CN105461974B - A kind of preparation method of modified attapulgite used for rubber reinforcement - Google Patents
A kind of preparation method of modified attapulgite used for rubber reinforcement Download PDFInfo
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- CN105461974B CN105461974B CN201410389714.6A CN201410389714A CN105461974B CN 105461974 B CN105461974 B CN 105461974B CN 201410389714 A CN201410389714 A CN 201410389714A CN 105461974 B CN105461974 B CN 105461974B
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Abstract
A method of filler used for rubber reinforcement is prepared using natural minerals attapulgite, natural recessed soil after centrifugation purification will be settled passes through the immersion of soluble carbon source solution, cladding, high temperature carbonization is carried out by drying, being ground up, sieved to be placed in reducing atmosphere, obtains the nano-attapulgite stone of surface charcoal cladding.Its technical process successively includes the following steps, A: the purification of attapulgite；B: the pre-coated of attapulgite；C: the superficial charring of attapulgite.This method is advantageous in that will be after natural recessed soil progress simple process, it can be under the premise of guaranteeing that its fibrous structure is not destroyed, change the polarity on its surface, enhance its compatibility with non-polar rubber, loading of the attapulgite in rubber matrix is increased, attapulgite/rubber composite material of excellent in mechanical performance is prepared.
Description
Technical field
Fields of the present invention are inorganic mineral material application, specially utilize natural inorganic mineral attapulgite preparation one
The method of kind modified attapulgite hardcore used for rubber reinforcement.
Background technique
The referred to as recessed soil of attapulgite clay also known as palygorskite, are a kind of silicate mineral of aqueous rich magnesium aluminium, typicalization
Formula is Mg5Si8O20(OH)2(OH2)4·4H2O, unique structure, the diameter of single fiber crystalline substance is in 20~70nm or so, and length is about
Be 0.5~5 μm, be a kind of natural monodimension nanometer material, there are many excellent properties, be it is a kind of have the function of special construction and
Important nonmetallic clay mineral, referred to as " king of thousand soil, the soil of general-purpose ".Product is directed not only to chemical industry, machinery, the energy, vapour
The traditional industries such as vehicle, light industry, metallurgy, building materials, and enter with information, biology, aerospace, ocean development, new material and new
The energy is the high-tech industry of representative.As new application requirement continuously emerges, application range also will be widened further.China
Recessed soil rich in mineral resources, it is cheap, but starting is studied than later, research and development, production and level of processing are relatively backward, recessed soil
Product is mainly used in comparing the industry (primary product and some low value-added products) of low side.Therefore, develop high technology content,
Diversification, the recessed native produce for being able to satisfy different industries demand will be the directions of the recessed native industry development in China.
In recent years, nanocomposite is the hot spot of materialogy area research, the Good All-around Property as possessed by it,
Have become the most important forward position research direction of composite material.And the monodimension nanometer material that attapulgite is natural as one kind,
Theoretically have to the good reinforcing effect of polymer, causes the extensive concern of researcher.
It is more with the research of nanometer reinforced filling for concave convex rod ground mass rubber, but theoretical research rank is rested on mostly
Section, does not find rubber/attapulgite composite material industry report also.This is because the traditional processing method of rubber industry is
Mechanical mixing method, and although attapulgite belongs to layer silicate mineral, but its structure is special is that a kind of inside is covered with and extends
The consistent duct in direction, fiber rich in zeolite water, water of coordination and constitution water, surface has stronger polarity, with rubber institute
The nonpolarity having cannot be compatible well, therefore, attapulgite cannot as montmorillonite simply by with macromolecular chain
Shear action expand interlamellar spacing, separate the lamella of nanoscale, it is difficult to obtain the composite material of function admirable, it is necessary to it
Surface is handled, its surface polarity is reduced, and increases the compatibility with non-polar material to reach the nanometer in basis material
Scale dispersion.
Attapulgite system of the present inventor to China's attapulgite main place of production Jiangsu Province and Gansu Province
The research of system after carrying out purification processes to it, by the modification to its surface, is prepared for the bumps used for rubber reinforcement of function admirable
Stick hardcore.Technical characterstic of the invention be by the methods of purifying, be modified, improve polarity attapulgite and non-polar rubber it
Between compatibility, obtain the composite material of good physical properties.This method coats attapulgite using soluble carbon source,
Charing is modified, and technique is relatively simple, and obtained modified attapulgite may be directly applied to the traditional mechanical blending of rubber industry
Preparation process, effectively improves the performance of rubber product, and reduces the cost of product.The research of this aspect has not been reported.
