CN108276687A - A kind of nano microcrystalline NCC enhancing rubber material and preparation method thereof - Google Patents

Abstract

The invention provides a nano-microcrystalline NCC reinforced rubber material and a preparation method thereof. The nano-microcrystalline NCC reinforced rubber material is composed of NCC, chemical auxiliary agents, modifiers and EPDM rubber masterbatch. The preparation method comprises the following steps: 1) treating NCC with a surface active agent; 2) adding EPDM rubber masterbatch, modifier and modified NCC solution into a mixer for mixing; 3) mixing antiaging agent and mixing Put the mixing material into the internal mixer and add rubber vulcanizing agent after internal mixing, knead and stir at a high speed and then transport it to the open mill; 4) Thinly pass the mixture in the open mill to make the EPDM rubber masterbatch, modifier and modified NCC is fully mixed and uniform, input into the screw extruder, and the product is formed through the extruder and the extrusion die; 5) The extruded product is vulcanized, and the product is obtained after vulcanization. The material toughness and wear resistance of the invention are significantly increased, and the raw material cost is low, and the material is clean and environment-friendly.

Description

A kind of nano-microcrystalline NCC reinforced rubber material and preparation method thereof

technical field

The invention belongs to the field of rubber materials, and relates to a rubber material and a preparation method thereof, in particular to a nano-microcrystalline NCC reinforced rubber material and a preparation method thereof.

Background technique

As a high-quality elastic material, rubber has been widely used in various fields. According to the composition of rubber, its performance and use are also different. There are ordinary rubber flooring and anti-slip mats for general household floors, and special reinforced rubber gaskets for container sealing and flange sealing. Glass fiber, carbon fiber, aramid fiber, synthetic fiber, carbon black, etc. are usually used to reinforce rubber materials, which have the advantages of temperature and pressure resistance, good wear resistance, good solvent resistance, etc., but there are also many problems, such as fiber Uneven dispersion, weak bonding of rubber and fiber, etc., resulting in unsatisfactory fiber reinforcement effect. Nanocrystals Cellulose (NCC) is a natural macromolecular compound derived from wood materials, with a single fiber strength as high as 57GPa and good affinity for rubber. It can be used to replace traditional glass fibers, carbon fibers, etc. Manufacture of reinforced rubber materials.

Patent document CN101555330A, published on 2009.10.14, provides a fiber-reinforced rubber, which is made of fiber-reinforced rubber products by masticating rubber raw materials, reinforcing agents, fibers and auxiliary agents. This patent solves the problem of uneven fiber dispersion in the traditional fiber-reinforced rubber preparation process, and the preparation process is simple. The prepared rubber has good elasticity, small compression deformation, and excellent physical and mechanical properties. However, this patent uses a large amount of glass fiber as the reinforcing fiber, and the hardness of the product is relatively high. During the long-term use of the prepared rubber, aging glass fiber will fall off, resulting in failure of the glass fiber reinforcement and reducing the service life of the reinforced rubber.

Patent document CN102002173A, publication date 2011.04.06, provides a preparation method of nano-microcrystalline cellulose/silica/rubber composite material, using rod-shaped nano-microcrystalline fibers with a diameter of 20-60 nm and an average length of 300 nm as a reinforcing material Reinforced rubber. In this patent, the reinforcing effect of NCC on natural rubber is better than that of white carbon black, which greatly improves the heat and oxygen aging resistance of natural rubber, and at the same time reduces the heat generation of composite materials, and can be prepared by traditional rubber processing technology. Composite rubber. However, this patent uses natural rubber as a raw material. Due to limited output, its price is high, and its temperature resistance range is narrow, which is not conducive to industrial large-scale production and application.

Patent document CN104761761A, published on 2015.07.08, provides a high-toughness nanofiber-reinforced rubber-based 3D printing material, which is prepared by mixing rubber, thermoplastic polymer nanofiber reinforcement and solvent. This patent solves the problems of traditional powder rubber materials such as low strength, poor toughness, and need to be modified before use. At the same time, the prepared rubber-based 3D printing materials also have the advantages of high bonding strength and simple production process. However, this patent uses toxic and harmful solvents such as acetone, dichloromethane, and carbon tetrachloride for production, which is harmful to the environment and not environmentally friendly. In addition, the increase in a large amount of powder will lead to greater brittleness of the rubber material, and the powder reinforced material will often fall. Falling down reduces the service life of the rubber.

