WO2019157767A1 - 一种纳米微晶ncc增强橡胶材料及其制备方法 - Google Patents

一种纳米微晶ncc增强橡胶材料及其制备方法 Download PDF

Info

Publication number
WO2019157767A1
WO2019157767A1 PCT/CN2018/077073 CN2018077073W WO2019157767A1 WO 2019157767 A1 WO2019157767 A1 WO 2019157767A1 CN 2018077073 W CN2018077073 W CN 2018077073W WO 2019157767 A1 WO2019157767 A1 WO 2019157767A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
ncc
reinforced
modifier
carbon black
Prior art date
Application number
PCT/CN2018/077073
Other languages
English (en)
French (fr)
Inventor
纪荣华
Original Assignee
太仓荣南密封件科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 太仓荣南密封件科技有限公司 filed Critical 太仓荣南密封件科技有限公司
Publication of WO2019157767A1 publication Critical patent/WO2019157767A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the invention belongs to the field of rubber materials, 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.
  • NCC Nanocrystals Cellulose
  • Patent Document CN101555330A published on Dec. 2009.10.14, provides a fiber reinforced rubber which is kneaded from a rubberized rubber raw material, a reinforcing agent, a fiber and an auxiliary agent to form a fiber reinforced rubber product.
  • the patent solves the problem of uneven fiber dispersion in the preparation process of the traditional fiber reinforced rubber, and the preparation process is simple, and the prepared rubber has good elasticity, small compression deformation and excellent physical and mechanical properties.
  • this patent uses a large amount of glass fiber as the reinforcing fiber, and the hardness of the product is large.
  • the rubber prepared in the long-term use process causes the glass fiber to be reinforced due to the aging of the glass fiber, which reduces the service life of the reinforced rubber.
  • Patent Document CN102002173A published on 2011.04.06, provides a method for preparing a nano microcrystalline cellulose/silica/rubber composite material, which uses a rod-shaped nano microcrystalline fiber having a diameter of 20 to 60 nm and an average length of 300 nm as a reinforcing material. Reinforce rubber.
  • NCC has better reinforcing effect on natural rubber than white carbon black, which improves the heat-resistant oxygen aging performance of natural rubber, and also reduces the heat generation of composite materials, and can be prepared by traditional rubber processing technology.
  • Composite rubber uses natural rubber as a raw material. Due to limited production, its high price and narrow temperature range are not conducive to industrial large-scale production applications.
  • Patent Document CN104761761A published on Dec. 2015.07.08, provides a high toughness nanofiber reinforced rubber-based 3D printing material prepared from a rubber compound, a thermoplastic polymer nanofiber reinforcement, and a solvent.
  • the patent solves the problem that the traditional powder rubber material has low strength, poor toughness and needs to be modified before use, and the rubber-based 3D printing material prepared has the advantages of high bonding strength and simple production process.
  • the patent uses toxic and harmful solvents such as acetone, methylene chloride and carbon tetrachloride for production. The production is harmful and not environmentally friendly.
  • the increase of a large amount of powder leads to the brittleness of the rubber material, and the powder reinforcement tends to fall. Falling down reduces the life of the rubber.
  • the patent document CN104629105A published on Dec. 2015.05.20, discloses a microcrystalline cellulose reinforced rubber wear-resistant material and a preparation method thereof, which are prepared from the following main raw materials by weight ratio: surface-modified microcrystalline cellulose 1 ⁇ 35 parts, the surface of which is coated with 1% to 2% by weight of microcrystalline cellulose, a sizing agent or a coupling agent, and a rubber matrix of 65 to 99 parts; the route is to suspend the nanocrystalline cellulose and spray the sizing agent Or a coupling agent, heated at 60-120 ° C until the sizing agent and the coupling agent are completely spread and infiltrated on the surface of the cellulose, and then the surface-modified microcrystalline cellulose is kneaded and vulcanized with a rubber matrix.
  • Patent document CN104530504A discloses a rubber composite material of nano microcrystalline cellulose based on waste cotton material and a preparation method thereof, the method is: stirring natural rubber latex; and cotton nano microcrystalline cellulose Adding to natural rubber latex, stirring and mixing, obtaining cotton nano-microcrystalline cellulose/natural rubber mixture; tiling, co-precipitating, washing and precipitating, drying to balance, to obtain solid cotton nano-microcrystalline cellulose / natural Rubber mixture; kneaded with silica to give the desired product.
  • the performance of the above reinforced rubber is still not satisfactory.
  • the object of the present invention is to provide a nano microcrystalline NCC reinforced rubber material with good toughness, high wear resistance, aging resistance, crack resistance and low cost, and clean and environmental protection, and a preparation method thereof.
  • the nanocrystalline CNC reinforced rubber material provided by the present invention is made of the following components by weight: 1% to 25% NCC, 2% to 15% chemical auxiliary, 5% to 30% modified
  • the balance is EPDM rubber masterbatch;
  • the NCC has a diameter of 2-15 nm and a length of 150-400 nm;
  • the chemical auxiliary comprises 0.01%-4% surfactant, 0.5%-5% anti-aging agent and 1.5 % to 6% of rubber vulcanizing agent, the percentage of the total weight of all the raw materials is 2% to 15%.
  • the EPDM rubber master batch is a powdery carbon black reinforced EPDM rubber.
  • the powdered carbon black-reinforced EPDM rubber has a powdery carbon black content of 20% to 50% by weight.
  • the modifier is selected from one, two or more selected from the group consisting of neoprene rubber, styrene-butadiene rubber, fluororubber, and silicone rubber.
  • the surfactant is one, two or more selected from the group consisting of KH550, KH560, stearic acid, n-butyl titanate, and ethyltrimethoxysilane.
  • the anti-aging agent is one, two or more selected from the group consisting of liquid paraffin, modified liquid paraffin, triethyl glycerol, and dibutyl phthalate.
  • the rubber vulcanizing agent is one, two or more selected from the group consisting of magnesium dimethacrylate, TMTD, epoxy resin, zinc chloride, and magnesium oxide.
  • the method for preparing a nanocrystalline CNC reinforced rubber material comprises the following steps:
  • the EPDM rubber masterbatch, modifier and modified NCC solution are added to the mixer for mixing.
  • the mixing temperature is 120-130 ° C
  • the mixing time is 3-8 min
  • the mixing time is 110-120. °C discharge, get a mixed material
  • step 4) After the mixture in step 3) is thinned 2 to 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder, and squeezed. Machine and extrusion molding products;
  • vulcanization temperature is 100-150 ° C
  • vulcanization pressure is 1.5-5 MPa
  • vulcanization time is 15-45 min
  • the nano-crystallite NCC reinforced rubber material can be prepared after vulcanization.
  • the EPDM rubber master batch is a powdery carbon black reinforced EPDM rubber, and the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 20% to 50% by weight.
  • the anti-aging agent is one, two or more selected from the group consisting of liquid paraffin, modified liquid paraffin, triethyl glycerol, and dibutyl phthalate.
  • the EPDM rubber masterbatch that is, ethylene propylene diene monomer, is a copolymer of ethylene, propylene and a small amount of a non-conjugated diene.
  • the KH550 is an amino functional silane, the chemical name ⁇ -aminopropyltriethoxysilane.
  • the KH560 is an epoxy group-containing coupling agent having the chemical name ⁇ -glycidyloxypropyltrimethoxysilane.
  • the TMTD is also known as N,N-tetramethyldithiobisthiocarbonylamine.
  • composition and ratio of the raw materials are scientific and reasonable, and the toughness of the prepared rubber material is remarkably increased, and the wear resistance is improved while the toughness is improved, and the rubber reinforcing purpose is achieved;
  • the anti-aging agent and the rubber vulcanizing agent have a certain synergistic effect
  • Raw materials do not contain toxic and harmful solvents, clean and environmentally friendly;
  • the material of the present invention is particularly suitable for the preparation of a seal.
  • the NCC was purchased from Israel; the chloroprene rubber was purchased from LANXESS Chemical (China) Co., Ltd.; the KH560, dibutyl phthalate, TMTD, and magnesia were purchased from Ningbo. Aikem New Materials Co., Ltd.; the powdered carbon black reinforced EPDM rubber was purchased from Cabot Corporation of the United States; the fluororubber was purchased from DuPont, USA; the ethyltrimethoxysilane was purchased from Wacker Chemicals ( China) Limited. Others are not described here, and are all commercially available raw materials.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percentage components: 5% NCC, 11.5% chemical auxiliaries, 5% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 2 nm and a length of 400 nm.
