted out after 120 seconds. It is then cooled and packaged.

[0062] Example 5

[0063] 1. Raw material formula for automotive wiring harness protective sleeve processing materials:

[0064]

[0065]

[0066] 2. Prepare the automotive wiring harness protective sleeve processing material according to the above formula, including the following steps:

[0067] (1) First stage of mixing: EPDM rubber is put into the internal mixer and mixed for 60s, then zinc oxide, stearic acid and activating dispersant are added and mixed for 30s, then reinforcing agent, filler and softener are added and mixed. When the internal mixer temperature reaches 130℃, the material is fed out and sheeted out of the open mill and left to stand for 24h.

[0068] (2) Two-stage mixing: After the rubber compound has been left to stand, it is put into the internal mixer, then vulcanizing agent and accelerator are added and mixed for 3 minutes. The mixture is then fed into the open mill and sheeted out after 120 seconds. It is then cooled and packaged.

[0069] Example 6

[0070] The only difference between Example 6 and Example 1 is that the modified paraffin oil A-1 prepared below is used instead of the paraffin oil in Example 1.

[0071] Preparation of modified paraffin oil A-1: ​​200g paraffin oil, 19.8g N-allyl isopropylamine, 20.6g acryloyloxypropyltrimethoxysilane and 1g azobisisobutyronitrile were added to a reaction vessel, and the mixture was heated to 100℃ for copolymerization. After the reaction was complete, it was naturally cooled to room temperature to obtain modified paraffin oil A-1.

[0072] Example 7

[0073] The only difference between Example 7 and Example 1 is that the modified paraffin oil A-2 prepared below is used instead of the paraffin oil in Example 1.

[0074] Preparation of modified paraffin oil A-2: 200g paraffin oil, 29.7g N-allyl isopropylamine, 20.6g acryloyloxypropyltrimethoxysilane and 1g azobisisobutyronitrile were added to a reaction vessel, and the mixture was heated to 100℃ for copolymerization. After the reaction was complete, it was naturally cooled to room temperature to obtain modified paraffin oil A-2.

[0075] Comparative Example 1

[0076] The only difference between Comparative Example 1 and Example 6 is that modified paraffin oil B-1 prepared below is used instead of modified paraffin oil A-1 in Example 6, that is, acryloyloxypropyltrimethoxysilane is not added as a comonomer, and the amount of acryloyloxypropyltrimethoxysilane is added to N-allyl isopropylamine.

[0077] Preparation of modified paraffin oil B-1: 200g paraffin oil, 40.4g N-allyl isopropylamine and 1g azobisisobutyronitrile were added to a reaction vessel, and the temperature was raised to 100℃ for copolymerization. After the reaction was complete, the mixture was naturally cooled to room temperature to obtain modified paraffin oil B-1.

[0078] Comparative Example 2

[0079] The only difference between Comparative Example 2 and Example 6 is that modified paraffin oil B-2 prepared below is used instead of modified paraffin oil A-1 in Example 6, that is, N-allyl isopropylamine is not added as a comonomer, and the amount of N-allyl isopropylamine is added to acryloyloxypropyltrimethoxysilane.

[0080] Preparation of modified paraffin oil B-2: 200g paraffin oil, 40.4g acryloyloxypropyltrimethoxysilane and 1g azobisisobutyronitrile were added to a reaction vessel, and the temperature was raised to 100℃ for copolymerization. After the reaction was complete, the mixture was naturally cooled to room temperature to obtain modified paraffin oil B-2.

[0081] Comparative Example 3

[0082] The only difference between Comparative Example 3 and Example 6 is that the modified paraffin oil A-1 in Example 6 is replaced by the following mixture D.

[0083] Preparation of copolymer C: 300g toluene, 29.7g N-allyl isopropylamine, 30.9g acryloyloxypropyltrimethoxysilane and 1.5g azobisisobutyronitrile were added to a reaction vessel, and the mixture was heated to 100℃ for copolymerization. After the reaction was complete, toluene was recovered by vacuum distillation and the mixture was naturally cooled to room temperature to obtain copolymer C.

[0084] Preparation of mixture D: Mix 200g of paraffin oil and 40.4g of copolymer C evenly to obtain mixture D.

[0085] The free sulfur content of the automotive wiring harness protective sleeve processing materials prepared in Examples 1-7 above was determined according to the standard GB / T 15251-2008 "Determination of Free Sulfur in Rubber". The results showed that there was no free sulfur.

[0086] Tests have shown that the content of harmful chemical substances in the automotive wiring harness protective sleeve processing materials prepared in Examples 1-7 complies with the EU RoHS 2.0 Directive and REACH regulations.

[0087] The tensile strength and elongation at break of the automotive wiring harness protective sleeve materials prepared in Examples 1-7 and Comparative Examples 1-3 were tested according to the standard GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber". The results are shown in Table 1.

[0088] Table 1

[0089]

[0090]

[0091] As can be seen from Table 1, Examples 6 and 7 can substantially improve the physical and mechanical properties of automotive wiring harness protective sleeve processing materials by modifying the paraffin oil as described above.

[0092] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A sulfur-free, environmentally friendly automotive wiring harness protective sleeve processing material, characterized in that, It is processed from the following raw materials in parts by weight: 100-150 parts of EPDM rubber 70-110 parts of reinforcing agent 20-40 parts of filler 50-90 parts of softener 3-10 parts zinc oxide 1-5 parts stearic acid 1-5 parts of activating dispersant 1-5 parts of vulcanizing agent Accelerator 2-8 parts; The softener is modified paraffin oil, which is prepared by adding paraffin oil, N-allyl isopropylamine, acryloyloxypropyltrimethoxysilane and an azo initiator to a reaction vessel, heating to carry out a copolymerization reaction, and obtaining modified paraffin oil.

2. The sulfur-free environmentally friendly automotive wiring harness protective sleeve processing material according to claim 1, characterized in that: The reinforcing agent is carbon black.

3. The sulfur-free environmentally friendly automotive wiring harness protective sleeve processing material according to claim 1, characterized in that: The filler is one or more of calcined clay, calcium carbonate, and talc.

4. The sulfur-free environmentally friendly automotive wiring harness protective sleeve processing material according to claim 1, characterized in that: The activating dispersant is polyethylene glycol.

5. The sulfur-free environmentally friendly automotive wiring harness protective sleeve processing material according to claim 1, characterized in that: The vulcanizing agent is predispersed sulfur.

6. The sulfur-free environmentally friendly automotive wiring harness protective sleeve processing material according to claim 1, characterized in that: The accelerator is EG3T-75GE.

7. The method for preparing the sulfur-free environmentally friendly automotive wiring harness protective sleeve processing material as described in any one of claims 1-6, characterized in that, Includes the following steps: (1) First stage of mixing: EPDM rubber is put into a mixer for mixing, then zinc oxide, stearic acid and activating dispersant are added for mixing, then reinforcing agent, filler and softener are added for mixing. When the temperature of the mixer reaches 130°C, the material is fed out and sheeted out of the open mill and left to stand for a period of time. (2) Two-stage mixing: After the rubber compound has been left to stand, it is put into an internal mixer, then vulcanizing agent and accelerator are added and mixed. The mixture is then fed into a two-roll mill to form sheets, which are then cooled and packaged.

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