In addition, the patent document CN104629105A, published on May 20, 2015, discloses a microcrystalline cellulose reinforced rubber wear-resistant material and its preparation method, which is made of the following main raw materials in the following weight ratio: surface-modified microcrystalline cellulose 1～ 35 parts, the surface is coated with sizing agent or coupling agent with 1% to 2% weight of microcrystalline cellulose, 65 to 99 parts of rubber matrix; the process route is to suspend and loosen the nano-microcrystalline cellulose and spray the sizing agent Or coupling agent, heated at 60-120°C until the sizing agent and coupling agent are completely spread and infiltrated on the cellulose surface, and then these surface-modified microcrystalline cellulose and rubber matrix are mixed and vulcanized. Patent document CN104530504A, publication date 2015.04.22, discloses a rubber composite material based on waste cotton material nano-microcrystalline cellulose and its preparation method, the method is: stirring the natural rubber latex; mixing cotton nano-microcrystalline cellulose Add it to natural rubber latex, stir and mix to obtain a cotton nano-microcrystalline cellulose/natural rubber mixture; spread it flat, undergo demulsification and co-precipitation, wash and precipitate, and dry to a constant weight to obtain solid cotton nano-microcrystalline cellulose/natural rubber. Rubber mixture; mixed with silica to obtain the desired product. However, the properties of the above-mentioned reinforced rubbers are still unsatisfactory.

To sum up, there is an urgent need for a reinforced rubber material with strong toughness, wear resistance, aging resistance, crack resistance, low cost, clean and environment-friendly.

Contents of the invention

The purpose of the present invention is to provide a kind of toughness, strong wear resistance, anti-aging, anti-crack and low cost, clean and environment-friendly nano-microcrystalline NCC reinforced rubber material and its preparation method for the deficiencies in the prior art.

In the first aspect, the nano-microcrystalline NCC reinforced rubber material provided by the present invention is made of the following components in weight percentage: 1% to 25% of NCC, 2% to 15% of chemical additives, 5% to 30% modified The balance is EPDM rubber masterbatch; the diameter of the NCC is 2-15nm, and the length is 150-400nm; the chemical auxiliary agent consists of 0.01%-4% surfactant, 0.5%-5% anti-aging agent and 1.5% % to 6% of rubber vulcanizing agent, and the percentage of the three to the total weight of all raw materials is 2% to 15%.

As another preferred example, the EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black.

As another preferred example, the weight content of powdered carbon black in the EPDM rubber reinforced with powdery carbon black is 20%-50%.

As another preferred example, the modifier is selected from one, two or more of chloroprene rubber, styrene-butadiene rubber, fluororubber and silicone rubber.

As another preferred example, the surfactant is selected from one, two or more of KH550, KH560, stearic acid, n-butyl titanate and ethyltrimethoxysilane.

As another preferred example, the anti-aging agent is selected from one, two or more of liquid paraffin, modified liquid paraffin, triethyl glycerol and dibutyl phthalate.

As another preferred example, the rubber vulcanizing agent is selected from one, two or more of magnesium dimethacrylate, TMTD, epoxy resin, zinc chloride and magnesium oxide.

In the second aspect, the preparation method of nano-microcrystalline NCC reinforced rubber material provided by the present invention comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing. The mixing temperature is 120-130°C and the mixing time is 3-8 minutes. After mixing, the mixing temperature is 110-120 ℃ discharge, to obtain a primary mixing material;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 2-10 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) Thinly pass the mixture in step 3) 2 to 4 times in the open mill, fully mix the EPDM rubber masterbatch, modifier and modified NCC, input them into the screw extruder, and Extrusion and extrusion molded products;

5) Vulcanize the molded product in step 4), the vulcanization temperature is 100-150°C, the vulcanization pressure is 1.5-5MPa, the vulcanization time is 15-45min, and the nano-microcrystalline NCC reinforced rubber material can be made after vulcanization .

As another preferred example, the EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, and the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 20%-50%.

As another preferred example, the anti-aging agent is selected from one, two or more of liquid paraffin, modified liquid paraffin, triethyl glycerol and dibutyl phthalate.