  • the chemical auxiliaries include 4% surfactant, 1.5% anti-aging agent and 6% rubber vulcanizing agent.
  • the modifier is a neoprene rubber.
  • the surfactant is KH560.
  • the anti-aging agent is dibutyl phthalate.
  • the rubber vulcanizing agent is TMTD.
  • the EPDM rubber masterbatch is a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 20% by weight.
  • the preparation method comprises the following steps:
  • step 4) After the mixture in step 3) is thinned 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 150 ° C, the vulcanization pressure is 2.5 MPa, and the vulcanization time is 15 min. After the vulcanization, the nano microcrystalline NCC reinforced rubber material can be prepared.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percent components: 5% NCC, 13.5% chemical auxiliaries, 5.5% modifier, and the balance EDPM rubber masterbatch.
  • the NCC has a diameter of 5 nm and a length of 150 nm.
  • the chemical auxiliaries include 4% surfactant, 4.5% anti-aging agent and 5% rubber vulcanizing agent.
  • the modifier is a fluororubber.
  • the surfactant is ethyltrimethoxysilane.
  • the anti-aging agent is dibutyl phthalate.
  • the rubber vulcanizing agent is magnesium oxide.
  • the EDPM rubber masterbatch is a powdery carbon black reinforced EDPM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 35% by weight.
  • the preparation method comprises the following steps:
  • step 4) After the mixture in step 3) is thinned twice in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 150 ° C, the vulcanization pressure is 1.5 MPa, the vulcanization time is 35 min, and the nano microcrystalline NCC reinforced rubber material can be prepared after vulcanization.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percent components: 1% NCC, 2.01% chemical auxiliaries, 30% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 15 nm and a length of 300 nm.
  • the chemical auxiliaries include 0.01% surfactant, 0.5% anti-aging agent and 1.5% rubber vulcanizing agent.
  • the modifier is a silicone rubber.
  • the surfactant is KH550.
  • the anti-aging agent is liquid paraffin.
  • the rubber vulcanizing agent is an epoxy resin.
  • the EPDM rubber masterbatch is a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 50% by weight.
  • the preparation method comprises the following steps:
  • EPDM rubber masterbatch, modifier and modified NCC solution are added to the mixer for mixing.
  • the mixing temperature is 125 ° C
  • the mixing time is 3 min
  • the mixture is discharged at 120 ° C after mixing.
  • step 4) After the mixture in step 3) is thinned three times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 100 ° C, the vulcanization pressure is 5 MPa, and the vulcanization time is 30 min. After the vulcanization, the nano microcrystalline NCC reinforced rubber material can be prepared.
  • the nanocrystalline CNC reinforced rubber material is made of the following weight percent components: 25% NCC, 10% chemical auxiliaries, 20% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 2 nm and a length of 400 nm.
  • the chemical auxiliaries include 1% surfactant, 5% anti-aging agent and 4% rubber vulcanizing agent.
  • the modifier is styrene butadiene rubber.
  • the surfactant is stearic acid.
  • the anti-aging agent is a modified liquid paraffin.
  • the rubber vulcanizing agent is magnesium dimethacrylate.
  • the EPDM rubber masterbatch is a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 20% by weight.
  • the preparation method comprises the following steps:
  • step 4) After the mixture in step 3) is thinned 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 120 ° C, the vulcanization pressure is 5 MPa, and the vulcanization time is 30 min. After the vulcanization, the nano microcrystalline NCC reinforced rubber material can be prepared.
  • the nanocrystalline CNC reinforced rubber material is made of the following weight percent components: 15% NCC, 15% chemical auxiliaries, 10% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 5 nm and a length of 150 nm.
  • the chemical auxiliaries include 4% surfactant, 5% anti-aging 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 was a mixture of KH550 and KH560, and the weight ratio of the two was 1:1.
  • the anti-aging agent is triethyl glycerol.
  • the rubber vulcanizing agent is zinc chloride.
  • the EPDM rubber masterbatch is a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 20% by weight.
  • the preparation method comprises the following steps:
  • step 4) After the mixture in step 3) is thinned 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 150 ° C, the vulcanization pressure is 2.5 MPa, and the vulcanization time is 15 min. After the vulcanization, the nano microcrystalline NCC reinforced rubber material can be prepared.
  • the nanocrystalline CNC reinforced rubber material is made of the following weight percent components: 5% NCC, 5% chemical auxiliaries, 10% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 2 nm and a length of 400 nm.
  • the chemical auxiliaries include 1% surfactant, 2% anti-aging agent and 2% rubber vulcanizing agent.
  • the modifier is a mixture of chloroprene rubber, styrene butadiene rubber and fluororubber, and the weight ratio of the three is 1:1:2.
  • the surfactant is n-butyl titanate.
  • the anti-aging 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 a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 50% by weight.
  • the preparation method comprises the following steps:
  • EPDM rubber masterbatch, modifier and modified NCC solution are added to the mixer for mixing.
  • the mixing temperature is 120 ° C
  • the mixing time is 5 min
  • the mixture is discharged at 110 ° C after mixing.
  • step 4) After the mixture in step 3) is thinned 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • step 4) The molded product in step 4) is vulcanized, the vulcanization temperature is 150 ° C, the vulcanization pressure is 5 MPa, the vulcanization time is 15 min, and the nanocrystalline CMC reinforced rubber material can be prepared after vulcanization.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percent components: 5% NCC, 10% chemical auxiliaries, 15% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 2 nm and a length of 400 nm.
  • the chemical auxiliaries include 4% surfactant, 4% anti-aging agent and 2% rubber vulcanizing agent.
  • the modifier is a neoprene rubber.
  • the surfactant is KH560.
  • the anti-aging agent is triethyl glycerol.
  • the rubber vulcanizing agent is a mixture of magnesium dimethacrylate, zinc chloride and magnesium oxide in a weight ratio of 1:1:1.
  • the EPDM rubber masterbatch is a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 35% by weight.
  • the preparation method comprises the following steps:
  • EPDM rubber masterbatch, modifier and modified NCC solution are added to the mixer for mixing.
  • the mixing temperature is 130 ° C
  • the mixing time is 3 min
  • the mixture is discharged at 120 ° C after mixing.
  • step 4) After the mixture in step 3) is thinned three times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 120 ° C, the vulcanization pressure is 5 MPa, and the vulcanization time is 30 min. After the vulcanization, the nano microcrystalline NCC reinforced rubber material can be prepared.
  • the nanocrystalline CNC reinforced rubber material is made of the following weight percent components: 5% NCC, 10% chemical auxiliaries, 5.5% modifier, and the balance EDPM rubber masterbatch.
  • the NCC has a diameter of 5 nm and a length of 150 nm.
  • the chemical auxiliaries include 1% surfactant, 3% anti-aging agent and 6% rubber vulcanizing agent.
  • the modifier is a fluororubber.
  • the surfactant is stearic acid.
  • the anti-aging agent is dibutyl phthalate.
  • the rubber vulcanizing agent is magnesium dimethacrylate.
  • the EDPM rubber masterbatch is a powdery carbon black reinforced EDPM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 20% by weight.
  • the preparation method comprises the following steps:
  • step 4) After the mixture in step 3) is thinned twice in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 150 ° C, the vulcanization pressure is 1.5 MPa, the vulcanization time is 35 min, and the nano microcrystalline NCC reinforced rubber material can be prepared after vulcanization.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percent components: 10% NCC, 8% chemical auxiliaries, 5.5% modifier, and the balance is EDPM rubber masterbatch.
  • the NCC has a diameter of 5 nm and a length of 150 nm.
  • the chemical auxiliaries include 4% surfactant, 2% anti-aging agent and 2% rubber vulcanizing agent.
  • the modifier is styrene butadiene rubber.
  • the surfactant was a mixture of KH550 and KH560, and the weight ratio of the two was 1:1.
  • the anti-aging agent is dibutyl phthalate.
  • the rubber vulcanizing agent is magnesium oxide.
