Green and environment-friendly automobile sealing strip rubber compound and preparation method thereof

Abstract

The invention discloses a green and environment-friendly automobile sealing strip rubber compound and a preparation method thereof, and belongs to the technical field of automobile sealing strips, the green and environment-friendly automobile sealing strip rubber compound comprises the following components by weight: 38.16-45.43 parts of ethylene propylene diene monomer, 18-26.3 parts of TPEE, 8.6-13.4 parts of a modified nano filler, 3.66-7.62 parts of an environment-friendly flame retardant, 5.15-6.70 parts of a green additive, and 3-5 parts of an auxiliary agent; the modified nano filler is prepared from nano carbon black, nano waste electrical porcelain and a boron-containing copolymer, and the boron-containing copolymer is synthesized from methacrylic acid stearate and isopropenyl boronic acid pinacol ester; the green additive is prepared from polydimethylsiloxane and polylactic acid fibers. The prepared green and environment-friendly automobile sealing strip rubber compound is good in high-temperature stability, and the sealing effect and the service life of an automobile sealing strip are guaranteed; meanwhile, by optimizing the modified nanofiller and the green additive, the flame retardance is effectively improved; and the material also has the advantages of excellent resistance, environmental protection and the like.

Description

Technical Field

[0001] The invention relates to the technical field of automobile sealing strips, and in particular to a green and environmentally friendly automobile sealing strip rubber compound and a preparation method thereof. Background Art

[0002] EPDM rubber sealing strips have the characteristics of good sealing, weather resistance, high and low temperature resistance, and chemical corrosion resistance. In order to improve the flame retardant properties of EPDM rubber, a certain amount of flame retardant additives need to be added.

[0003] However, flame retardant additives may decompose and produce harmful gases under high temperature conditions. On the one hand, this affects the stability of the rubber molecular structure, thereby affecting the sealing effect and service life of the automotive sealing strips. On the other hand, these harmful gases will increase the production of smoke during combustion, affecting the flame retardant effect.

[0004] Based on this, the present invention designs a green and environmentally friendly automobile sealing strip rubber compound and a preparation method thereof to solve the above problems. Summary of the Invention

[0005] In view of the above-mentioned shortcomings of the prior art, the present invention provides a green and environmentally friendly automobile sealing strip rubber compound and a preparation method thereof.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0007] A green and environmentally friendly automotive sealing strip rubber compound comprises the following components, measured by weight: 38.16-45.43 parts of EPDM rubber, 18-26.3 parts of TPEE, 8.6-13.4 parts of a modified nanofiller, 3.66-7.62 parts of an environmentally friendly flame retardant, 5.15-6.70 parts of a green additive, and 3-5 parts of an auxiliary agent. The modified nanofiller is prepared from nano carbon black, nano waste electrical porcelain, and a boron-containing copolymer, the boron-containing copolymer being synthesized from methacrylate stearate and isopropenyl boric acid pinacol ester. The green additive is prepared from polydimethylsiloxane and polylactic acid fiber.

[0008] Furthermore, the modified nano filler comprises the following components in parts by weight: 4-6.8 parts of nano carbon black, 4-5.5 parts of nano waste electrical porcelain, and 0.6-1.1 parts of boron-containing copolymer.

[0009] Furthermore, the green additive comprises the following components by weight: 2.15-3 parts of polydimethylsiloxane and 3-3.7 parts of polylactic acid fiber.

[0010] Further, the preparation method of the boron-containing copolymer is as follows: Mix 6-8 parts of stearyl methacrylate and 1 part of isopropenylboronic acid pinacol ester, add them to 0.071-0.082 parts of azobisisobutyronitrile pre-dissolved in 5-7 parts of toluene, conduct degassing treatment, and react at 62-64 °C for 15-20 h; then cool and pour into a mixed solvent composed of 77-81 parts of ice methanol and 26-29 parts of acetone. After precipitation, a crude product is obtained. Then, dissolve the crude product in 8-10 parts of dichloromethane again, pour it into the mixed solvent composed of ice methanol and acetone, precipitate and dry to obtain the boron-containing copolymer.