Summary of the invention
The present invention provides a kind of methods for preparing filler used for rubber reinforcement using natural minerals attapulgite, i.e., will sedimentation
Natural recessed soil after centrifugation purification passes through the immersion of soluble carbon source solution, cladding, is placed on reduction by drying, being ground up, sieved
High temperature carbonization is carried out in atmosphere, obtains the nano-attapulgite stone of surface charcoal cladding.This method is advantageous in that will natural recessed soil
After carrying out simple process, it can change the polarity on its surface under the premise of guaranteeing that its fibrous structure is not destroyed, enhance it
With the compatibility of non-polar rubber, loading of the attapulgite in rubber matrix is increased.
The technical scheme is that the purification and modification of attapulgite, technical process include attapulgite dispersion,
It is centrifuged, impregnates, drying, being sieved and surface high-temp in a reducing atmosphere carbonizes.
The step of specific preparation, is as follows:
1) attapulgite: (a) being distributed in aqueous solution by the purification of attapulgite, is made into the solution that concentration is 3-50%；
Dispersing agent is added, wherein the additional amount of dispersing agent is the 1-6% of attapulgite quality；The heating water bath at 40-90 DEG C stirs 5-
60 minutes, revolving speed was 500-5000 revs/min；(b) scattered attapulgite slurries are centrifuged, centrifugal rotational speed 300-4500
Rev/min；Upper layer attapulgite slurries are taken after the completion of centrifugation, are filtered；(c) product is placed in a vacuum drying oven 40~85 DEG C of dryings
Ground 200 mesh, spare after 3~48h.
2) pre-coated of attapulgite: soluble carbon source is soluble in water, the attapulgite after being gradually added into purification,
It stirs evenly, product is placed in a vacuum drying oven ground 200 mesh after 40~85 DEG C of dry 3~48h, spare.
3) charing of attapulgite: the pre-coated attapulgite after drying, sieving is placed in crucible, in reducing atmosphere
(5%H2+ 95%N2) under be cooled to room temperature after 300~800 DEG C of 1~12h of calcining, it is recessed up to modification used for rubber reinforcement to cross 200 meshes
Convex stick stone.
It, cannot after causing attapulgite and rubber compound since palygorskite nano crystal grain is easy aggregation in general
Dispersion well, cannot give full play to the nano material effect of attapulgite crystal grain.The dispersion of nanoscale be prepare mineral with
The key of polymer based nanocomposites.The invention firstly uses aqueous solutions to be swollen attapulgite crystal grain, dispersing agent with
It is dissociated under the action of high speed machine stirring, is then removed large particulate matter by high speed centrifugation, only collect suspendability
Excellent, the lesser high-purity attapulgite particle of particle size, with out to out plays its structural advantage.
Due to attapulgite be hydrophilic inorganic substance, poor compatibility different from the interfacial property of natural rubber matrix,
Be difficult to it is evenly dispersed in rubber, directly filling be easy to cause certain mechanical performances of rubber product to decline.It is answered to improve it
With performance, it is necessary to be modified processing to attapulgite.The present invention using soluble carbon source solution to high-purity attapulgite into
Row is impregnated, is coated, and carries out high temperature carbonization to it under reducing atmosphere, its surface is made to be covered with nonpolar layer of charcoal, is realized concave-convex
Stick stone and non-polar rubber are in the compound of nanoscale, to improve the comprehensive performance of rubber product.
Detailed description of the invention
The infrared spectrogram of Fig. 1 Concave-convex clay rod charing front and back
The SEM photograph of Fig. 2 Concave-convex clay rod charing front and back
Specific implementation method:
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is further explained.
Embodiment
1. raw material and experimental facilities
(1) experimental raw:
Xuyi County of attapulgite Jiangsu Province
The commercially available analysis of glucose is pure
Natural rubber is commercially available
(2) experimental facilities
The Hefei high-temperature tubular atmosphere furnace WLS-1600 Ke Jing Instrument Ltd.；
Vacuum oven DZF-6020 Shanghai Yiheng Scientific Instruments Co., Ltd；
Electric-heated thermostatic water bath: DK-98-1 type, Tianjin Stettlen Instrument Ltd.；
Open mill: SK-160B type, Shanghai light industry and machinery limited liability company；
Vulcanizing press: QLB-350 × 350 × 2 types, the first rubber machinery plant of Shanghai.