  • the EDPM rubber masterbatch is a powdery carbon black reinforced EDPM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 50% by weight.
  • the preparation method comprises the following steps:
  • step 4) After the mixture in step 3) is thinned twice in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 150 ° C, the vulcanization pressure is 1.5 MPa, the vulcanization time is 35 min, and the nano microcrystalline NCC reinforced rubber material can be prepared after vulcanization.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percent components: 15% NCC, 5% chemical auxiliaries, 20% modifier, and the balance is EDPM rubber masterbatch.
  • the NCC has a diameter of 5 nm and a length of 150 nm.
  • the chemical auxiliaries include 1% surfactant, 1% anti-aging 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 in a weight ratio of 2:1:2.
  • the EDPM rubber masterbatch is a powdery carbon black reinforced EDPM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 20% by weight.
  • the preparation method comprises the following steps:
  • step 4) After the mixture in step 3) is thinned three times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • step 4) The molded product in step 4) is vulcanized, the vulcanization temperature is 150 ° C, the vulcanization pressure is 5 MPa, the vulcanization time is 15 min, and the nanocrystalline CMC reinforced rubber material can be prepared after vulcanization.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percent components: 1% NCC, 2.01% chemical auxiliaries, 30% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 20 nm and a length of 500 nm.
  • the chemical auxiliaries include 0.01% surfactant, 0.5% anti-aging agent and 1.5% rubber vulcanizing agent.
  • the modifier is a silicone rubber.
  • the surfactant is KH550.
  • the anti-aging agent is liquid paraffin.
  • the rubber vulcanizing agent is an epoxy resin.
  • the EPDM rubber masterbatch is a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 50% by weight.
  • the preparation method comprises the following steps:
  • EPDM rubber masterbatch, modifier and modified NCC solution are added to the mixer for mixing.
  • the mixing temperature is 125 ° C
  • the mixing time is 3 min
  • the mixture is discharged at 120 ° C after mixing.
  • step 4) After the mixture in step 3) is thinned three times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 100 ° C, the vulcanization pressure is 5 MPa, and the vulcanization time is 30 min. After the vulcanization, the nano microcrystalline NCC reinforced rubber material is prepared.
  • the nanocrystalline CNC reinforced rubber material is made of the following weight percentage components: 5% NCC, 11.5% chemical auxiliaries, 5% modifier, and the balance is natural rubber.
  • the NCC has a diameter of 2 nm and a length of 400 nm.
  • the chemical auxiliaries include 4% surfactant, 1.5% anti-aging agent and 6% rubber vulcanizing agent.
  • the modifier is a neoprene rubber.
  • the surfactant is KH560.
  • the anti-aging agent is dibutyl phthalate.
  • the rubber vulcanizing agent is TMTD.
  • the preparation method comprises the following steps:
  • step 4) After the mixture in step 3) is thinned 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 150 ° C, the vulcanization pressure is 2.5 MPa, and the vulcanization time is 15 min. After the vulcanization, the nano microcrystalline NCC reinforced rubber material is prepared.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percent components: 30% NCC, 10% chemical auxiliaries, 20% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 2 nm and a length of 400 nm.
  • the chemical auxiliaries include 1% surfactant, 5% anti-aging agent and 4% rubber vulcanizing agent.
  • the modifier is styrene butadiene rubber.
  • the surfactant is stearic acid.
  • the anti-aging agent is a modified liquid paraffin.
  • the rubber vulcanizing agent is magnesium dimethacrylate.
  • the EPDM rubber masterbatch is a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 20% by weight.
  • the preparation method comprises the following steps:
  • step 4) After the mixture in step 3) is thinned 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 120 ° C, the vulcanization pressure is 5 MPa, and the vulcanization time is 30 min. After the vulcanization, the nano microcrystalline NCC reinforced rubber material is prepared.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percent components: 5% NCC, 11.5% chemical auxiliaries, 5% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 2 nm and a length of 400 nm.
  • the chemical auxiliaries include 4% surfactant, 1.5% anti-aging agent and 6% rubber vulcanizing agent.
  • the modifier is a neoprene rubber.
  • 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 a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 20% by weight.
  • the preparation method comprises the following steps:
  • step 4) After the mixture in step 3) is thinned 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 150 ° C, the vulcanization pressure is 2.5 MPa, and the vulcanization time is 15 min. After the vulcanization, the nano microcrystalline NCC reinforced rubber material is prepared.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percentage components: 5% NCC, 11.5% chemical auxiliaries, 5% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 2 nm and a length of 400 nm.
  • the chemical auxiliaries include 2% anti-aging agent and 9.5% rubber vulcanizing agent.
  • the modifier is a neoprene rubber.
  • the anti-aging agent is dibutyl phthalate.
  • the rubber vulcanizing agent is TMTD.
  • the EPDM rubber masterbatch is a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 20% by weight.
  • the preparation method comprises the following steps:
  • the NCC, EPDM rubber masterbatch and modifier are added to the mixer for mixing.
  • the mixing temperature is 120 ° C
  • the mixing time is 8 min
  • the mixture is discharged at 110 ° C after mixing to obtain a mixed material.
  • step 2) After the mixture in step 2) is thinned 4 times in the mill, the EPDM rubber masterbatch, modifier and NCC are thoroughly mixed and fed into the screw extruder, through the extruder and squeezed. Out of mold molding products;
  • the molded product in the step 3) is vulcanized, the vulcanization temperature is 150 ° C, the vulcanization pressure is 2.5 MPa, and the vulcanization time is 15 min. After the vulcanization, the nano microcrystalline NCC reinforced rubber material is prepared.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percentage components: 5% NCC, 11.5% chemical auxiliaries, 5% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 2 nm and a length of 400 nm.
  • the chemical auxiliaries include 8% surfactant, 3.5% anti-aging agent.
  • the modifier is a neoprene rubber.
  • the surfactant is KH560.
  • the anti-aging agent is dibutyl phthalate.
  • the EPDM rubber masterbatch is a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 20% by weight.
  • the preparation method comprises the following steps:
  • step 4) After the mixture in step 3) is thinned 4 times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • step 4) The shaped product in step 4) is treated at a temperature of 150 ° C and a pressure of 2.5 MPa for 15 minutes to prepare a nanocrystalline CMC reinforced rubber material.
  • the nanocrystalline MNC reinforced rubber material is made of the following weight percent components: 1% NCC, 2.01% chemical auxiliaries, 30% modifier, and the balance is EPDM rubber masterbatch.
  • the NCC has a diameter of 15 nm and a length of 300 nm.
  • the chemical auxiliaries include 0.01% surfactant, 0.5% anti-aging agent and 1.5% rubber vulcanizing agent.
  • the modifier is a silicone rubber.
  • the surfactant is KH550.
  • the anti-aging agent is liquid paraffin.
  • the rubber vulcanizing agent is an epoxy resin.
  • the EPDM rubber masterbatch is a powdery carbon black reinforced EPDM rubber, wherein the powdery carbon black reinforced EPDM rubber has a powdery carbon black content of 55% by weight.
  • the preparation method comprises the following steps:
  • EPDM rubber masterbatch, modifier and modified NCC solution are added to the mixer for mixing.
  • the mixing temperature is 125 ° C
  • the mixing time is 3 min
  • the mixture is discharged at 120 ° C after mixing.
  • step 4) After the mixture in step 3) is thinned three times in the open mill, the EPDM rubber masterbatch, modifier and modified NCC are thoroughly mixed and fed into the screw extruder through the extruder. And extrusion molding products;
  • the molded product in the step 4) is vulcanized, the vulcanization temperature is 100 ° C, the vulcanization pressure is 5 MPa, and the vulcanization time is 30 min. After the vulcanization, the nano microcrystalline NCC reinforced rubber material can be prepared.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种纳米微晶NCC增强橡胶材料及其制备方法，所述的纳米微晶NCC增强橡胶材料由NCC、化学助剂、改性剂和EPDM橡胶母料组成。其制备方法包括以下步骤：1)使用表面活化剂处理NCC；2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼；3)将抗老化剂和混炼料加入密炼机中密炼后加入橡胶硫化剂，高速捏合搅拌后输送至开炼机；4)在开炼机中对混合料薄通，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；5)将挤出成型产品进行硫化，硫化后即得。材料韧性和耐磨性均显著增加，且原料成本低，清洁环保。

