CN100355826C - Preparation process for improving bonding capacity of carbon nanotube with rubber molecule - Google Patents
Preparation process for improving bonding capacity of carbon nanotube with rubber molecule Download PDFInfo
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- CN100355826C CN100355826C CNB2005101115126A CN200510111512A CN100355826C CN 100355826 C CN100355826 C CN 100355826C CN B2005101115126 A CNB2005101115126 A CN B2005101115126A CN 200510111512 A CN200510111512 A CN 200510111512A CN 100355826 C CN100355826 C CN 100355826C
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Abstract
The present invention relates to a preparation method for improving the bonding capacity of carbon nanometer tube and a rubber molecule, which belongs to the field of nanometer technology. Polysulfide is covalently combined on the surface of an acidrefined carbon nanometer tube, and the carbon nanometer tube modified by the polysulfide is blended with rubber to prepare carbon nanometer tube/rubber nanometer composite material. The carbon nanometer tube modified by the polysulfide is obtained by any one of the following methods which comprise method 1: the carbon nanometer tube is processed by acid, then the carbon nanometer tube is reacted with an acylating agent, and a product is reacted with the polysulfide to obtain the carbon nanometer tube modified by the polysulfide; method 2: the acidrefined carbon nanometer tube is directly reacted with the polysulfide to obtain the carbon nanometer tube modified by the polysulfide; method 3: a functional carbon nanometer tube is reacted with sodium polysulfide to obtain the carbon nanometer tube modified by the polysulfide. A polymer molecule is covalently grafted on the tube wall of the carbon nanometer tube in the carbon nanometer tube/rubber nanometer composite material obtained by the present invention, the carbon nanometer tube and a polymer have the intense interaction, and the performance of the nanometer composite material can be improved.
Description
Technical field
What the present invention relates to is a kind of method of field of nanometer technology, particularly a kind of preparation method who improves carbon nanotube and rubber molecule binding ability.
Background technology
Carbon nanotube is because its excellent mechanics and electric property since finding, have just caused the great interest of people.Carbon nanotube is dispersed in the polymer materials, improves the mechanics of polymer materials and electric property and be the focus of nano composite material research field in recent years.Preparation carbon nanotube composite materials key is to improve carbon nanotube dispersing property in polymkeric substance, strengthen the interaction between carbon nanotube and the polymer materials, prior art for preparing carbon nanotube/rubber nano composite material mainly is directly to use carbon nanotube and blend rubber.
Find through literature search prior art, people such as M.A.L ó pez-Manchado are at " Journal ofApplied Polymer Science " (using polymer magazine, 2004,92, a kind of way for preparing carbon nanotube composite materials with carbon nanotube and the direct blend of natural rubber is disclosed 3394-3400), because carbon nano tube surface is smooth, a little less than the reactive force in the nano composite material that this method prepares between carbon nanotube and the rubber molecule, carbon nanotube is dispersed in difficulty in the rubber, and carbon nanotube improves limited to rubber performance.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method who improves carbon nanotube and rubber molecule binding ability is provided.Make it by carbon nano tube surface is carried out chemically modified, at carbon nano tube surface covalence graft polysulfide, this polysulfide and blend rubber can make high performance nano composite material.
The present invention is achieved by the following technical solutions: at acid-treated carbon nano tube surface covalent attachment polysulfide, carbon nanotube and blend rubber that this polysulfide is modified prepare carbon nanotube/rubber nano composite material, and the carbon nanotube that described polysulfide is modified obtains by following any one method:
Method one: with acid carbon nanotube is handled, then with acylation reaction, product and polysulfide reaction obtain the carbon nanotube that polysulfide is modified;
Method two: the carbon nanotube that directly obtains the polysulfide modification with the acidifying carbon nanotube with the polysulfide reaction;
Method three: with the acidifying carbon nanotube earlier with have X-R-Y or NH
2-R-Si-(OB)
3The compound reaction of structure obtains the carbon nanotube that polysulfide is modified with the polysulfide reaction again.Wherein X is single hydroxyl, carboxyl, amido, and Y is a halogen atom, and R is an alkane, and Si is a Siliciumatom; O is a Sauerstoffatom; B is methyl or ethyl.
