CN105754159A - High-strength antistatic emulsion composite and preparation and application thereof - Google Patents
High-strength antistatic emulsion composite and preparation and application thereof Download PDFInfo
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
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- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 5
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- 238000009864 tensile test Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Abstract
The invention relates to a high-strength antistatic emulsion composite and preparation and application thereof and belongs to the field of preparation of polymer nano composites.The high-strength antistatic emulsion composite is made by: physically coating the surface of carbon nanotubes with a water-soluble polymer by using a simple mechanical grinding method, adding the carbon nanotubes into an aqueous solution for ultrasonic treatment, mixing carbon nanotube dispersion and pre-vulcanized emulsion, and mixing well by mechanical stirring to obtain an emulsion; the stability of the emulsion is high such that the properties of CNTs can be given to full play, the viscosity of an emulsion system is not increased, and leveling performance is good; impregnation film laying process may be employed, the composite is also suitable for impregnation production on a linkage line, large-scale production of emulsion products is facilitated, and emulsion products are high in strength, piercing-resistant and antistatic.
Description
Technical field
The present invention relates to a kind of high intensity, the latex composite of antistatic, preparation and application, belong to the preparation field of polymer nanocomposites.
Background technology
CNT (CNTs) is because of structure and the characteristic such as high-flexibility, low mass density and big L/D ratio (usual 300-1000) of its uniqueness, also as it has outstanding electrical property, heat conductivity and high mechanical properties.Single conductivity restrainting CNT can reach 104The value of S/cm, (copper is 59 × 10 with the conductivity of metal4S/cm, ferrum is 9.9 × 104S/cm) close, and the density of CNT is non-normally low, it is possible to significantly alleviate weight.It is known that, material with carbon element is generally of high thermal conductivity, and CNT (experimental measurements of single nanotube thermal conductivity is 3000W/ (m K), the predictive value calculated in theory is up to 6600W/ (m K), then make this uncommon advantageous characteristic more prominent, therefore this kind of material is classified as the material that thermal conductivity is the highest since the dawn of human civilization.Due to the covalency sp formed between its single carbon atom2Key, CNT is rated as that the intensity found so far is the highest, rigidity best material, its hot strength is that (Kevlar is 3.5MPa to 10～150MPa by contrast, rustless steel is 1MPa), elastic modelling quantity is about 1TPa (Kevlar is about 0.15TPa by contrast, and rustless steel is about 0.2TPa).
There is between CNT (CNTs) very strong Van der Waals interact, so that hundreds of carbon pipe tied up in knots, form bigger aggregate, be difficult to separately, greatly weaken excellent mechanics and electrology characteristic that single carbon pipe shows.By CNT is carried out effective finishing, then can overcome above-mentioned problem, thus improving the dispersive property of CNT, improve the compatibility between it and matrix material, and strengthening the interaction between them.Additionally, the performance that CNT is new is can also impart to by it is carried out finishing, the molecule realizing CNT assembles, it is thus achieved that the nano material of various excellent performances, has broad application prospects in molectronics, nanoelectronics and nano biological molecules etc..
The surface-functionalized of CNT mainly has covalent bond method and non-covalent bond method two kinds.Covalent bond method modified carbon nano-tube mainly by chemical modification, in carbon nano tube surface with the form of covalent bond in conjunction with a number of chemical functional group to reach modified purpose.And non-covalent bond rule is, by modes such as surfactant modified, polymer wrapped, winding and absorption, CNT is carried out finishing.For modifying relative to covalent bond method, the main advantage of the method is exactly be prevented from the sp of carbon pipe2Atomic structure of carbon and conjugated system are destroyed, and maintain the electronic structure of CNT, thus without influence on the electricity of its excellence, optics, magnetics, calorifics and mechanical performance.
At present, in rubber industry, the shortcomings such as latex product is very big in its production scale of China, but there is also with low content of technology, and quality is unstable.Carrying out modified latex goods inorganic filler can be brought easily to deposit the industrialized production being not easy to infusion process by adding the method for inorganic filler in latex, production efficiency is low, and owing to the accumulation of inorganic filler easily makes goods defect occur, the problem reducing Mechanical Properties of Products.Little about the Chinese patent of inorganic filler modified latex at present.Chinese patent 201010200667.8,2007100492970,2007100492932 preparation method that mainly research inorganic powder mill base modified latex prepares color latex goods.