Herein, the EPDM rubber masterbatch, that is, EPDM rubber, is a copolymer of ethylene, propylene and a small amount of non-conjugated diene. The KH550 is an amino functional silane with a chemical name of γ-aminopropyltriethoxysilane. The KH560 is an epoxy group-containing coupling agent with a chemical name of γ-glycidyl etheroxypropyltrimethoxysilane. The TMTD is also called N,N-tetramethyldithiobisthiocarbamide.

The beneficial effects of the present invention are:

(1) The composition and ratio of raw materials are scientific and reasonable, and the toughness of the prepared rubber material is significantly increased. While improving the toughness, the wear resistance is improved, and the purpose of rubber reinforcement is achieved;

(2) The bonding strength between rubber molecules is high, which avoids the stress concentration at the interface in the reinforced rubber, which leads to the problem of cracking, failure and destruction;

(3) in the material of the present invention, anti-aging agent and rubber vulcanizing agent have certain synergy;

(4) There are fewer types of raw materials, low cost and simple preparation process;

(5) The raw materials do not contain toxic and harmful solvents, and are clean and environmentally friendly;

(6) The material of the invention is particularly suitable for the production of seals.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention, should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention, after having read the present invention, those skilled in the art will understand various equivalent forms of the present invention All modifications are within the limits of the appended claims of this application.

In the following examples and comparative examples, the NCC was purchased from Israel; the neoprene rubber was purchased from Lanxess Chemical (China) Co., Ltd.; the KH560, dibutyl phthalate, TMTD, and magnesium oxide were purchased from Ningbo Acme New Materials Co., Ltd.; the EPDM rubber that the powdered carbon black reinforces is purchased from U.S. Cabot Corporation; the fluorine rubber is purchased from DuPont; China) Co., Ltd. Others will not be described in detail here, and are all commercially available raw materials.

Example 1

The nano-microcrystalline NCC reinforced rubber material is made of the following components by weight percentage: 5% of NCC, 11.5% of chemical auxiliary agents, 5% of modifiers, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 2 nm and a length of 400 nm.

The chemical auxiliary agent includes 4% surface active agent, 1.5% antiaging agent and 6% rubber vulcanizing agent.

The modifier is neoprene.

The surfactant is KH560.

The anti-aging agent is dibutyl phthalate.

The rubber vulcanizing agent is TMTD.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 20%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 120°C, the mixing time is 8min, and the material is discharged at 110°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 5 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed and evenly input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 150° C., the vulcanization pressure is 2.5 MPa, and the vulcanization time is 15 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material can be made.

Example 2

The nano-microcrystalline NCC reinforced rubber material is made of the following components in weight percentage: 5% of NCC, 13.5% of chemical additives, 5.5% of modifiers, and the balance is EDPM rubber masterbatch.

The NCC has a diameter of 5 nm and a length of 150 nm.

The chemical auxiliary agent includes 4% surface active agent, 4.5% antiaging agent and 5% rubber vulcanizing agent.

The modifier is fluorine rubber.

The surfactant is ethyltrimethoxysilane.

The anti-aging agent is dibutyl phthalate.

The rubber vulcanizing agent is magnesium oxide.

The EDPM rubber masterbatch is EDPM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 35%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EDPM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 130°C, the mixing time is 8min, and the material is discharged at 110°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 10 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed twice in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed evenly, input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized. The vulcanization temperature is 150° C., the vulcanization pressure is 1.5 MPa, and the vulcanization time is 35 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material can be made.

Example 3

The nano-microcrystalline NCC reinforced rubber material is made of the following components in weight percentage: 1% of NCC, 2.01% of chemical auxiliary agents, 30% of modifiers, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 15 nm and a length of 300 nm.

The chemical auxiliary agent includes 0.01% surface active agent, 0.5% antiaging agent and 1.5% rubber vulcanizing agent.

The modifier is silicone rubber.

The surfactant is KH550.

The anti-aging agent is liquid paraffin.

The rubber vulcanizing agent is epoxy resin.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 50%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 125°C, the mixing time is 3min, and the material is discharged at 120°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 2 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 3 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed evenly, input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 100° C., the vulcanization pressure is 5 MPa, and the vulcanization time is 30 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material can be made.

Example 4

The nano-microcrystalline NCC reinforced rubber material is made of the following components in weight percentage: 25% of NCC, 10% of chemical auxiliary agent, 20% of modifier, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 2 nm and a length of 400 nm.