Description

一种纳米微晶NCC增强橡胶材料及其制备方法 技术领域
本发明属于橡胶材料领域，涉及一种橡胶材料及其制备方法，具体地说，是一种纳米微晶NCC增强橡胶材料及其制备方法。
背景技术
作为一种优质的弹性材料，橡胶已被广泛地用于各个领域。根据橡胶的组成不同，其性能、用途也不一样，有用于一般家居地板的普通橡胶地板、防滑垫，也有容器密封、法兰密封用的特种增强橡胶垫圈。玻纤、碳纤维、芳纶纤维、合成纤维、炭黑等通常被用于增强橡胶材料，具有耐温耐压、耐磨性好、耐溶剂性好等优点，但其也存在诸多问题，如纤维分散不均、橡胶与纤维粘合不牢等，从而导致纤维增强效果并不理想。纳米微晶纤维素(Nanocrystals Cellulose，简称NCC)作为一种来源于木质材料的天然大分子化合物，单根纤维强度高达57GPa，对橡胶亲和性好，可应用于替代传统玻纤、碳纤维等来制造增强橡胶材料。
专利文献CN101555330A，公开日2009.10.14，提供了一种纤维增强橡胶，由塑炼橡胶原料、补强剂、纤维和助剂混炼后制成纤维增强橡胶制品。该专利解决了传统纤维增强橡胶制备过程中的纤维分散不均问题，并且制备工艺流程简单，所制备橡胶弹性好、压缩形变小、物理机械性能优异。但是，该专利使用大量玻璃纤维作为增强纤维，制品硬度较大，所制备橡胶在长期使用过程中以发生老化玻纤脱落导致玻纤增强失效，降低了增强橡胶的使用寿命。
专利文献CN102002173A，公开日2011.04.06，提供了一种纳米微晶纤维素/白炭黑/橡胶复合材料的制备方法，采用直径20～60nm，平均长度300nm的棒状纳米微晶纤维作为补强材料补强橡胶。该专利中NCC对天然橡胶的补强效果优于白炭黑，很好地改善了天然橡胶的耐热氧老化性能，同时还降低了复合材料的生热，并可采取传统的橡胶加工工艺制备复合橡胶。但是，该专利使用了天然橡胶作为原材料，由于产量有限，其价格高昂，且耐温范围窄，不利于工业化大规模生产应用。
专利文献CN104761761A，公开日2015.07.08，提供了一种高韧性的纳米纤维增强橡胶基3D打印用材料，由混炼橡胶、热塑性聚合物纳米纤维增强材料和溶剂制备而成。该专利解决了传统粉末橡胶材料强度低、韧性差、使用前需要改性的问题，同时所制备的橡胶基3D打印用材料还具有粘结强度高、生产工艺简单等优点。但是该专利使用丙酮、二氯甲烷、四氯化碳等有毒有害溶剂进行生产，生产危害较大且不环保，加之大量粉体的增加会导致橡胶材料脆性较大，粉体增强材料往往会掉落下来，降低了橡胶的使用寿 命。
此外，专利文献CN104629105A，公开日2015.05.20，公开了一种微晶纤维素增强橡胶耐磨材料及其制备方法，由下列重量份比的主要原料制成：表面修饰的微晶纤维素1～35份，其表面涂覆有微晶纤维素重量1％～2％的浸润剂或偶联剂，橡胶基体65～99份；工艺路线是将纳米微晶纤维素悬浮开松并喷淋浸润剂或偶联剂，在60～120℃加热至浸润剂和偶联剂在纤维素表面完全铺展浸润，然后将这些表面修饰的微晶纤维素与橡胶基体进行混炼、硫化制得。专利文献CN104530504A，公开日2015.04.22，公开了一种基于废棉材料的纳米微晶纤维素的橡胶复合材料及其制备方法，该方法为：将天然橡胶胶乳搅拌；将棉纳米微晶纤维素加入到天然橡胶胶乳中，搅拌混合，得到棉纳米微晶纤维素/天然橡胶混合物；平铺，经破乳共沉、洗涤沉淀，烘至衡重，即得到固体棉纳米微晶纤维素/天然橡胶混合物；与白炭黑混炼，得到所要产物。然而上述增强橡胶的性能仍不理想。
综上，亟需一种韧性、耐磨性强，耐老化，抗裂且成本低，清洁环保的增强橡胶材料。
发明内容
本发明的目的是针对现有技术中的不足，提供一种韧性、耐磨性强，耐老化，抗裂且成本低，清洁环保的纳米微晶NCC增强橡胶材料及其制备方法。
第一方面，本发明提供的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：1％～25％的NCC，2％～15％的化学助剂，5％～30％改性剂，余量为EPDM橡胶母料；所述NCC直径为2～15nm，长度为150～400nm；所述化学助剂由0.01％～4％表面活化剂，0.5％～5％抗老化剂和1.5％～6％橡胶硫化剂组成，三者占所有原料总重量的百分比为2％～15％。
作为另一优选例，所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶。
作为另一优选例，所述粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％～50％。
作为另一优选例，所述改性剂选自氯丁橡胶、丁苯橡胶、氟橡胶和硅橡胶中的一种、两种或两种以上。
作为另一优选例，所述表面活化剂选自KH550、KH560、硬脂酸、钛酸正丁酯和乙基三甲氧基硅烷中的一种、两种或两种以上。
作为另一优选例，所述抗老化剂选自液体石蜡、改性液体石蜡、甘油三乙酯和邻苯二甲酸二丁酯中的一种、两种或两种以上。
作为另一优选例，所述橡胶硫化剂选自二甲基丙烯酸镁、TMTD、环氧树脂、氯化 锌和氧化镁中的一种、两种或两种以上。
第二方面，本发明提供的纳米微晶NCC增强橡胶材料的制备方法，包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为120～130℃，混炼时间为3～8min，混炼后在110～120℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼2～10min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通2～4次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为100～150℃，硫化压力为1.5～5MPa，硫化时间为15～45min，硫化后即可制成所述纳米微晶NCC增强橡胶材料。
作为另一优选例，所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，所述粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％～50％。
作为另一优选例，所述抗老化剂选自液体石蜡、改性液体石蜡、甘油三乙酯和邻苯二甲酸二丁酯中的一种、两种或两种以上。
本文中，所述EPDM橡胶母料即三元乙丙橡胶，是乙烯、丙烯和少量的非共轭二烯烃的共聚物。所述KH550为氨基官能团硅烷，化学名称γ―氨丙基三乙氧基硅烷。所述KH560是一种含环氧基的偶联剂，化学名称γ-缩水甘油醚氧丙基三甲氧基硅烷。所述TMTD又称N,N-四甲基二硫双硫羰胺。
本发明的有益效果是：
(1)原料组成和配比科学合理，制备的橡胶材料的韧性显著增加，在提升韧性的同时，提高了耐磨性，达到了橡胶增强目的；
(2)橡胶分子间结合强度高，避免了增强橡胶中的界面处发生应力集中，导致开裂失效破坏的问题；
(3)本发明的材料中，抗老化剂和橡胶硫化剂具有一定的协同作用；
(4)原料种类较少，成本低，制备工艺简单；
(5)原料不含有毒有害溶剂，清洁环保；
(6)本发明的材料尤其适合制备密封件。
具体实施方式
下面结合具体实施例，进一步阐明本发明，应理解这些实施例仅用于说明本发明而不用于限制本发明的范围，在阅读了本发明之后，本领域技术人员对本发明的各种等价 形式的修改均落于本申请所附权利要求所限定。
以下实施例和对比例中，所述NCC购于以色列；所述氯丁橡胶购于朗盛化学(中国)有限公司；所述KH560、邻苯二甲酸二丁酯、TMTD、氧化镁购于宁波艾克姆新材料有限公司；所述粉状炭黑增强的EPDM橡胶购于美国卡博特公司；所述氟橡胶购于美国杜邦公司；所述乙基三甲氧基硅烷购于瓦克化学(中国)有限公司。其他在此不再赘述，均为市售原料。
实施例1
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：5％的NCC、11.5％的化学助剂、5％改性剂、余量为EPDM橡胶母料。
所述NCC直径为2nm，长度400nm。
所述化学助剂包括4％表面活化剂，1.5％抗老化剂和6％橡胶硫化剂。
所述改性剂为氯丁橡胶。
所述表面活化剂为KH560。
所述抗老化剂为邻苯二甲酸二丁酯。
所述橡胶硫化剂为TMTD。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为120℃，混炼时间为8min，混炼后在110℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼5min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通4次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为150℃，硫化压力为2.5MPa，硫化时间为15min，硫化后即可制成纳米微晶NCC增强橡胶材料。
实施例2
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：5％的NCC、13.5％的化学助剂、5.5％改性剂、余量为EDPM橡胶母料。
所述NCC直径为5nm，长度150nm。
所述化学助剂包括4％表面活化剂，4.5％抗老化剂和5％橡胶硫化剂。
所述改性剂为氟橡胶。
所述表面活化剂为乙基三甲氧基硅烷。
所述抗老化剂为邻苯二甲酸二丁酯。
所述橡胶硫化剂为氧化镁。
所述EDPM橡胶母料为粉状炭黑增强的EDPM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为35％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EDPM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为130℃，混炼时间为8min，混炼后在110℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼10min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通2次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为150℃，硫化压力为1.5MPa，硫化时间为35min，硫化后即可制成纳米微晶NCC增强橡胶材料。