[0011] Further, calculated by weight parts, the components of the auxiliary agent are as follows: 2-4 parts of plasticizer and 1 part of vulcanization accelerator.

[0012] Further, the flame retardant uses the halogen-free flame retardant MM-X1 rubber.

[0013] In order to better achieve the purpose of the present invention, the present invention also provides a preparation method of a green environmental protection automobile sealing strip mixing rubber, including the following steps:

[0014] (1) Synthesize a boron-containing copolymer using stearyl methacrylate and isopropenylboronic acid pinacol ester, and prepare a modified nano-filler using nano-carbon black, nano-waste electric porcelain and the boron-containing copolymer;

[0015] (2) Prepare a green additive using polydimethylsiloxane and polylactic acid fiber;

[0016] (3) Weigh the following raw materials: 38.16-45.43 parts of ethylene propylene diene monomer rubber, 18-26.3 parts of TPEE, 8.6-13.4 parts of modified nano-filler, 3.66-7.62 parts of environmental protection flame retardant, 5.15-6.70 parts of green additive, 2-4 parts of plasticizer, and 1 part of vulcanization accelerator;

[0017] (4) Mix the modified nano-filler and the green additive, place them in a toluene solvent with a volume 2-3 times that of the mixture, then put the mixture into a microwave reactor, set the microwave power at 300-400 W, the temperature at 80-90 °C, the time at 20-35 min, and the stirring speed at 200-350 r / min, and stir and react under microwave conditions; after centrifugation and washing, product A is obtained;

[0018] (5) First mixing: Put ethylene propylene diene monomer rubber, TPEE, product A, environmental protection flame retardant, and plasticizer into a mixer to mix and make A mixing rubber;

[0019] (6) Second mixing: Add the vulcanization accelerator to the A mixing rubber and mix to obtain the product.

[0020] Further, steps (5) and (6) are specifically as follows: (5) First-stage mixing: First, ethylene propylene diene monomer (EPDM), thermoplastic polyester elastomer (TPEE) and product A are put into an internal mixer for mixing for 60 - 75 s; then, an environmentally friendly flame retardant is put into the internal mixer for mixing for 60 - 75 s, and then a plasticizer is put into the internal mixer for mixing for 60 - 75 s. After the mixing temperature reaches 150 - 155 °C and is maintained for 30 - 35 s, the upper ram is used for cleaning; then, it is mixed for another 30 - 50 s and cleaned again; finally, it is mixed for 60 - 75 s and then discharged and sheeted to prepare A mixed rubber for standby; (6) Second-stage mixing: The A mixed rubber is added with a vulcanization accelerator and mixed for 60 - 80 s. After cleaning, it is mixed again for 40 - 60 s. After ensuring sufficient mixing and dispersion, it is sheeted and set aside for standby.

[0021] To better achieve the object of the present invention, the present invention also provides a green and environmentally friendly automotive sealing strip mixed rubber prepared according to the described preparation method.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows: The green and environmentally friendly automotive sealing strip mixed rubber prepared by the present invention has good high-temperature stability, is not easily decomposed, and has strong stability of the rubber molecular structure, ensuring the sealing effect and service life of the automotive sealing strip; at the same time, by optimizing the modified nano-fillers and green additives, the flame retardancy is effectively increased; and it also has excellent electrical resistance, green environmental protection and other advantages, and is suitable for the preparation of automotive sealing strips. Specific embodiments

[0023] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0024] Example 1: A preparation method of a green and environmentally friendly automotive sealing strip mixed rubber includes the following steps:

[0025] (1) 6 parts of stearyl methacrylate and 1 part of isopropenylboronic acid pinacol ester are mixed, and 0.071 part of azobisisobutyronitrile pre-dissolved in 5 parts of toluene is added, and degassing treatment is carried out, and the reaction is carried out at 62 °C for 15 h; then it is cooled and poured into a mixed solvent composed of 77 parts of ice methanol and 26 parts of acetone. After precipitation, a crude product is obtained. Then the crude product is re-dissolved in 8 parts of dichloromethane and poured into a mixed solvent composed of ice methanol and acetone again. After precipitation, it is dried to obtain a boron-containing copolymer. Weigh 4 parts of nano carbon black, 4 parts of nano waste electric porcelain, and 0.6 part of boron-containing copolymer, and mix them to prepare modified nano-fillers.