The chemical auxiliary agent includes 1% surface active agent, 5% antiaging agent and 4% rubber vulcanizing agent.

The modifier is styrene-butadiene rubber.

Described surfactant is stearic acid.

The antiaging agent is modified liquid paraffin.

The rubber vulcanizing agent is magnesium dimethacrylate.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 20%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing. The mixing temperature is 120°C and the mixing time is 5min. After mixing, it is discharged at 115°C to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 10 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed and evenly input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 120° C., the vulcanization pressure is 5 MPa, and the vulcanization time is 30 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material can be made.

Example 5

The nano-microcrystalline NCC reinforced rubber material is made of the following components in weight percentage: 15% of NCC, 15% of chemical auxiliary agent, 10% of modifier, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 5 nm and a length of 150 nm.

The chemical auxiliary agent includes 4% surface active agent, 5% antiaging agent and 6% rubber vulcanizing agent.

The modifier is a mixture of chloroprene rubber and styrene-butadiene rubber, and the weight ratio of the two is 1:1.

The surfactant is a mixture of KH550 and KH560 with a weight ratio of 1:1.

The anti-aging agent is triethylglyceride.

The rubber vulcanizing agent is zinc chloride.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 20%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 120°C, the mixing time is 8min, and the material is discharged at 110°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 5 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed and evenly input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 150° C., the vulcanization pressure is 2.5 MPa, and the vulcanization time is 15 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material can be made.

Example 6

The nano-microcrystalline NCC reinforced rubber material is made of the following components by weight percentage: 5% of NCC, 5% of chemical auxiliary agent, 10% of modifier, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 2 nm and a length of 400 nm.

The chemical auxiliary agent includes 1% surface active agent, 2% antiaging agent and 2% rubber vulcanizing agent.

The modifier is a mixture of chloroprene rubber, styrene-butadiene rubber and fluorine rubber, and the weight ratio of the three is 1:1:2.

The surfactant is n-butyl titanate.

The antiaging agent is a mixture of dibutyl phthalate and liquid paraffin, and the weight ratio of the two is 1:1.

The rubber vulcanizing agent is a mixture of TMTD and magnesium oxide, and the weight ratio of the two is 1:3.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 50%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 120°C, the mixing time is 5min, and the material is discharged at 110°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 5 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed and evenly input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 150° C., the vulcanization pressure is 5 MPa, and the vulcanization time is 15 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material can be made.

Example 7

The nano-microcrystalline NCC reinforced rubber material is made of the following components in weight percentage: 5% of NCC, 10% of chemical auxiliary agent, 15% of modifier, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 2 nm and a length of 400 nm.

The chemical auxiliary agent includes 4% surface active agent, 4% antiaging agent and 2% rubber vulcanizing agent.

The modifier is neoprene.

The surfactant is KH560.

The anti-aging agent is triethylglyceride.

The rubber vulcanizing agent is a mixture of magnesium dimethacrylate, zinc chloride and magnesium oxide, and the weight ratio of the three is 1:1:1.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 35%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 130°C, the mixing time is 3min, and the material is discharged at 120°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 10 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 3 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed evenly, input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 120° C., the vulcanization pressure is 5 MPa, and the vulcanization time is 30 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material can be made.

Example 8

The nano-microcrystalline NCC reinforced rubber material is made of the following components in weight percentage: 5% of NCC, 10% of chemical auxiliary agent, 5.5% of modifier, and the balance of EDPM rubber masterbatch.

The NCC has a diameter of 5 nm and a length of 150 nm.

The chemical auxiliary agent includes 1% surface active agent, 3% antiaging agent and 6% rubber vulcanizing agent.

The modifier is fluorine rubber.

Described surfactant is stearic acid.

The anti-aging agent is dibutyl phthalate.

The rubber vulcanizing agent is magnesium dimethacrylate.

The EDPM rubber masterbatch is EDPM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 20%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EDPM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 130°C, the mixing time is 8min, and the material is discharged at 110°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 10 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed twice in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed evenly, input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized. The vulcanization temperature is 150° C., the vulcanization pressure is 1.5 MPa, and the vulcanization time is 35 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material can be made.