CNT (CNTs) is purposes functional material very widely, because of structure and characteristic such as high intensity, high-flexibility, low mass density and the big L/D ratio of its uniqueness, also as it has outstanding electrical property, heat conductivity and high mechanical properties.We adopt water soluble polymer reason cladding CNTs, make it dispersed in latex, do not affect the steady statue of emulsion, do not increase the viscosity of latex, linkage production line continuous prodution can be adopted, CNTs is uniformly dispersed in latex product simultaneously, and gained latex product intensity height, being folded without breaking, simultaneously antistatic, for the generation of the frictional static that the latex products such as altex glove are possible to prevent in work.
Chinese patent 201210450491.0 " a kind of High-conductivity carbon nanotube/rubber composite and preparation method thereof " adopts a kind of oriented growth of carbon nanometer tube bundle, add it to aqueous surfactant solution and successively carry out supersound process with different power, make CNT be dispersed in water.Carbon nano tube dispersion liquid is mixed with prevulcanized latex, utilizes " dipping plastic film mulch " technique to be poured onto in lucite grinding tool by CNT/latex mixed liquor after mechanical agitation mix homogeneously, drying at room temperature sulfidization molding.Adopting CNT in this method gained CNT/rubber composite to have higher draw ratio and good dispersibility, and the compatibility of rubber matrix is good, the electrical conductivity of its vulcanizate is significantly increased.
The method add in emulsion CNT containing aqueous surfactant solution, make the solid content of emulsion reduce, therefore the method is mainly for natural concentrating glue that solid content is 60% breast, and the preparation technology of goods adopts dipping plastic film mulch technique.And latex product adopts linkage production line dipping to produce in a large number, production scale is big, and this process conditions are to emulsion intercalation method requirement height, and viscosity requirement is low.
Summary of the invention
In order to overcome problem of the prior art and shortcoming, it is an object of the invention to provide a kind of preparation preparing novel C NTs/ latex composite article.The principle that the method utilizes is that CNT (CNTs) surface is carried out physical modification, namely simple mechanical milling method is adopted CNTs surface physics cladding to be processed water soluble polymer, add it to supersound process in aqueous solution, this carbon nano tube dispersion liquid is mixed with prevulcanized latex, mechanical agitation mix homogeneously, emulsion intercalation method is high, such that it is able to fully play the performance of CNTs, and the viscosity of latex system will not increase, good leveling property, dipping plastic film mulch technique can be adopted, it also is adapted for linkage production line dipping to produce, be conducive to the large-scale production of latex product, make the latex product intensity prepared high, being folded without breaking, static electricity resistance.
It is an object of the invention to be achieved through the following technical solutions:
A kind of high intensity, antistatic latex composite, adopt polymer emulsion and CNT be blended makes.
Preferably: adopt polishing water soluble polymer that carbon nano tube surface is carried out cladding process, then blended with polymer emulsion.After adopting technique scheme, CNTs can be distributed in latex sufficiently uniformly, and the viscosity of latex system will not increase, good leveling property, dipping plastic film mulch technique can be adopted, it also is adapted for linkage production line dipping to produce, is conducive to the large-scale production of latex product, prepared latex product intensity height, being folded without breaking, static electricity resistance.
Chinese patent 201210450491.0 method adds aqueous surfactant solution, makes the solid content of emulsion reduce.For the natural concentrating glue breast that solid content is 60%, dipping plastic film mulch technique can only be adopted, emulsion intercalation method is less demanding.The CNT of water soluble polymer reason cladding prepared by this patent method dissolubility in water is high, the solid content of available latex can at 60-40%, emulsion intercalation method is good, and the viscosity of latex system will not increase, good leveling property, dipping plastic film mulch technique can be adopted, also be adapted for linkage production line dipping and produce, be conducive to the large-scale production of latex product.Gained latex product is except having certain electric conductivity, and intensity increases further, and cutting resistance is obviously improved.
Preferably: polymer emulsion is at least one in Heveatex, styrene-butadiene latex, acrylonitrile-butadiene-phenylethylene copolymer emulsion, styrene-butadiene-styrene latex, NBR latex, polyvinyl acetate emulsion, polyaminoester emulsion, Voncoat R 3310 or copolymer emulsion, methacrylic acid homo thing or copolymer emulsion.