[0026] (2) Weigh 2.15 parts of polydimethylsiloxane and 3 parts of polylactic acid fiber, and mix them to prepare a green additive.

[0027] (3) Weigh the following raw materials: 38.16 parts of ethylene propylene diene monomer rubber, 18 parts of TPEE, 8.6 parts of modified nano filler, 3.66 parts of environmentally friendly flame retardant (MM-X1 halogen-free flame retardant), 5.15 parts of green additive, 2 parts of plasticizer, and 1 part of vulcanization accelerator.

[0028] (4) Mix the modified nano filler and the green additive, place them in toluene solvent with a volume 2 times that of the mixture, then put the mixture into a microwave reactor, set the microwave power at 300 W, the temperature at 90 °C, the time at 20 min, and the stirring speed at 350 r / min, and stir and react under microwave conditions; after centrifugation and washing, product A is obtained.

[0029] (5) The first stage of mixing: First put ethylene propylene diene monomer rubber, TPEE and product A into an internal mixer for mixing, with a mixing time of 60 s; then put the environmentally friendly flame retardant into the internal mixer for mixing, and after a mixing time of 60 s, put the plasticizer into the internal mixer, with a mixing time of 60 s. When the mixing temperature reaches 150 °C and is maintained for 30 s, perform top plug cleaning; mix for another 30 s and then clean again; finally mix for 60 s and then discharge and sheet out to prepare A mixed rubber for standby.

[0030] (6) The second stage of mixing: Add the vulcanization accelerator to the A mixed rubber, mix for 60 seconds, clean, and then mix for another 40 seconds. After ensuring sufficient mixing and dispersion, sheet out and set aside for standby.

[0031] Example 2: A method for preparing a green and environmentally friendly automotive sealing strip mixed rubber, comprising the following steps:

[0032] (1) Mix 8 parts of stearyl methacrylate and 1 part of isopropenylboronic acid pinacol ester, add them to 0.082 parts of azobisisobutyronitrile pre-dissolved in 7 parts of toluene, perform degassing treatment, and react at 64 °C for 20 h; then cool, and pour into a mixed solvent composed of 81 parts of ice methanol and 29 parts of acetone. After precipitation, a crude product is obtained. Then redissolve the crude product in 10 parts of dichloromethane, and pour it into the mixed solvent composed of ice methanol and acetone again. After precipitation, dry it to obtain a boron-containing copolymer. Weigh 6.8 parts of nano carbon black, 5.5 parts of nano waste electric porcelain, and 1.1 parts of boron-containing copolymer, and mix them to prepare a modified nano filler.

[0033] (2) Weigh 3 parts of polydimethylsiloxane and 3.7 parts of polylactic acid fiber, and mix them to prepare a green additive.

[0034] (3) Weigh the following raw materials: 45.43 parts of ethylene propylene diene monomer rubber, 26.3 parts of TPEE, 13.4 parts of modified nano filler, 7.62 parts of environmental protection flame retardant (MM-X1 halogen-free flame retardant), 6.70 parts of green additive, 4 parts of plasticizer, and 1 part of vulcanization accelerator;

[0035] (4) Mix the modified nano filler and the green additive, place them in toluene solvent with a volume 3 times that of the mixture, then put the mixture into a microwave reactor, set the microwave power at 400 W, temperature at 80 °C, time at 35 min, stirring speed at 200 r / min, and stir and react under microwave conditions; after centrifugation and washing, product A is obtained;