Example 9

The nano-microcrystalline NCC reinforced rubber material is made of the following components by weight percentage: 10% of NCC, 8% of chemical auxiliary agents, 5.5% of modifiers, and the balance of EDPM rubber masterbatch.

The NCC has a diameter of 5 nm and a length of 150 nm.

The chemical auxiliary agent includes 4% surfactant, 2% antiaging agent and 2% rubber vulcanizing agent.

The modifier is styrene-butadiene rubber.

The surfactant is a mixture of KH550 and KH560 with a weight ratio of 1:1.

The anti-aging agent is dibutyl phthalate.

The rubber vulcanizing agent is magnesium oxide.

The EDPM rubber masterbatch is EDPM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 50%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EDPM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 130°C, the mixing time is 8min, and the material is discharged at 110°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material to the internal mixer for 10 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed twice in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed evenly, input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized. The vulcanization temperature is 150° C., the vulcanization pressure is 1.5 MPa, and the vulcanization time is 35 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material can be made.

Example 10

The nano-microcrystalline NCC reinforced rubber material is made of the following components by weight percentage: 15% of NCC, 5% of chemical auxiliary agents, 20% of modifiers, and the balance of EDPM rubber masterbatch.

The NCC has a diameter of 5 nm and a length of 150 nm.

The chemical auxiliary agent includes 1% surface active agent, 1% antiaging agent and 3% rubber vulcanizing agent.

The modifier is a mixture of chloroprene rubber, styrene-butadiene rubber and silicone rubber, and the weight ratio of the three is 2:1:1.

The surfactant is ethyltrimethoxysilane.

The anti-aging agent is dibutyl phthalate.

The rubber vulcanizing agent is a mixture of magnesium dimethacrylate, TMTD and magnesium oxide, and the weight ratio of the three is 2:1:2.

The EDPM rubber masterbatch is EDPM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 20%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EDPM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 130°C, the mixing time is 8min, and the material is discharged at 110°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 10 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 3 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed evenly, input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 150° C., the vulcanization pressure is 5 MPa, and the vulcanization time is 15 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material can be made.

Comparative example 1

The nano-microcrystalline NCC reinforced rubber material is made of the following components in weight percentage: 1% of NCC, 2.01% of chemical auxiliary agents, 30% of modifiers, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 20 nm and a length of 500 nm.

The chemical auxiliary agent includes 0.01% surface active agent, 0.5% antiaging agent and 1.5% rubber vulcanizing agent.

The modifier is silicone rubber.

The surfactant is KH550.

The anti-aging agent is liquid paraffin.

The rubber vulcanizing agent is epoxy resin.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 50%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 125°C, the mixing time is 3min, and the material is discharged at 120°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 2 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 3 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed evenly, input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 100° C., the vulcanization pressure is 5 MPa, and the vulcanization time is 30 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material is produced.

Comparative example 2

The nano-microcrystalline NCC reinforced rubber material is made of the following components by weight percentage: 5% of NCC, 11.5% of chemical auxiliary agents, 5% of modifiers, and the balance of natural rubber.

The NCC has a diameter of 2 nm and a length of 400 nm.

The chemical auxiliary agent includes 4% surface active agent, 1.5% antiaging agent and 6% rubber vulcanizing agent.

The modifier is neoprene.

The surfactant is KH560.

The anti-aging agent is dibutyl phthalate.

The rubber vulcanizing agent is TMTD.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 120°C, the mixing time is 8min, and the material is discharged at 110°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 5 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed and evenly input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 150° C., the vulcanization pressure is 2.5 MPa, and the vulcanization time is 15 minutes. After vulcanization, nano-microcrystalline NCC reinforced rubber material is produced.

Comparative example 3

The nano-microcrystalline NCC reinforced rubber material is made of the following components by weight percentage: 30% of NCC, 10% of chemical auxiliary agent, 20% of modifier, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 2 nm and a length of 400 nm.

The chemical auxiliary agent includes 1% surface active agent, 5% antiaging agent and 4% rubber vulcanizing agent.

The modifier is styrene-butadiene rubber.

Described surfactant is stearic acid.

The antiaging agent is modified liquid paraffin.

The rubber vulcanizing agent is magnesium dimethacrylate.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 20%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing. The mixing temperature is 120°C and the mixing time is 5min. After mixing, it is discharged at 115°C to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 10 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed and evenly input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 120° C., the vulcanization pressure is 5 MPa, and the vulcanization time is 30 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material is produced.