实施例3
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：1％的NCC、2.01％的化学助剂、30％改性剂、余量为EPDM橡胶母料。
所述NCC直径为15nm，长度300nm。
所述化学助剂包括0.01％表面活化剂，0.5％抗老化剂和1.5％橡胶硫化剂。
所述改性剂为硅橡胶。
所述表面活化剂为KH550。
所述抗老化剂为液体石蜡。
所述橡胶硫化剂为环氧树脂。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为50％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温 度为125℃，混炼时间为3min，混炼后在120℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼2min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通3次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为100℃，硫化压力为5MPa，硫化时间为30min，硫化后即可制成纳米微晶NCC增强橡胶材料。
实施例4
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：25％的NCC、10％的化学助剂、20％改性剂、余量为EPDM橡胶母料。
所述NCC直径为2nm，长度400nm。
所述化学助剂包括1％表面活化剂，5％抗老化剂和4％橡胶硫化剂。
所述改性剂为丁苯橡胶。
所述表面活化剂为硬脂酸。
所述抗老化剂为改性液体石蜡。
所述橡胶硫化剂为二甲基丙烯酸镁。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为120℃，混炼时间为5min，混炼后在115℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼10min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通4次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为120℃，硫化压力为5MPa，硫化时间为30min，硫化后即可制成纳米微晶NCC增强橡胶材料。
实施例5
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：15％的NCC、15％的化学助剂、10％改性剂、余量为EPDM橡胶母料。
所述NCC直径为5nm，长度150nm。
所述化学助剂包括4％表面活化剂，5％抗老化剂和6％橡胶硫化剂。
所述改性剂为氯丁橡胶和丁苯橡胶的混合物，两者重量比为1:1。
所述表面活化剂为KH550和KH560的混合物，两者重量比为1:1。
所述抗老化剂为甘油三乙酯。
所述橡胶硫化剂为氯化锌。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为120℃，混炼时间为8min，混炼后在110℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼5min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通4次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为150℃，硫化压力为2.5MPa，硫化时间为15min，硫化后即可制成纳米微晶NCC增强橡胶材料。
实施例6
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：5％的NCC、5％的化学助剂、10％改性剂、余量为EPDM橡胶母料。
所述NCC直径为2nm，长度400nm。
所述化学助剂包括1％表面活化剂，2％抗老化剂和2％橡胶硫化剂。
所述改性剂为氯丁橡胶、丁苯橡胶和氟橡胶的混合物，三者重量比为1:1:2。
所述表面活化剂为钛酸正丁酯。
所述抗老化剂为邻苯二甲酸二丁酯和液体石蜡的混合物，两者重量比为1:1。
所述橡胶硫化剂为TMTD和氧化镁的混合物，两者重量比为1:3。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为50％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为120℃，混炼时间为5min，混炼后在110℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼5min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通4次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为150℃，硫化压力为5MPa，硫化时间为15min，硫化后即可制成纳米微晶NCC增强橡胶材料。
实施例7
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：5％的NCC、10％的化学助剂、15％改性剂、余量为EPDM橡胶母料。
所述NCC直径为2nm，长度400nm。
所述化学助剂包括4％表面活化剂，4％抗老化剂和2％橡胶硫化剂。
所述改性剂为氯丁橡胶。
所述表面活化剂为KH560。
所述抗老化剂为甘油三乙酯。
所述橡胶硫化剂为二甲基丙烯酸镁、氯化锌和氧化镁的混合物，三者重量比为1:1:1。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为35％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为130℃，混炼时间为3min，混炼后在120℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼10min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通3次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为120℃，硫化压力为5MPa，硫化时间为30min，硫化后即可制成纳米微晶NCC增强橡胶材料。
实施例8
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：5％的NCC、10％ 的化学助剂、5.5％改性剂、余量为EDPM橡胶母料。
所述NCC直径为5nm，长度150nm。
所述化学助剂包括1％表面活化剂，3％抗老化剂和6％橡胶硫化剂。
所述改性剂为氟橡胶。
所述表面活化剂为硬脂酸。
所述抗老化剂为邻苯二甲酸二丁酯。
所述橡胶硫化剂为二甲基丙烯酸镁。
所述EDPM橡胶母料为粉状炭黑增强的EDPM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EDPM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为130℃，混炼时间为8min，混炼后在110℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼10min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通2次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为150℃，硫化压力为1.5MPa，硫化时间为35min，硫化后即可制成纳米微晶NCC增强橡胶材料。
实施例9
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：10％的NCC、8％的化学助剂、5.5％改性剂、余量为EDPM橡胶母料。
所述NCC直径为5nm，长度150nm。
所述化学助剂包括4％表面活化剂，2％抗老化剂和2％橡胶硫化剂。
所述改性剂为丁苯橡胶。
所述表面活化剂为KH550和KH560的混合物，两者重量比为1:1。
所述抗老化剂为邻苯二甲酸二丁酯。
所述橡胶硫化剂为氧化镁。
所述EDPM橡胶母料为粉状炭黑增强的EDPM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为50％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EDPM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为130℃，混炼时间为8min，混炼后在110℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼10min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通2次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为150℃，硫化压力为1.5MPa，硫化时间为35min，硫化后即可制成纳米微晶NCC增强橡胶材料。
实施例10
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：15％的NCC、5％的化学助剂、20％改性剂、余量为EDPM橡胶母料。
所述NCC直径为5nm，长度150nm。
所述化学助剂包括1％表面活化剂，1％抗老化剂和3％橡胶硫化剂。
所述改性剂为氯丁橡胶、丁苯橡胶和硅橡胶的混合物，三者重量比为2:1:1。
所述表面活化剂为乙基三甲氧基硅烷。
所述抗老化剂为邻苯二甲酸二丁酯。
所述橡胶硫化剂为二甲基丙烯酸镁、TMTD和氧化镁的混合物，三者重量比为2:1:2。