Described carbon nanotube is single wall or multi-walled carbon nano-tubes, and rubber is natural or synthetic rubber.
Described polysulfide has following structure:
X-R-(S)n-R-X；Na
2(S)
n；(BO)
3-Si-R-(S)n-R-Si-(OB)
3
Wherein R is phenyl ring, naphthalene or alkane; X is functional groups such as single hydroxyl, carboxyl, amido; S is a sulphur atom; Si is a Siliciumatom; O is a Sauerstoffatom; B is methyl or ethyl; N is between 2-6.
Described synthetic rubber is meant one or several of cis-butadiene cement, isoamyl glue, butadiene-styrene rubber, neoprene latex, second third glue, butadiene-acrylonitrile rubber, butyl rubber.
Described method one is handled carbon nanotube with acid, introduces carboxyl in carbon nano tube surface, functional groups such as hydroxyl, and the acid of usefulness is nitric acid, sulfuric acid or their mixture.1 weight part carbon nanometer tube material and 10～1000 weight part acid, 20～100 ℃ of reaction 10min～100h.Acidifying carbon nanotube and acylting agent reaction, with the polysulfide reaction, acylating reagent is sulfur oxychloride or oxalyl chloride again.1 weight part acidification carbon nanotube and 0.1～100 weight part acylating reagent, 20～100 ℃ of reaction 10min～100h.
Described method two, at this moment direct the and polysulfide reaction of acidifying carbon nanotube adds dicyclohexylcarbodiimide as dewatering agent.
The reaction of carbon nanotube and polysulfide, when carbon nanotube and sodium polysulphide or (BO)
3-Si-R-(S) n-R-Si-(OB)
3When the compound of structure reacts, carbon nanotube elder generation functionalization, carbon nanotube and 0.1～100 weight part X-R-Y structural compounds or NH that 1 weight part acid, acylting agent are handled
2-R-Si-(OB)
3The structural compounds reaction, 20～150 ℃ of reaction 10min～100h.
Carbon nanotube and blend rubber that polysulfide is modified can add packing materials such as carbon black, white carbon black in the system simultaneously, also can add compositions such as zinc oxide, stearic acid, Sulfur, vulcanization accelerator, antiager.
The present invention obtains in carbon nanotube/rubber nano composite material, polymer molecule is the tube wall of covalence graft at carbon nanotube, there is intensive to interact between carbon nanotube and the polymkeric substance, can improve the dispersing property of carbon nanotube in rubber, can be less than the tensile strength and the modulus that make rubber under 10% (w/w) situation at CNT (carbon nano-tube) content and improve more than the twice.
Embodiment
Provide following examples in conjunction with content of the present invention:
Embodiment 1
Get multi-walled carbon nano-tubes 0.12g, add 60% nitric acid 1.2g, vitriol oil 120g, 100 ℃ were stirred 10 minutes, filtered, and got product 0.1g, added sulfur oxychloride 0.01g, and 50 ℃ were reacted 10 minutes, and removed unnecessary sulfur oxychloride.Get product 0.1g, add 3-propylene chlorohydrin 0.01g, 150 ℃ of stirring reactions 10 minutes are crossed and are filtered out unnecessary 3-propylene chlorohydrin, get product 0.1g, add Na
2S
20.01g 20 milliliters of ethanol reacted 10 minutes, filtered separated product.Rubber unvulcanizate prescription: 0.1 part of the carbon nanotube of modification, 75 parts of natural gums, 15 parts of butadiene-styrene rubbers, 5 parts of cis-butadiene cements, 5 parts of butyl rubbers, 10 parts of medium super abrasion furnace blacks, 10 parts of white carbon blacks, 5 parts in zinc oxide, 2 parts of stearic acid, 1.6 parts of Sulfurs, 1.3 parts of promotor.145 ℃ were vulcanized 35 minutes.The performance of cross-linked rubber is: stretching 32.1MPa, 300% stress at definite elongation 18.4MPa.