[0036] (5) The first stage of mixing: First put ethylene propylene diene monomer rubber, TPEE and product A into a mixer for mixing, with a mixing time of 75 s; then put the environmental protection flame retardant into the mixer for mixing, after a mixing time of 75 s, then put the plasticizer into the mixer, with a mixing time of 75 s. When the mixing temperature reaches 155 °C and is maintained for 35 s, perform upper plug cleaning; mix for another 50 s and then clean again; finally, mix for 75 s and then unload and sheet out to prepare A mixed rubber for standby;

[0037] (6) The second stage of mixing: Add the vulcanization accelerator to the A mixed rubber, mix for 80 seconds, clean and then mix for another 60 seconds. After ensuring sufficient mixing and dispersion, sheet out and set aside.

[0038] Example 3: A preparation method of a green environmental protection automotive sealing strip mixed rubber, comprising the following steps:

[0039] (1) Mix 7 parts of stearyl methacrylate and 1 part of isopropenylboronic acid pinacol ester, add 0.08 part of azobisisobutyronitrile pre-dissolved in 6 parts of toluene, perform degassing treatment, and react at 63 °C for 18 h; then cool and pour into a mixed solvent composed of 79 parts of ice methanol and 28 parts of acetone. After precipitation, the crude product is obtained. Then dissolve the crude product in 9 parts of dichloromethane again, and pour it into the mixed solvent composed of ice methanol and acetone. After precipitation, dry it to obtain the boron-containing copolymer. Weigh 5 parts of nano carbon black, 5 parts of nano waste electric porcelain, and 1 part of boron-containing copolymer, and mix them to prepare the modified nano filler.

[0040] (2) Weigh 2.5 parts of polydimethylsiloxane and 3.5 parts of polylactic acid fiber, and mix them to prepare the green additive.

[0041] (3) Weigh the following raw materials: 44 parts of ethylene propylene diene monomer rubber, 25 parts of TPEE, 11 parts of modified nano filler, 4.52 parts of environmental protection flame retardant (MM-X1 halogen-free flame retardant), 6 parts of green additive, 3 parts of plasticizer, and 1 part of vulcanization accelerator;

[0042] (4) Mix the modified nano-fillers with the green additive, place them in toluene solvent with a volume 2.5 times that of the mixture, then put the mixture into a microwave reactor, set the microwave power at 350 W, the temperature at 85 °C, the time at 25 min, and the stirring speed at 280 r / min, and stir and react under microwave conditions; after centrifugation and washing, product A is obtained.

[0043] (5) First-stage mixing: First put ethylene propylene diene monomer (EPDM), thermoplastic polyester elastomer (TPEE) and product A into a mixer for mixing for 65 s; then put the environmental protection flame retardant into the mixer for mixing for 65 s, and then put the plasticizer into the mixer for mixing for 65 s. When the mixing temperature reaches 152 °C and is maintained for 32 s, the upper ram is used for cleaning; after mixing for another 40 s, cleaning is carried out again; finally, after mixing for 65 s, the material is discharged and sheeted to prepare A mixed rubber for standby.

[0044] (6) Second-stage mixing: Add the vulcanization accelerator to the A mixed rubber, mix for 70 seconds, clean and then mix for another 50 seconds. After ensuring sufficient mixing and dispersion, the sheet is taken off for standby.

[0045] Comparative Example 1: A preparation method of a green environmental protection automotive sealing strip mixed rubber, comprising the following steps:

[0046] (1) Mix 7 parts of stearyl methacrylate and 1 part of isopropenylboronic acid pinacol ester, add them to 0.08 part of azobisisobutyronitrile pre-dissolved in 6 parts of toluene, carry out degassing treatment, and react at 63 °C for 18 h; then cool and pour into a mixed solvent composed of 79 parts of ice methanol and 28 parts of acetone. After precipitation, the crude product is obtained. Then the crude product is re-dissolved in 9 parts of dichloromethane and poured into the mixed solvent composed of ice methanol and acetone again. After precipitation, it is dried to obtain the boron-containing copolymer. Weigh 5 parts of nano-carbon black, 5 parts of nano-waste electric porcelain, and 1 part of boron-containing copolymer, and mix them to prepare modified nano-fillers.