所述EDPM橡胶母料为粉状炭黑增强的EDPM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EDPM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为130℃，混炼时间为8min，混炼后在110℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼10min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通3次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为150℃，硫化压力为5MPa，硫化时间为15min，硫化后即可制成纳米微晶NCC增强橡胶材料。
对比例1
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：1％的NCC、2.01％的化学助剂、30％改性剂、余量为EPDM橡胶母料。
所述NCC直径为20nm，长度500nm。
所述化学助剂包括0.01％表面活化剂，0.5％抗老化剂和1.5％橡胶硫化剂。
所述改性剂为硅橡胶。
所述表面活化剂为KH550。
所述抗老化剂为液体石蜡。
所述橡胶硫化剂为环氧树脂。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为50％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为125℃，混炼时间为3min，混炼后在120℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼2min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通3次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为100℃，硫化压力为5MPa，硫化时间为30min，硫化后即制成纳米微晶NCC增强橡胶材料。
对比例2
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：5％的NCC、11.5％的化学助剂、5％改性剂、余量为天然橡胶。
所述NCC直径为2nm，长度400nm。
所述化学助剂包括4％表面活化剂，1.5％抗老化剂和6％橡胶硫化剂。
所述改性剂为氯丁橡胶。
所述表面活化剂为KH560。
所述抗老化剂为邻苯二甲酸二丁酯。
所述橡胶硫化剂为TMTD。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为120℃，混炼时间为8min，混炼后在110℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼5min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通4次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为150℃，硫化压力为2.5MPa，硫化时间为15min，硫化后即制成纳米微晶NCC增强橡胶材料。
对比例3
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：30％的NCC、10％的化学助剂、20％改性剂、余量为EPDM橡胶母料。
所述NCC直径为2nm，长度400nm。
所述化学助剂包括1％表面活化剂，5％抗老化剂和4％橡胶硫化剂。
所述改性剂为丁苯橡胶。
所述表面活化剂为硬脂酸。
所述抗老化剂为改性液体石蜡。
所述橡胶硫化剂为二甲基丙烯酸镁。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为120℃，混炼时间为5min，混炼后在115℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼10min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通4次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为120℃，硫化压力为5MPa，硫化时间为30min，硫化后即制成纳米微晶NCC增强橡胶材料。
对比例4
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：5％的NCC、 11.5％的化学助剂、5％改性剂、余量为EPDM橡胶母料。
所述NCC直径为2nm，长度400nm。
所述化学助剂包括4％表面活化剂，1.5％抗老化剂和6％橡胶硫化剂。
所述改性剂为氯丁橡胶。
所述表面活化剂为KH560。
所述抗老化剂为4-甲基-6-叔丁基苯酚。
所述橡胶硫化剂为TMTD。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为120℃，混炼时间为8min，混炼后在110℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼5min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通4次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为150℃，硫化压力为2.5MPa，硫化时间为15min，硫化后即制成纳米微晶NCC增强橡胶材料。
对比例5
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：5％的NCC、11.5％的化学助剂、5％改性剂、余量为EPDM橡胶母料。
所述NCC直径为2nm，长度400nm。
所述化学助剂包括2％抗老化剂和9.5％橡胶硫化剂。
所述改性剂为氯丁橡胶。
所述抗老化剂为邻苯二甲酸二丁酯。
所述橡胶硫化剂为TMTD。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％。
其制备方法包括以下步骤：
1)将NCC、EPDM橡胶母料、改性剂加入到混炼机中进行混炼，混炼温度为120℃， 混炼时间为8min，混炼后在110℃出料，得到一次混炼料；
2)将抗老化剂和一次混炼料加入密炼机中密炼5min后加入橡胶硫化剂，高速捏合后输送至开炼机；
3)在开炼机中对步骤2)中的混合料薄通4次后，使EPDM橡胶母料、改性剂和NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
4)将步骤3)中的成型产品进行硫化，硫化温度为150℃，硫化压力为2.5MPa，硫化时间为15min，硫化后即制成纳米微晶NCC增强橡胶材料。
对比例6
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：5％的NCC、11.5％的化学助剂、5％改性剂、余量为EPDM橡胶母料。
所述NCC直径为2nm，长度400nm。
所述化学助剂包括8％表面活化剂，3.5％抗老化剂。
所述改性剂为氯丁橡胶。
所述表面活化剂为KH560。
所述抗老化剂为邻苯二甲酸二丁酯。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为120℃，混炼时间为8min，混炼后在110℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼5min，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通4次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品在温度150℃，压力2.5MPa下处理15min，即制成纳米微晶NCC增强橡胶材料。
对比例7
所述的纳米微晶NCC增强橡胶材料由以下重量百分比的组分制成：1％的NCC、2.01％的化学助剂、30％改性剂、余量为EPDM橡胶母料。
所述NCC直径为15nm，长度300nm。
所述化学助剂包括0.01％表面活化剂，0.5％抗老化剂和1.5％橡胶硫化剂。
所述改性剂为硅橡胶。
所述表面活化剂为KH550。
所述抗老化剂为液体石蜡。
所述橡胶硫化剂为环氧树脂。
所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，其中粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为55％。
其制备方法包括以下步骤：
1)使用表面活化剂处理NCC得到改性NCC溶液；
2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为125℃，混炼时间为3min，混炼后在120℃出料，得到一次混炼料；
3)将抗老化剂和一次混炼料加入密炼机中密炼2min后加入橡胶硫化剂，高速捏合后输送至开炼机；
4)在开炼机中对步骤3)中的混合料薄通3次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
5)将步骤4)中的成型产品进行硫化，硫化温度为100℃，硫化压力为5MPa，硫化时间为30min，硫化后即可制成纳米微晶NCC增强橡胶材料。
实施例11性能测试
根据国家标准测试实施例1-10及对比例1-7制备的纳米微晶NCC增强橡胶材料的机械性能，结果见表1。数据表明，本申请选择了科学合理的材料组成和配比，使得实施例1-10制备的纳米微晶NCC增强橡胶材料橡胶分子间结合强度高，韧性和耐磨性均显著增加，相比于对比例1-7的材料机械性能均显著提升。
表1实施例1-10及对比例1-7制备的NCC增强橡胶材料的机械性能
Figure PCTCN2018077073-appb-000001
Figure PCTCN2018077073-appb-000002
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。