Preferably: CNT is at least one of single armed CNT or multi-walled carbon nano-tubes.
Preferably: length of carbon nanotube is 5-10 μm.It is demonstrated experimentally that length is too short, for instance less than 5 μm, reinforced effects is bad；Length is excessive, for instance more than 10 μm, easily snap off in process of lapping.The preparation method that the present invention also provides for above-mentioned latex composite, comprises the following steps:
1) preparation of water soluble polymer parcel CNTs
Water soluble polymer is ground with CNTs, adds water, ultrasonic disperse, obtain finely dispersed mixed solution；
2) preparation of CNTs/ latex composite
Adding the above-mentioned CNTs of 0.5%～5% mass fraction at dry rubber content in the presulfurization centrifugal concentrate of 35%-45%, stir 10～30min, mix homogeneously makes blendlatex.
In preferably: step 1), the mass ratio of water soluble polymer and CNTs is 1:4-4:1.
In preferably: step 1), the preparation condition of water soluble polymer parcel CNTs is: with CNTs, water soluble polymer is ground 15min～5h, add CNT: water quality mark is 1:100-1:1000, when power 50～500W, frequency are 10～10000HZ, temperature 10～100 DEG C, ultrasonic disperse 15min～2h.
Preferably: testing according to GB GB7544-2009 annex I, the film thickness of composite is between 0.170-0.180mm, and strength ratio does not add the material lift 30-40% of CNT.
Preferably: the volume resistance of composite is 1.0 × 1012Ω·cm--1×1011Ω·cm。
Preferably: water soluble polymer is at least one of polyvinylpyrrolidone, Polyethylene Glycol, kayexalate, starch derivatives, carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, polyacrylic acid, polyvinyl alcohol, polymaleic anhydride, polyquaternium, starch, arabic gum, algin sodium, bone meal, gelatin, casein.
The present invention also provides for a kind of latex product, according to blendlatex prepared by method described above, utilizes conventional linkage production line vulcanization process to prepare.
The present invention also provides for the application in high intensity altex glove, latex mould, conductive material, electromagnetic shielding material or barrier material of the above-mentioned latex product.
Accompanying drawing explanation
Fig. 1 is from left to right respectively as follows: in Heveatex, the latex of embodiment 1, comparative example 1 MWCNTs and is directly blended in Heveatex the photo after standing 48h；
Fig. 2 is the scanning electron microscope (SEM) photograph of unmodified CNTs/ latex composite article Tensile fracture；
Fig. 3 is the scanning electron microscope (SEM) photograph of modified CNTs/ latex composite article Tensile fracture.
Detailed description of the invention
Below by specific embodiment, the present invention will be further described, and embodiment is just to illustrating the present invention, being not limiting as the present invention.The protected content of the present invention is not limited to following example, and following example water soluble polymer is polyvinylpyrrolidone (PVP), and latex is Heveatex.
Comparative example 1 and embodiment 1
The change of CNTs dispersibility after process
Embodiment 1: by the PVP/CNTs mechanical lapping 15min that weight ratio is 3:1, is that CNT 0.5mg/ml adds appropriate weight parts water, ultrasonic disperse 15min according to concentration, obtains finely dispersed mixed solution.Latex adds the above-mentioned CNTs of 0.5% mass fraction, join dry rubber content in the presulfurization centrifugal concentrate of 45%, stirring 30min, it is configured to the presulfurization centrifugal concentrate that dry rubber content is 45%, draw a small amount of blended liquid, dropping, on PE film, utilizes thickness and the size of the surface tension transition drop of blended liquid self.
The preparation method of comparative example 1: add the above-mentioned CNTs of 0.5% mass fraction at dry rubber content in the presulfurization centrifugal concentrate of 45%, stirring 30min, drawing a small amount of blended liquid, dropping, on PE film, utilizes thickness and the size of the surface tension transition drop of blended liquid self.
Fig. 1 is it can be seen that the MWCNTs/PVP/NR rubber latex sample that thus method prepares has reached intended dispersion effect.