[0047] (2) Weigh 2.5 parts of polydimethylsiloxane and 3.5 parts of polylactic acid fiber, and mix them to prepare a green additive.

[0048] (3) Weigh the following raw materials: 44 parts of ethylene propylene diene monomer (EPDM), 2,5 parts of thermoplastic polyester elastomer (TPEE), 11 parts of modified nano-fillers, 4.52 parts of environmental protection flame retardant (MM-X1 halogen-free flame retardant), 6 parts of green additive, 3 parts of plasticizer, and 1 part of vulcanization accelerator;

[0049] (4) First-stage mixing: Ethylene propylene diene monomer rubber, TPEE, modified nano-fillers and green additives are first put into an internal mixer for mixing for 65 s; then the environmentally friendly flame retardant is put into the internal mixer for mixing. After 65 s of mixing, the plasticizer is put into the internal mixer and mixed for 65 s. When the mixing temperature reaches 152 °C and is maintained for 32 s, the upper ram is used for cleaning; after mixing for another 40 s, cleaning is carried out again; finally, after mixing for 65 s, discharging and sheeting are carried out to prepare A mixed rubber for standby;

[0050] (5) Second-stage mixing: The vulcanization accelerator is added to the A mixed rubber and mixed for 70 s. After cleaning, mixing is carried out again for 50 s. After ensuring sufficient mixing and dispersion, sheeting is carried out for standby.

[0051] Comparative Example 2: Different from Example 3, the boron-containing copolymer is missing when preparing the modified nano-fillers.

[0052] Comparative Example 3: Different from Example 3, polydimethylsiloxane is missing when preparing the green additives.

[0053] Experimental Example: The properties of the green environmental protection automotive sealing strip mixed rubber prepared in Examples 1 - 3 and Comparative Examples 1 - 3 were tested. The results are shown in Tables 1 - 2:

[0054] Table 1 Performance test results

[0055]

[0056]

[0057] Table 2 Flame retardant performance test results

[0058] Project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Oxygen Index (%) 37.6 35.1 37.2 28.6 27.9 26.3 Smoke Density (Ds4 ignition) 70.3 69.4 68.8 184.9 256.7 306.7 Smoke Density (Ds4 non-ignition) 128.4 125.3 134.9 259.4 337.1 376.1

[0059] The mixed rubber of the green environmental protection automotive sealing strip prepared by the present invention has good high-temperature stability, is not easily decomposed, has strong stability of the rubber molecular structure, and ensures the sealing effect and service life of the automotive sealing strip; at the same time, by optimizing the modified nano-fillers and green additives, the flame retardancy is effectively increased; and it also has excellent resistance and is green and environmentally friendly, etc., and is suitable for the preparation of automotive sealing strips.

[0060] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A green environmental protection automotive sealing strip mixing rubber, characterized in that, By weight parts, its components are as follows: ethylene propylene diene monomer (EPDM) 38.16 - 45.43 parts, TPEE 18 - 26.3 parts, modified nano filler 8.6 - 13.4 parts, environment-friendly flame retardant 3.66 - 7.62 parts, green additive 5.15 - 6.70 parts, auxiliary agent 3 - 5 parts; the modified nano filler is prepared from nano carbon black, nano waste electric porcelain and boron-containing copolymer, and the boron-containing copolymer is synthesized from stearic acid methyl acrylate and isopropenylboronic acid pinacol ester; the green additive is prepared from polydimethylsiloxane and polylactic acid fiber.

2. The green environmental protection automotive sealing strip mixing rubber according to claim 1, characterized in that, By weight parts, the components of the modified nano filler are as follows: nano carbon black 4 - 6.8 parts, nano waste electric porcelain 4 - 5.5 parts, boron-containing copolymer 0.6 - 1.1 parts.