2. the purification of attapulgite
100g attapulgite is taken, the aqueous solution of 10% mass concentration is configured to, 3g sodium hexametaphosphate dispersant is added, in 60
It heats, stirs 30 minutes in DEG C water-bath, revolving speed is 500 revs/min；
Scattered attapulgite slurries are centrifuged, centrifugal rotational speed is 1500 revs/min；Take upper layer concave-convex after the completion of centrifugation
Stick stone slurries cross filtered product and are placed in a vacuum drying oven 75 DEG C of dryings for 24 hours, and ground 200 mesh is spare.
3. the pre-coated of attapulgite
Attapulgite glucose is soluble in water, after being gradually added into purification, stirs evenly, product is placed in vacuum oven
In 75 DEG C of dryings for 24 hours after ground 200 mesh, it is spare.
4. the charing of attapulgite
Pre-coated attapulgite after drying, sieving is placed in crucible, in reducing atmosphere (5%H2+ 95%N2) under 650
DEG C calcining 4h after be cooled to room temperature, cross 200 meshes up to modified attapulgite used for rubber reinforcement.
5. the preparation of modified attapulgite/native rubber composite material
It is kneaded: superficial charring attapulgite obtained is mixed on the double roll mill with natural rubber and various auxiliary agents
Refining, is made the uniform rubber compound of quality, the quality formula of rubber compound are as follows: 2~12 parts of superficial charring attapulgite；Natural rubber
100 parts；50 parts of carbon black；5 parts of zinc oxide；1 part of stearic acid；1 part of altax；0.5 part of accelerant CZ；2 parts of sulphur.
The two-roll mill is SK-160B type open mill.
Vulcanization: rubber compound is vulcanized on vulcanizing press, and attapulgite/native rubber composite material, sulphur is made
Change time 35min, 143 DEG C of curing temperature, 16 megapascal of sulfide stress.
The vulcanizing press is QLB-350 × 350 × 2 type vulcanizing presses.
Table 1: the ratio of each main component in embodiment and comparative example
| Title | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Natural rubber | 100 | 100 | 100 | 100 |
| Modified attapulgite | 0 | 4 | 8 | 12 |
6. performance test
(a) examination of infrared spectrum: using the Nexus670 type Fourier infrared spectrograph of Nicolet company of the U.S. to bumps
The structure and composition of stick coalization cladding front and back carries out qualitative analysis, 11000~50cm of wave-number range-1, resolution ratio 0.06cm-1,
Wave number precision≤± 0.01cm-1；
(b) SEM is tested: the table of sample is observed in the JSM-5600 type scanning electron microscope of Japanese JEOL company production
Face pattern；
(c) GB/T 528-1998 " measurement of vulcanized rubber tensile stress-strain performance ", GB/ Mechanics Performance Testing: are pressed
The DXLL-50000 that T529-1991 " measurement of vulcanized rubber tearing strength " is produced in Shanghai City moral outstanding person's experimental instruments and equipment limited
Its mechanical property is tested on type electronic tension tester, wherein tensile speed is 500mm/min；
Product mechanical property is shown in Table 2.
Table 2: attapulgite/native rubber composite material mechanical property
2 are shown in Table according to attapulgite/native rubber composite material mechanical property prepared by above-mentioned formula and technique, by table
2 it is found that the mechanical property of composite material of addition 4,8,12 parts of modified attapulgites preparation is superior to pure natural rubber, illustrates to make
Standby attapulgite/native rubber composite material excellent in mechanical performance.
Fig. 1 is the Fourier transform infrared spectroscopy figure of attapulgite charing front and back.It will be seen from figure 1 that being located at 1024cm-1
The bands of a spectrum of left and right form a pincerlike absorption peak, this is because being concave convex rod caused by the stretching vibration of Si-O-Si and Si-O key
The major diagnostic peak in the area Shi Gai, and absorption peak herein illustrates that attapulgite is protected basic after treatment without significant change
Its structure feature is held.1461cm-1The absorption peak at place belongs to carbonate CO in mineral3 2-Absorption of vibrations, can from figure
Out, after Overheating Treatment, absorption peak herein almost disappears, illustrate into Overheating Treatment, in the attapulgite of effective place to go
The impurity such as carbonate.1649cm-1The absorption peak at place belongs to the bending vibration of water of coordination and adsorbed water molecule in attapulgite, this
The absorption peak at place slightly reduces, and illustrates through Overheating Treatment, and the loss of water of coordination is little in attapulgite.And 3410cm-1Left and right
Caused by absorption peak is the physical absorption waters such as mineral adsorbed water and surface adsorption water, the obvious drop of this position absorption peak
It is low, it may be said that it is bright through Overheating Treatment, it can physical absorption water contained in the attapulgite of a large amount of places to go.Attapulgite is before and after the processing
The variation of infared spectrum can illustrate that, through Overheating Treatment, there is no the feature structures for destroying attapulgite, and reduce wherein
The impurity such as contained physical absorption water and carbonate.