In documents 1, being directly blended in Heveatex by CNT, the viscosity of latex is big, and carbon pipe agglomeration wherein is serious.
The emulsion viscosity of the embodiment 1 that falling ball method measures is 12Pa.s, consistent with the viscosity 11-13Pa.s of the emulsion of the identical solid content not adding CNT.
As can be seen here, present invention, avoiding CNT and add the agglomeration caused and viscosity of latex increase phenomenon, CNT dispersibility and flow leveling are good.
Embodiment 2 and comparative example 2
The change of CNTs dispersibility after process
Embodiment 2: by the PVP/CNTs mechanical lapping 15min that weight ratio is 3:1, add appropriate weight parts water, ultrasonic disperse 15min, obtain finely dispersed mixed solution.Latex adds the above-mentioned CNTs of 0.5% mass fraction, join dry rubber content in the presulfurization centrifugal concentrate of 45%, stirring 30min, be configured to dry rubber content 35% presulfurization centrifugal concentrate prepare latex product according to the linkage production line vulcanization process that latex is conventional.
The preparation method of comparative example 2: add the above-mentioned CNTs of 0.5% mass fraction at dry rubber content in the presulfurization centrifugal concentrate of 35%, stirs 30min, and the linkage production line vulcanization process conventional according to latex prepares latex product.
Fig. 2 and Fig. 3 is the sem test result of CNTs/ latex composite article Tensile fracture.Can be seen that from the scanning electron microscope (SEM) photograph amplified, CNT deployment conditions in rubber matrix is different.In Fig. 2, unmodified CNT occurs that in rubber matrix agglomeration is obvious.In Fig. 3, the CNT dispersibility of PVP cladding substantially improves, and " wire drawing " phenomenon that can also be clearly visible, illustrate that CNT becomes strong with the adhesion of rubber interface.
Embodiment 3-4 and comparative example 3-4
The CNTs impact on latex product mechanical property
The preparation method of embodiment 3-4: by the PVP/CNTs mechanical lapping 15min that weight ratio is 3:1, add appropriate weight parts water, ultrasonic disperse 15min, obtain finely dispersed mixed solution.In the presulfurization centrifugal concentrate of 45%, add the above-mentioned CNTs of 0.4% and 0.5% mass fraction at dry rubber content, stir 30min, be configured to the presulfurization centrifugal concentrate that dry rubber content is 40% and prepare latex product according to the linkage production line vulcanization process that latex is conventional.Sample is tubbiness annulus, wall width 20mm, thick 0.170-0.180mm, girth 103mm.
The preparation method of comparative example 3: dry rubber content 40% presulfurization centrifugal concentrate prepare latex product according to the linkage production line vulcanization process that latex is conventional.Sample is tubbiness annulus, wall width 20mm, thick 0.170-0.180mm, girth 103mm.
The preparation method of comparative example 4: add the above-mentioned CNT of 0.5% mass fraction at dry rubber content in the presulfurization centrifugal concentrate of 40%, stirs 30 minutes, and the linkage production line vulcanization process conventional according to latex prepares latex product.Sample is tubbiness annulus, wall width 20mm, thick 0.170-0.180mm, girth 103mm.
With QC-II-DS type electronic tensile test machine, experimental condition: temperature 23 ± 2 DEG C, humidity 55 ± 15%, annular tensile test specimen, draw speed 500 ± 50mm/min.
Table 1. sample pull-off force and elongation rate of tensile failure
As shown in Table 1 addition process after pull-off force and the elongation rate of tensile failure of latex product of CNTs be improved, it is possible to reason be the good dispersion in latex of the CNTs after processing, CNTs has potentiation, therefore improves toughness and the intensity of sample.
Embodiment 5 and comparative example 5
The CNTs impact on latex product electric conductivity
The preparation method of embodiment 5: by the PVP/CNTs mechanical lapping 15min of the 4:1 that weight ratio is, add appropriate weight parts water, ultrasonic disperse 15min, obtain finely dispersed mixed solution.The presulfurization centrifugal concentrate latex of dry rubber content 45% adds the above-mentioned CNTs aqueous solution of 0.5% mass fraction, 30min is stood after shaking up, it is configured to the presulfurization centrifugal concentrate of dry rubber content 40%, draw a small amount of above-mentioned emulsion to drip on PE film, utilize thickness and the size of the surface tension transition drop of blended liquid self.Prepared drop is positioned over fume hood place natural air drying 48h, obtains the sample of embodiment 4.