Embodiment 2
Get multi-walled carbon nano-tubes 0.11g, the nitric acid 110g of adding 60%, vitriol oil 10g, 20 ℃ were stirred 100 minutes, filtered, and got product 0.1g, add sulfur oxychloride 10g, 20 ℃ of reaction 100h remove unnecessary sulfur oxychloride, get product 0.1g, 3-(triethoxyl silane) propyl group amine 10g, 20 ℃ of reaction 100h remove unnecessary 3-(triethoxyl silane) propyl group amine, get product 0.1g, add two [3-(Ethoxysilane) propyl group] four sulphur 5g, 20 ℃ of stirring reaction 100h cross and filter out unnecessary [3-(Ethoxysilane) propyl group] four sulphur filtration, separated product.Rubber unvulcanizate prescription: 0.1 part of the carbon nanotube of modification, 65 parts of natural gums, 5 parts of butadiene-styrene rubbers, 10 parts of cis-butadiene cements, 5 parts of butyl rubbers, 5 parts of neoprene latexs, 10 parts of carbon blacks, 10 parts of white carbon blacks, 3 parts in zinc oxide, 2 parts of stearic acid, 1.5 parts of antioxidant 4010NAs, 1.7 parts of Sulfurs.140 ℃ were vulcanized 45 minutes.The performance of cross-linked rubber is: stretching 35.1MPa, 300% stress at definite elongation 17.7MPa.
Embodiment 3
Get multi-walled carbon nano-tubes 0.13g, add 30% nitric acid 65g, stir 100h, filter, get product 0.1g, add sulfur oxychloride 5g, 100 ℃ were reacted 50 minutes, remove unnecessary sulfur oxychloride, get product 0.1g, add 3-chlorine propylamine 5g, 50 ℃ of stirring reaction 30h, cross and filter out unnecessary 3-chlorine propylamine, get product 0.1g, add Na
2S
610g, 40 milliliters of ethanol, reaction 100h filters separated product.Rubber unvulcanizate prescription: 0.1 part of the carbon nanotube of modification, 85 parts of natural gums, 10 parts of butadiene-styrene rubbers, 10 parts of cis-butadiene cements, 20 parts of carbon blacks, 1 part in zinc oxide, 2 parts of stearic acid, 1.4 parts of antioxidant 4010NAs, 1.6 parts of Sulfurs.140 ℃ were vulcanized 45 minutes.The performance of cross-linked rubber is: stretching 33.3MPa, 300% stress at definite elongation 19.4MPa.
Embodiment 4
Get multi-walled carbon nano-tubes 0.11g, add 60% nitric acid 1.2g, vitriol oil 120g, 100 ℃ were stirred 10 minutes, filtered, and got product 0.1g, added sulfur oxychloride 0.01g, and 50 ℃ were reacted 10 minutes, and removed unnecessary sulfur oxychloride.Get product 0.1g, add 3-propylene chlorohydrin 0.01g, 100 ℃ of stirring reactions 10 minutes are crossed and are filtered out unnecessary 3-propylene chlorohydrin, get product 0.1g, add Na
2S
40.01g 20 milliliters of ethanol reacted 10 minutes, filtered separated product.Rubber unvulcanizate prescription: 0.1 part of the carbon nanotube of modification, 100 parts of natural gums, 10 parts of medium super abrasion furnace blacks, 10 parts of white carbon blacks, 5 parts in zinc oxide, 2 parts of stearic acid, 1.5 parts of antioxidant 4010NAs, 1.4 parts of Sulfurs, 1.5 parts of promotor.140 ℃ were vulcanized 30 minutes.The performance of cross-linked rubber is: stretching 35.1MPa, 300% stress at definite elongation 14.0MPa.
Embodiment 5
Get Single Walled Carbon Nanotube 0.12g, add 10% nitric acid 140g, vitriol oil 10g, handled 50 hours, and filtered, get product 0.1g, add sulfur oxychloride 10g, 20 ℃ were reacted 100 minutes, and removed unnecessary sulfur oxychloride, get product 0.1g, 2,2 '-two sulphur (naphthalidine) 5g, 20 ℃ of stirring reaction 100h, cross and filter out 2,2 '-two unnecessary sulphur (naphthalidine).Rubber unvulcanizate prescription: 0.1 part of the carbon nanotube of modification, 80 parts of natural gums, 10 parts in chlorobutyl glue, 5 parts in second third glue, 5 parts of butadiene-acrylonitrile rubbers, 10 parts of carbon blacks, 10 parts of white carbon blacks, 3 parts in zinc oxide, 2 parts of stearic acid, 4,020 1.6 parts in anti-aging agent, 1.5 parts of Sulfurs, 1.3 parts of promotor.135 ℃ were vulcanized 40 minutes.The performance of cross-linked rubber is: stretching 34.1MPa, 300% stress at definite elongation 17.5MPa.