Claims (10)

  1. 一种纳米微晶NCC增强橡胶材料，其特征在于，由以下重量百分比的组分制成：1％～25％的NCC，2％～15％的化学助剂，5％～30％改性剂，余量为EPDM橡胶母料；所述NCC直径为2～15nm，长度为150～400nm；所述化学助剂由0.01％～4％表面活化剂，0.5％～5％抗老化剂和1.5％～6％橡胶硫化剂组成。
  2. 根据权利要求1所述的纳米微晶NCC增强橡胶材料，其特征在于，所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶。
  3. 根据权利要求2所述的纳米微晶NCC增强橡胶材料，其特征在于，所述粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％～50％。
  4. 根据权利要求1所述的纳米微晶NCC增强橡胶材料，其特征在于，所述改性剂选自氯丁橡胶、丁苯橡胶、氟橡胶和硅橡胶中的一种、两种或两种以上。
  5. 根据权利要求1所述的纳米微晶NCC增强橡胶材料，其特征在于，所述表面活化剂选自KH550、KH560、硬脂酸、钛酸正丁酯和乙基三甲氧基硅烷中的一种、两种或两种以上。
  6. 根据权利要求1所述的纳米微晶NCC增强橡胶材料，其特征在于，所述抗老化剂选自液体石蜡、改性液体石蜡、甘油三乙酯和邻苯二甲酸二丁酯中的一种、两种或两种以上。
  7. 根据权利要求1所述的纳米微晶NCC增强橡胶材料，其特征在于，所述橡胶硫化剂选自二甲基丙烯酸镁、TMTD、环氧树脂、氯化锌和氧化镁中的一种、两种或两种以上。
  8. 权利要求1所述的纳米微晶NCC增强橡胶材料的制备方法，其特征在于，包括以下步骤：
    1)使用表面活化剂处理NCC得到改性NCC溶液；
    2)将EPDM橡胶母料、改性剂和改性NCC溶液加入到混炼机中进行混炼，混炼温度为120～130℃，混炼时间为3～8min，混炼后在110～120℃出料，得到一次混炼料；
    3)将抗老化剂和一次混炼料加入密炼机中密炼2～10min后加入橡胶硫化剂，高速捏合后输送至开炼机；
    4)在开炼机中对步骤3)中的混合料薄通2～4次后，使EPDM橡胶母料、改性剂和改性NCC充分混合均匀，输入到螺杆挤出机中，通过挤出机和挤出模具成型产品；
    5)将步骤4)中的成型产品进行硫化，硫化温度为100～150℃，硫化压力为1.5～5MPa，硫化时间为15～45min，硫化后即可制成所述纳米微晶NCC增强橡胶材料。
  9. 根据权利要求8所述的制备方法，其特征在于，所述EPDM橡胶母料为粉状炭黑增强的EPDM橡胶，所述粉状炭黑增强的EPDM橡胶中粉状炭黑重量含量为20％～50％。
  10. 根据权利要求8所述的制备方法，其特征在于，所述抗老化剂选自液体石蜡、改性液体石蜡、甘油三乙酯和邻苯二甲酸二丁酯中的一种、两种或两种以上。
PCT/CN2018/077073 2018-02-13 2018-02-24 一种纳米微晶ncc增强橡胶材料及其制备方法 WO2019157767A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810148888.1A CN108276687B (zh) 2018-02-13 2018-02-13 一种纳米微晶ncc增强橡胶材料及其制备方法
CN201810148888.1 2018-02-13