Comparative example 4

The nano-microcrystalline NCC reinforced rubber material is made of the following components by weight percentage: 5% of NCC, 11.5% of chemical auxiliary agents, 5% of modifiers, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 2 nm and a length of 400 nm.

The chemical auxiliary agent includes 4% surface active agent, 1.5% antiaging agent and 6% rubber vulcanizing agent.

The modifier is neoprene.

The surfactant is KH560.

The anti-aging agent is 4-methyl-6-tert-butylphenol.

The rubber vulcanizing agent is TMTD.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 20%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 120°C, the mixing time is 8min, and the material is discharged at 110°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 5 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed and evenly input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 150° C., the vulcanization pressure is 2.5 MPa, and the vulcanization time is 15 minutes. After vulcanization, nano-microcrystalline NCC reinforced rubber material is produced.

Comparative example 5

The nano-microcrystalline NCC reinforced rubber material is made of the following components by weight percentage: 5% of NCC, 11.5% of chemical auxiliary agents, 5% of modifiers, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 2 nm and a length of 400 nm.

The chemical auxiliary agent includes 2% anti-aging agent and 9.5% rubber vulcanizing agent.

The modifier is chloroprene rubber.

The anti-aging agent is dibutyl phthalate.

The rubber vulcanizing agent is TMTD.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 20%.

Its preparation method comprises the following steps:

1) Add NCC, EPDM rubber masterbatch and modifier to the mixer for mixing, the mixing temperature is 120°C, the mixing time is 8min, and the material is discharged at 110°C after mixing to obtain a primary mixed material ;

2) Add the anti-aging agent and the primary mixing material into the internal mixer for 5 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

3) After the mixture in step 2) is thinly passed 4 times in the open mill, the EPDM rubber masterbatch, modifier and NCC are fully mixed evenly, input into the screw extruder, and passed through the extruder and the extruder. Out of the mold forming products;

4) The molded product in step 3) is vulcanized. The vulcanization temperature is 150° C., the vulcanization pressure is 2.5 MPa, and the vulcanization time is 15 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material is produced.

Comparative example 6

The nano-microcrystalline NCC reinforced rubber material is made of the following components by weight percentage: 5% of NCC, 11.5% of chemical auxiliary agents, 5% of modifiers, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 2 nm and a length of 400 nm.

The chemical auxiliary agent includes 8% surfactant and 3.5% antiaging agent.

The modifier is neoprene.

The surfactant is KH560.

The anti-aging agent is dibutyl phthalate.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 20%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 120°C, the mixing time is 8min, and the material is discharged at 110°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for internal mixing for 5 minutes, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed and evenly input into the screw extruder, and passed through the extruder and extrusion molded products;

5) Treat the molded product in step 4) at a temperature of 150° C. and a pressure of 2.5 MPa for 15 minutes to produce a nanocrystalline NCC reinforced rubber material.

Comparative example 7

The nano-microcrystalline NCC reinforced rubber material is made of the following components in weight percentage: 1% of NCC, 2.01% of chemical auxiliary agents, 30% of modifiers, and the balance of EPDM rubber masterbatch.

The NCC has a diameter of 15 nm and a length of 300 nm.

The chemical auxiliary agent includes 0.01% surface active agent, 0.5% antiaging agent and 1.5% rubber vulcanizing agent.

The modifier is silicone rubber.

The surfactant is KH550.

The anti-aging agent is liquid paraffin.

The rubber vulcanizing agent is epoxy resin.

The EPDM rubber masterbatch is EPDM rubber reinforced with powdered carbon black, wherein the weight content of powdered carbon black in the EPDM rubber reinforced with powdered carbon black is 55%.

Its preparation method comprises the following steps:

1) use a surfactant to process NCC to obtain a modified NCC solution;

2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing, the mixing temperature is 125°C, the mixing time is 3min, and the material is discharged at 120°C after mixing to obtain a Mixture;

3) Add the anti-aging agent and the primary mixing material into the internal mixer for 2 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer;

4) After the mixture in step 3) is thinly passed 3 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are fully mixed evenly, input into the screw extruder, and passed through the extruder and extrusion molded products;

5) The molded product in step 4) is vulcanized, the vulcanization temperature is 100° C., the vulcanization pressure is 5 MPa, and the vulcanization time is 30 minutes. After vulcanization, the nano-microcrystalline NCC reinforced rubber material can be made.