Embodiment 6.
Get Single Walled Carbon Nanotube 0.14g, the nitric acid 130g of adding 10% handled 40 hours, filtered, get product 0.1g, add sulfur oxychloride 10g, 20 ℃ were reacted 100 minutes, remove unnecessary sulfur oxychloride, get product 0.1g, add 6,6 '-two sulphur (beta naphthal) 0.01g, 2,2 '-two sulphur (naphthalidine) 5g, 20 ℃ of stirring reaction 100h cross and filter out 2,2 '-two unnecessary sulphur (naphthalidine).Rubber unvulcanizate prescription: the carbon nanotube 0.1g of modification, butadiene-styrene rubber 100g, 25 parts of carbon blacks, 25 parts of white carbon blacks, 2 parts in zinc oxide, 1 part of stearic acid, 2 parts of Sulfurs, 1.3 parts of promotor.140 ℃ were vulcanized 40 minutes.The performance of cross-linked rubber is: stretching 33.6MPa, 300% stress at definite elongation 17.8MPa.
Embodiment 7.
Get Single Walled Carbon Nanotube 0.13g, the nitric acid 140g of adding 30% handled 50 hours, filtered, get product 0.1g, add sulfur oxychloride 10g, 50 ℃ were reacted 100 minutes, remove unnecessary sulfur oxychloride, get product 0.1g, add 6,6 '-two sulphur (beta naphthal) 5g, 2,2 '-two sulphur (naphthalidine) 0.01g, 150 ℃ of stirring reaction 10min, cross and filter out 6,6 '-two unnecessary sulphur (beta naphthal) and 2,2 '-two sulphur (naphthalidine).Rubber unvulcanizate prescription: 0.1 part of the carbon nanotube of modification, 100 parts in isoamyl glue, 5 parts in zinc oxide, 3 parts of stearic acid, 1.2 parts of Sulfurs.140 ℃ were vulcanized 40 minutes.The performance of cross-linked rubber is: stretching 36.1MPa, 300% stress at definite elongation 18.7MPa.
Embodiment 8
Get Single Walled Carbon Nanotube 0.12g, the nitric acid 100g of adding 10% handled 100 hours, filtered, get product 0.12g, add oxalyl chloride 12g, be heated to 50 ℃, reaction 100h removes unnecessary oxalyl chloride, gets product 0.12g, add 3,3 '-two sulphur propionic acid 6g, 2,2 '-two sulphur phenylformic acid 12g, 150 ℃ of stirring reactions 10 minutes are crossed and are filtered out unnecessary 3,3 '-two sulphur propionic acid and 2,2 '-two sulphur phenylformic acid.Rubber unvulcanizate prescription: 0.1 part of the carbon nanotube of modification, 85 parts of natural gums, 5 parts of butadiene-styrene rubbers, 5 parts in chlorobutyl glue, 5 parts of butadiene-acrylonitrile rubbers, 30 parts of carbon blacks, 3 parts in zinc oxide, 2 parts of stearic acid, 4,020 1.5 parts in anti-aging agent, 1.3 parts of Sulfurs, 1.4 parts of promotor, 130 ℃ were vulcanized 40 minutes down.The performance of cross-linked rubber is: stretching 29.1MPa, 300% stress at definite elongation 16.6MPa.