3. The green environmental protection automotive sealing strip mixing rubber according to claim 1, wherein, By weight parts, the components of the green additive are as follows: polydimethylsiloxane 2.15 - 3 parts, polylactic acid fiber 3 - 3.7 parts.

4. The green environmental protection automotive sealing strip mixing rubber according to claim 1, wherein, The preparation method of the boron-containing copolymer is: mix 6 - 8 parts of stearic acid methyl acrylate and 1 part of isopropenylboronic acid pinacol ester, add 0.071 - 0.082 parts of azobisisobutyronitrile pre-dissolved in 5 - 7 parts of toluene, conduct degassing treatment, and react at 62 - 64 °C for 15 - 20 h; then cool and pour into a mixed solvent composed of 77 - 81 parts of ice methanol and 26 - 29 parts of acetone, precipitate to obtain the crude product, then re-dissolve the crude product in 8 - 10 parts of dichloromethane, pour it into the mixed solvent composed of ice methanol and acetone again, precipitate and dry to obtain the boron-containing copolymer.

5. The green environmental protection automotive sealing strip mixing rubber according to claim 1, characterized in that, By weight parts, the components of the auxiliary agent are as follows: plasticizer 2 - 4 parts, vulcanization accelerator 1 part.

6. The green environmental protection automotive sealing strip mixing rubber according to claim 1, characterized in that, The flame retardant uses MM-X1 rubber halogen-free flame retardant.

7. A preparation method of a green environmental protection automotive sealing strip mixing rubber, characterized in that, It includes the following steps: (1) Synthesize the boron-containing copolymer from stearic acid methyl acrylate and isopropenylboronic acid pinacol ester, and prepare the modified nano filler from nano carbon black, nano waste electric porcelain and the boron-containing copolymer; (2) Prepare the green additive from polydimethylsiloxane and polylactic acid fiber; (3) Weigh the following raw materials: ethylene propylene diene monomer (EPDM) 38.16 - 45.43 parts, TPEE 18 - 26.3 parts, modified nano filler 8.6 - 13.4 parts, environment-friendly flame retardant 3.66 - 7.62 parts, green additive 5.15 - 6.70 parts, plasticizer 2 - 4 parts, vulcanization accelerator 1 part; (4) Mix the modified nano filler and the green additive, place them in a toluene solvent with 2 - 3 times the volume, then put the mixture into a microwave reactor, set the microwave power at 300 - 400 W, temperature at 80 - 90 °C, time at 20 - 35 min, stirring speed at 200 - 350 r / min, and stir and react under microwave conditions; after centrifugation and washing, obtain product A; (5) The first stage of mixing: Put ethylene propylene diene monomer (EPDM), TPEE, product A, environment-friendly flame retardant, and plasticizer into a mixer to mix and make A mixed rubber; (6) The second stage of mixing: Add the vulcanization accelerator to the A mixed rubber and mix to obtain the product.

8. The preparation method of the green environmental protection automobile sealing strip mixing rubber according to claim 7, characterized in that, Steps (5) and (6) are specifically as follows: (5) The first stage of mixing: First, put ethylene propylene diene monomer (EPDM), thermoplastic polyester elastomer (TPEE) and product A into a Banbury mixer for mixing for 60 - 75 s; then put the environmentally friendly flame retardant into the Banbury mixer for mixing. After 60 - 75 s of mixing, then put the plasticizer into the Banbury mixer for mixing for 60 - 75 s. When the mixing temperature reaches 150 - 155 °C and is maintained for 30 - 35 s, perform upper ram cleaning; then mix for another 30 - 50 s and clean again; finally, mix for 60 - 75 s and then discharge and sheet out to prepare A mixed rubber for use; (6) The second stage of mixing: Add the vulcanization accelerator to the A mixed rubber, mix for 60 - 80 s, clean and then mix again for 40 - 60 s. After ensuring sufficient mixing and dispersion, sheet out and set aside for use.

9. A green and environmentally friendly automotive sealing strip mixed rubber prepared by the preparation method according to claim 7 or 8.

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