Fig. 2 is the SEM photograph of Concave-convex clay rod charing front and back.It is viscous to can be seen that the attapulgite before charing from Fig. 2 a
Soil is the raphioid fiber structure of its feature, and for length at 1 μm or so, diameter is well dispersed in 50nm or so.Concave convex rod after charing
Stone clay have occurred must agglomeration, as shown in Figure 2 b, but remain to find out the structure of its threadiness, length slightly reduces,
And diameter slightly increases.Illustrate during the milled processed after being dried to Concave-convex clay rod cladding, a part of needle-shaped fibre
Dimension is broken, and declines its length dimension；And to being coated, after high temperature carbonization, because its surface covers one layer of charcoal, so that
Its diameter increases, and the collective effect of the two declines the draw ratio of Concave-convex clay rod, and still, it still maintains original
Club shaped structure can be used as a kind of to fibrous inorganic filler used for rubber reinforcement.
Claims (3)
1. a kind of preparation method of modified attapulgite used for rubber reinforcement, preparation process are successively as follows:
1) attapulgite: (a) being distributed in aqueous solution by the purification of attapulgite, is made into the solution that concentration is 3-50%；It is added
Dispersing agent, wherein the additional amount of dispersing agent is the 1-6% of attapulgite quality；The heating water bath at 40-90 DEG C, 5-60 points of stirring
Clock, revolving speed are 500-5000 revs/min；(b) by scattered attapulgite slurries be centrifuged, centrifugal rotational speed be 300-4500 turn/
Minute；Upper layer attapulgite slurries are taken after the completion of centrifugation, are filtered；(c) product be placed in a vacuum drying oven 40~85 DEG C of dryings 3~
Ground 200 mesh, spare after 48h；
2) pre-coated of attapulgite: soluble carbon source is soluble in water, the attapulgite after being gradually added into purification, stirring
Uniformly, product is placed in a vacuum drying oven ground 200 mesh after 40~85 DEG C of dry 3~48h, spare；
3) superficial charring of attapulgite: the pre-coated attapulgite after drying, sieving is placed in crucible, under reducing atmosphere
It is cooled to room temperature after 300~800 DEG C of 1~12h of calcining, crosses 200 meshes up to modified attapulgite used for rubber reinforcement.
2. preparation method described in accordance with the claim 1, wherein the attapulgite dispersing agent is that Sodium Polyacrylate and six are inclined
Sodium phosphate.
3. preparation method described in accordance with the claim 1, wherein the soluble carbon source is starch or glucose.
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| CN106832612A (en) * | 2017-02-15 | 2017-06-13 | 江苏中业登泰新材料科技有限公司 | A kind of attapulgite modified ternary ethlene propyene rubbercompound material of organic inorganic hybridization |
| CN111019404A (en) * | 2019-11-29 | 2020-04-17 | 淮阴工学院 | Modified attapulgite for rubber reinforcement and preparation method thereof |
| CN110976503A (en) * | 2019-12-16 | 2020-04-10 | 湖南大学 | Modified attapulgite and preparation method and application thereof |
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| CN101492165A (en) * | 2009-03-09 | 2009-07-29 | 合肥工业大学 | Organic modification method for attapulgite stone and uses of organic modified attapulgite stone |
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| CN103055806A (en) * | 2011-10-18 | 2013-04-24 | 中国科学技术大学 | Carbon-coated attapulgite clay composite material and its preparation method |
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| CN101492165A (en) * | 2009-03-09 | 2009-07-29 | 合肥工业大学 | Organic modification method for attapulgite stone and uses of organic modified attapulgite stone |
| CN101508801A (en) * | 2009-03-19 | 2009-08-19 | 兰州大学 | Method for preparing oil-filled styrene butadiene rubber SBR1712/attapulgite stone nano-composite material |
| CN102250395A (en) * | 2010-05-19 | 2011-11-23 | 兰州大学 | Preparation method of oil-filled chemigum/attapulgite nanocomposite |
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