The preparation method of comparative example 5: the presulfurization centrifugal concentrate drawing a small amount of 40% dry rubber content drips on PE film, utilizes thickness and the size of the surface tension transition drop of emulsion self.Prepared drop is positioned over fume hood place natural air drying 48h, obtains the sample of embodiment 5.
Table 2.CNTs before modified after the electrical property of latex film
Test sample size: 15 × 15 × (1.0 ± 0.1) mm
Through formulaCalculate resistance sizes, it is possible to the resistance calculating latex film modified for CNTs reduces, illustrate that adding CNTs can improve the electric conductivity of Heveatex.
Claims (9)
1. the latex composite of a high intensity, antistatic, it is characterised in that: adopt polymer emulsion and CNT is blended makes.
2. the latex composite of a kind of high intensity as claimed in claim 1, antistatic, it is characterised in that: adopt polishing water soluble polymer that carbon nano tube surface is carried out cladding process, then blended with polymer emulsion.
3. the latex composite of a kind of high intensity as claimed in claim 1, antistatic, it is characterised in that: polymer emulsion is at least one in Heveatex, styrene-butadiene latex, acrylonitrile-butadiene-phenylethylene copolymer emulsion, styrene-butadiene-styrene latex, NBR latex, polyvinyl acetate emulsion, polyaminoester emulsion, Voncoat R 3310 or copolymer emulsion, methacrylic acid homo thing or copolymer emulsion.
4. preparation as arbitrary in claim 1-3 as described in the method for latex composite, it is characterised in that: comprise the following steps:
1) preparation of water soluble polymer parcel CNTs
Water soluble polymer is ground with CNTs, adds water, ultrasonic disperse, obtain finely dispersed mixed solution；
2) preparation of CNTs/ latex composite
Adding the above-mentioned CNTs of 0.5%～5% mass fraction at dry rubber content in the presulfurization centrifugal concentrate of 35%-45%, stir 10～30min, mix homogeneously makes blendlatex.
5. method as claimed in claim 4, it is characterised in that: step 1) in, the mass ratio of water soluble polymer and CNTs is 1:4-4:1.
6. method as claimed in claim 4, it is characterized in that: step 1) in, the preparation condition of water soluble polymer parcel CNTs is: with CNTs, water soluble polymer is ground 15min～5h, add CNT: water quality mark is 1:100-1:1000, when power 50～500W, frequency are 10～10000HZ, temperature 10～100 DEG C, ultrasonic disperse 15min～2h.
7. method as claimed in claim 4, it is characterised in that: water soluble polymer is at least one of polyvinylpyrrolidone, Polyethylene Glycol, kayexalate, starch derivatives, carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, polyacrylic acid, polyvinyl alcohol, polymaleic anhydride, polyquaternium, starch, arabic gum, algin sodium, bone meal, gelatin, casein.
8. a latex product, it is characterised in that: the blendlatex prepared according to method as described in as arbitrary in claim 4-7, utilize conventional linkage production line vulcanization process to prepare.
9. the application in high intensity altex glove, latex mould, conductive material, electromagnetic shielding material or barrier material of the latex product described in claim 8.
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| CN111941710A (en) * | 2020-08-21 | 2020-11-17 | 安丹达工业技术(上海)有限公司 | Antistatic antichemical latex gloves and preparation method thereof |
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| CN106432850A (en) * | 2016-08-31 | 2017-02-22 | 邝月辉 | Rubber material for making gloves |
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| CN114921202B (en) * | 2022-04-28 | 2023-09-22 | 深圳市通泰盈科技股份有限公司 | High-temperature-resistant acrylic pressure-sensitive adhesive and preparation method thereof, pressure-sensitive adhesive tape and preparation method thereof |
| CN115975273A (en) * | 2022-12-26 | 2023-04-18 | 江苏恒辉安防股份有限公司 | Biodegradable latex composite material and preparation method thereof |
| CN115975273B (en) * | 2022-12-26 | 2023-10-20 | 江苏恒辉安防股份有限公司 | Biodegradable latex composite material and preparation method thereof |
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