Embodiment 9
Get multi-walled carbon nano-tubes 0.14g, the nitric acid 100g of adding 20% handled 50 hours, filtered, get product 0.1g, add oxalyl chloride 12g, be heated to 50 ℃, reaction 100h, remove unnecessary oxalyl chloride, get product 0.12g, add 3,3 '-two sulphur propionic acid 6g, 50 ℃ of stirring reactions 100 minutes are crossed and are filtered out 3,3 '-two unnecessary sulphur propionic acid.The rubber unvulcanizate prescription: 0.1 part of the carbon nanotube of modification, 85 parts of natural gums, 15 parts of butadiene-styrene rubbers, 10 parts of carbon blacks, 10 parts of white carbon blacks, 3 parts in zinc oxide, 2 parts of stearic acid, 1.3 parts of Sulfurs, 1.4 parts of promotor, 130 ℃ were vulcanized 40 minutes down.The performance of cross-linked rubber is: stretching 35.1MPa, 300% stress at definite elongation 18.5MPa.
Embodiment 10
Get Single Walled Carbon Nanotube 0.11g, add 40% nitric acid 100g, sulfuric acid 10g, handled 100 hours, and filtered, get product 0.12g, add oxalyl chloride 12g, stirring reaction 100h removes unnecessary oxalyl chloride, get product 0.12g, add 4,4 '-two thioaniline 10g, 2,2 '-two sulphur ethanol 0.01g, 20 ℃ of stirring reaction 100h, cross and filter out 4,4 '-two unnecessary thioanilines and 2,2 '-two sulphur ethanol.The rubber unvulcanizate prescription: 0.1 part of the carbon nanotube of modification, 100 parts of natural gums, 20 parts of carbon blacks, 3 parts in zinc oxide, 2 parts of stearic acid, 40201.5 parts in anti-aging agent, 1.6 parts of Sulfurs, 135 ℃ were vulcanized 40 minutes down.The performance of cross-linked rubber is: stretching 32.1MPa, 300% stress at definite elongation 14.6MPa.
Embodiment 11
Get Single Walled Carbon Nanotube 0.22g, add 20% nitric acid 50g, 50% sulfuric acid 50g handled 100 hours, filter, get product 0.1g, add 4,4 '-two thioaniline 10g, dicyclohexylcarbodiimide 10g, stirring reaction 50h crosses and filters out 4,4 '-two unnecessary thioanilines.Rubber unvulcanizate prescription: 0.1 part of the carbon nanotube of modification, 85 parts of natural gums, 10 parts of butadiene-styrene rubbers, 5 parts of butadiene-acrylonitrile rubbers, 10 parts of carbon blacks, 10 parts of white carbon blacks, 2 parts in zinc oxide, 2 parts of stearic acid, 1.7 parts of Sulfurs, 1.5 parts of promotor.140 ℃ were vulcanized 40 minutes down.The performance of cross-linked rubber is: stretching 30.1MPa, 300% stress at definite elongation 13.6MPa.
Embodiment 12
Get multi-walled carbon nano-tubes 0.23g, add 20% nitric acid 50g, 50% sulfuric acid 50g, handled 100 hours, and filtered, get product 0.1g, add 4,4 '-two thioaniline 10g, 2,2 '-two sulphur ethanol 0.01g, dicyclohexylcarbodiimide 10g, stirring reaction 50h crosses and to filter out unnecessary 4,4 '-two thioanilines and 2,2 '-two sulphur ethanol.Rubber unvulcanizate prescription: 0.1 part of the carbon nanotube of modification, 100 parts of cis-butadiene cements, 20 parts of carbon blacks, 10 parts of white carbon blacks, 3 parts in zinc oxide, 2 parts of stearic acid, 4,020 1.3 parts in anti-aging agent, 2 parts of Sulfurs, 1.5 parts of promotor.140 ℃ were vulcanized 35 minutes down.The performance of cross-linked rubber is: stretching 32.1MPa, 300% stress at definite elongation 15.6MPa.
Claims (9)
1, a kind of preparation method who improves carbon nanotube and rubber molecule binding ability, it is characterized in that, at acid-treated carbon nano tube surface covalent attachment polysulfide, carbon nanotube and blend rubber that this polysulfide is modified prepare carbon nanotube/rubber nano composite material, and the carbon nanotube that described polysulfide is modified obtains by following any one method:
Method one: with acid carbon nanotube is handled, then with acylation reaction, product and polysulfide reaction obtain the carbon nanotube that polysulfide is modified;
Method two: the carbon nanotube that directly obtains the polysulfide modification with the acidifying carbon nanotube with the polysulfide reaction;
Method three: with the acidifying carbon nanotube earlier with have X-R-Y or NH
2-R-Si-(OB)
3The compound reaction of structure obtains the carbon nanotube that polysulfide is modified with the polysulfide reaction again, and wherein X is single hydroxyl, carboxyl, amido, and Y is a halogen atom, and R is an alkane, and Si is a Siliciumatom; O is a Sauerstoffatom; B is methyl or ethyl.