Publications (1)

Publication Number Publication Date
WO2019157767A1 true WO2019157767A1 (zh) 2019-08-22

Family

ID=62808511

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/077073 WO2019157767A1 (zh) 2018-02-13 2018-02-24 一种纳米微晶ncc增强橡胶材料及其制备方法

Country Status (2)

Country Link
CN (1) CN108276687B (zh)
WO (1) WO2019157767A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113861883A (zh) * 2021-10-05 2021-12-31 襄阳封神新材料有限公司 一种可降解密封胶生产工艺
CN114193883A (zh) * 2021-12-24 2022-03-18 苏州瑞高新材料有限公司 一种低压注塑用内饰材料及其制备方法
CN114213723A (zh) * 2021-12-22 2022-03-22 浙江三益鞋业有限公司 一种耐磨高强度的鞋材及其制备方法
CN114854103A (zh) * 2022-05-14 2022-08-05 桂林理工大学 一种改性剑麻纤维素微晶增强天然橡胶复合材料的制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138724B (zh) * 2019-12-11 2022-08-26 太仓荣南密封件科技有限公司 一种马来酸酐改性纳米微晶纤维素增强天然橡胶及其制备方法
CN112266539A (zh) * 2020-10-20 2021-01-26 上海荣南科技有限公司 一种少炭黑型三元乙丙橡胶及其制备方法
CN112300421A (zh) * 2020-10-20 2021-02-02 上海荣南科技有限公司 一种增强型三元乙丙橡胶及其制备方法
CN113958085A (zh) * 2021-11-08 2022-01-21 广东丰能环保科技股份有限公司 一种高弹性高耐老化性的三层橡胶地砖

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002173A (zh) * 2010-10-26 2011-04-06 华南理工大学 一种纳米微晶纤维素/白炭黑/橡胶复合材料的制备方法
US20130274406A1 (en) * 2012-04-13 2013-10-17 Xerox Corporation Reinforced fluoropolymer composites comprising surface functionalized nanocrystalline cellulose
CN104629105A (zh) * 2015-01-27 2015-05-20 山东大学 一种微晶纤维素增强橡胶耐磨材料及其制备方法
CN105754155A (zh) * 2016-03-28 2016-07-13 宿州学院 一种耐老化高阻燃天然橡胶复合材料

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101974172B (zh) * 2010-10-26 2012-10-31 华南理工大学 一种纳米微晶纤维素/炭黑/天然橡胶复合材料的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002173A (zh) * 2010-10-26 2011-04-06 华南理工大学 一种纳米微晶纤维素/白炭黑/橡胶复合材料的制备方法
US20130274406A1 (en) * 2012-04-13 2013-10-17 Xerox Corporation Reinforced fluoropolymer composites comprising surface functionalized nanocrystalline cellulose
CN104629105A (zh) * 2015-01-27 2015-05-20 山东大学 一种微晶纤维素增强橡胶耐磨材料及其制备方法
CN105754155A (zh) * 2016-03-28 2016-07-13 宿州学院 一种耐老化高阻燃天然橡胶复合材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MIAO, CHUANWEI ET AL.: "Alkenylation of Cellulose Nanocrystals (CNC) and Their Applications", POLYMER, vol. 101, 29 August 2016 (2016-08-29), XP029732277, doi:10.1016/j.polymer.2016.08.099 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113861883A (zh) * 2021-10-05 2021-12-31 襄阳封神新材料有限公司 一种可降解密封胶生产工艺
CN114213723A (zh) * 2021-12-22 2022-03-22 浙江三益鞋业有限公司 一种耐磨高强度的鞋材及其制备方法
CN114213723B (zh) * 2021-12-22 2023-02-10 浙江三益鞋业有限公司 一种耐磨高强度的鞋材及其制备方法
CN114193883A (zh) * 2021-12-24 2022-03-18 苏州瑞高新材料有限公司 一种低压注塑用内饰材料及其制备方法
CN114193883B (zh) * 2021-12-24 2023-05-26 苏州瑞高新材料有限公司 一种低压注塑用内饰材料及其制备方法
CN114854103A (zh) * 2022-05-14 2022-08-05 桂林理工大学 一种改性剑麻纤维素微晶增强天然橡胶复合材料的制备方法

Also Published As

Publication number Publication date
CN108276687B (zh) 2020-01-24
CN108276687A (zh) 2018-07-13

Similar Documents

Publication Publication Date Title
WO2019157767A1 (zh) 一种纳米微晶ncc增强橡胶材料及其制备方法
CN100487033C (zh) 氯丁橡胶共混物及其制备方法
CN101831090B (zh) 含碳纳米管的高性能天然橡胶硫化胶及其制备方法
CN101555330B (zh) 纤维增强橡胶
CN107189236A (zh) 一种耐热老化、低压变的硫磺硫化三元乙丙橡胶组合物、制备方法、用途及其应用产品
CN108192155A (zh) 用于输送带覆盖胶的石墨烯天然橡胶复合材料及制备方法
CN110591175B (zh) 一种高力学性能和低滞后损失的非填充橡胶组合物及其制备方法
CN105968588A (zh) 一种化肥造粒罐专用输送带
CN107418002A (zh) 一种高品质橡胶密封圈
CN105694153B (zh) 一种高填充轮胎再生胶的农业轮胎胎侧胶
CN102532673A (zh) 一种乙烯-乙酸乙烯酯共聚物的补强方法
CN102161788B (zh) 一种补强防老腈类弹性体的制备方法
CN109503894A (zh) 一种耐磨耐低温的橡胶的制备方法
CN100572431C (zh) 一种改进橡胶气密性的方法
CN106674631A (zh) 一种烯烃类橡胶/填料共混硫化胶的制备方法
CN107446160B (zh) 功能化蒙脱土增强pvc/nbr弹性体密封条及其制备方法
CN105566702B (zh) 一种高填充轮胎再生胶的农业轮胎胎冠胶
CN105199164B (zh) 汽车真空助力器橡胶皮膜
CN108084522A (zh) 一种高强度丁苯橡胶及其制备方法
TWI611912B (zh) 彈性物質強化用複合材料及其製造方法
CN104629191B (zh) 橡塑共混组合物、动态硫化热塑性弹性体及其制备方法
CN104312019A (zh) 一种玻璃纤维耐高热输送带覆盖胶及其制备方法
CN109648725B (zh) 混炼胶制造方法
CN114456456A (zh) 一种耐低温耐油的丁腈橡胶复合材料及其制备方法
CN104098804B (zh) 一种短纤维填充橡胶母料及制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18906104

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18906104

Country of ref document: EP

Kind code of ref document: A1