Embodiment 11 performance test

The mechanical properties of the nano-microcrystalline NCC reinforced rubber materials prepared in Examples 1-10 and Comparative Examples 1-7 were tested according to national standards, and the results are shown in Table 1. The data shows that the present application has selected scientific and reasonable material composition and proportioning, so that the nano-microcrystalline NCC reinforced rubber material rubber intermolecular bonding strength prepared in Examples 1-10 is high, and the toughness and wear resistance are all significantly increased. The mechanical properties of the materials in Comparative Examples 1-7 were all significantly improved.

The mechanical properties of the NCC reinforced rubber material prepared by table 1 embodiment 1-10 and comparative examples 1-7

The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the method of the present invention, some improvements and supplements can also be made, and these improvements and supplements should also be considered Be the protection scope of the present invention.

Claims (10)

1. A nano-microcrystalline NCC reinforced rubber material is characterized in that it is made of the following components in weight percent: 1% to 25% of NCC, 2% to 15% of chemical additives, 5% to 30% modified The balance is EPDM rubber masterbatch; the diameter of the NCC is 2-15nm, and the length is 150-400nm; the chemical additive consists of 0.01%-4% surfactant, 0.5%-5% anti-aging agent and 1.5% to 6% rubber vulcanizing agent composition. 2. The nano-microcrystalline NCC reinforced rubber material according to claim 1, characterized in that, the EPDM rubber masterbatch is the EPDM rubber reinforced by powdery carbon black. 3. The nano-microcrystalline NCC reinforced rubber material according to claim 2, characterized in that the weight content of powdered carbon black in the EPDM rubber reinforced with powdery carbon black is 20% to 50%. 4. The nano-microcrystalline NCC reinforced rubber material according to claim 1, wherein the modifying agent is selected from one, two or both of chloroprene rubber, styrene-butadiene rubber, fluororubber and silicon rubber. more than one species. 5. The nano-microcrystalline NCC reinforced rubber material according to claim 1, wherein the surfactant is selected from KH550, KH560, stearic acid, n-butyl titanate and ethyltrimethoxysilane One, two or more than two. 6. nano microcrystalline NCC reinforced rubber material according to claim 1, is characterized in that, described anti-aging agent is selected from liquid paraffin, modified liquid paraffin, triethyl glyceride and dibutyl phthalate One, two or more than two. 7. nano-microcrystalline NCC reinforced rubber material according to claim 1, is characterized in that, described rubber vulcanizing agent is selected from the one in magnesium dimethacrylate, TMTD, epoxy resin, zinc chloride and magnesium oxide , two or more. 8. the preparation method of nano-microcrystalline NCC reinforced rubber material according to claim 1, is characterized in that, comprises the following steps: 1) use a surfactant to process NCC to obtain a modified NCC solution; 2) Add the EPDM rubber masterbatch, modifier and modified NCC solution into the mixer for mixing. The mixing temperature is 120-130°C and the mixing time is 3-8 minutes. After mixing, the mixing temperature is 110-120 ℃ discharge, to obtain a primary mixing material; 3) Add the anti-aging agent and the primary mixing material into the internal mixer for 2-10 minutes, then add the rubber vulcanizing agent, knead at high speed and transport to the open mixer; 4) Thinly pass the mixture in step 3) 2 to 4 times in the open mill, fully mix the EPDM rubber masterbatch, modifier and modified NCC, input them into the screw extruder, and Extrusion and extrusion molded products; 5) Vulcanize the molded product in step 4), the vulcanization temperature is 100-150°C, the vulcanization pressure is 1.5-5MPa, the vulcanization time is 15-45min, and the nano-microcrystalline NCC reinforced rubber material can be made after vulcanization . 9. preparation method according to claim 8, is characterized in that, described EPDM rubber masterbatch is the EPDM rubber that powdery carbon black strengthens, and in the EPDM rubber that described powdery carbon black strengthens, powdery carbon black weight content is 20% to 50%. 10. preparation method according to claim 8, is characterized in that, described antiaging agent is selected from one, two kinds in liquid paraffin, modified liquid paraffin, triethyl glyceride and dibutyl phthalate or two or more.