2, the preparation method of raising carbon nanotube according to claim 1 and rubber molecule binding ability is characterized in that, described carbon nanotube is single wall or multi-walled carbon nano-tubes, and rubber is natural or synthetic rubber.
3, the preparation method of raising carbon nanotube according to claim 2 and rubber molecule binding ability, it is characterized in that described synthetic rubber is meant one or several of cis-butadiene cement, isoamyl glue, butadiene-styrene rubber, neoprene latex, second third glue, butadiene-acrylonitrile rubber, butyl rubber.
4, the preparation method of raising carbon nanotube according to claim 1 and rubber molecule binding ability is characterized in that, described polysulfide has following structure:
X-R-(S)n-R-X；Na
2(S)
n；(BO)
3-Si-R-(S)n-R-Si-(OB)
3
Wherein R is phenyl ring, naphthalene or alkane; X is single hydroxyl, amido; S is a sulphur atom; Si is a Siliciumatom; O is a Sauerstoffatom; B is methyl or ethyl; N is between 2-6.
5, the preparation method of raising carbon nanotube according to claim 1 and rubber molecule binding ability, it is characterized in that, described method one, with acid carbon nanotube is handled, with acid be nitric acid, sulfuric acid or their mixture, 1 weight part carbon nanometer tube material and 10～1000 weight part acid, 20～150 ℃ of reaction 10min～100h.
6, according to the preparation method of claim 1 or 5 described raising carbon nanotubes and rubber molecule binding ability; it is characterized in that; described method one; acidifying carbon nanotube and acylting agent reaction; react with polysulfide again; acylating reagent is sulfur oxychloride or oxalyl chloride, 1 weight part acidification carbon nanotube and 0.1～100 weight part acylating reagent, 20～100 ℃ of reaction 10min～100h.
7, the preparation method of raising carbon nanotube according to claim 1 and rubber molecule binding ability is characterized in that, described method two, and at this moment direct the and polysulfide reaction of acidifying carbon nanotube adds dicyclohexylcarbodiimide as dewatering agent.
8, the preparation method of raising carbon nanotube according to claim 1 and rubber molecule binding ability is characterized in that, the reaction of carbon nanotube and polysulfide, when carbon nanotube and sodium polysulphide or (BO)
3-Si-R-(S) n-R-Si-(OB)
3When the compound of structure reacts, carbon nanotube elder generation functionalization, carbon nanotube and 0.1～100 weight part X-R-Y structural compounds or NH that 1 weight part acid, acylting agent are handled
2-R-Si-(OB)
3The structural compounds reaction, 20～150 ℃ of reaction 10min～100h.
9, the preparation method of raising carbon nanotube according to claim 1 and rubber molecule binding ability is characterized in that, carbon nanotube and blend rubber that polysulfide is modified add carbon black, white carbon black or their mixture simultaneously in the system.
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| CN102321279B (en) * | 2011-09-29 | 2013-01-23 | 北京化工大学 | Dopamine modified carbon nanotube/rubber composite material and preparation method thereof |
| JP2015501361A (en) | 2011-10-24 | 2015-01-15 | アディティア ビルラ ヌーヴォ リミテッドＡｄｉｔｙａ Ｂｉｒｌａ Ｎｕｖｏ Ｌｉｍｉｔｅｄ | Improved process for producing carbon black |
| BR112014024263B1 (en) | 2012-03-30 | 2021-03-09 | Aditya Birla Science And Technology Company Ltd | process for obtaining carbon black powder |
| CN105924705A (en) * | 2016-05-13 | 2016-09-07 | 赛轮金宇集团股份有限公司 | Highly filled white carbon black tread rubber having good electric and thermal conductivity and used for pneumatic tire |
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