CN104877178B - A kind of method that utilization galapectite sustained release age resistor prepares ageing-resistant rubber - Google Patents
A kind of method that utilization galapectite sustained release age resistor prepares ageing-resistant rubber Download PDFInfo
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- CN104877178B CN104877178B CN201510128852.3A CN201510128852A CN104877178B CN 104877178 B CN104877178 B CN 104877178B CN 201510128852 A CN201510128852 A CN 201510128852A CN 104877178 B CN104877178 B CN 104877178B
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- galapectite
- age resistor
- halloysite nanotubes
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Abstract
The method that age resistor prepares ageing-resistant rubber is sustained the invention discloses a kind of utilization galapectite, i.e.,：Age resistor is loaded inside galapectite tube chamber by the use of the method that the natural nano tubular structure of galapectite is adsorbed as carrier using physical vacuum and prepares functional stuffing, and by the functional stuffing with it is rubber combined, the ageing-resistant rubber composite of processing machinery excellent performance, long-term effect and the controllability of composite functionalization are realized from the sustained release in halloysite nanotubes using age resistor, method provided by the present invention is easy to operate, time-consuming short, and the mechanical performance of prepared composite and ageing-resistant performance are excellent.
Description
Technical field
The invention belongs to prepare functional composite material field, and in particular to one kind is prepared resistance to using galapectite sustained release age resistor
The method of aging rubber, the method that the halloysite nanotubes for preparing load age resistor are adsorbed particularly by physical vacuum.
Background technology
Elastomeric material is caused during processing, storage and use due to the comprehensive function aging by internal and external factor
Progressively degenerating for its physicochemical properties and mechanical performance, finally loses use value.Be mainly shown as cracking, it is tacky, hardening,
Softening, efflorescence, discoloration, mildew etc..It is most importantly thermo-oxidative ageing in elastomeric material aging techniques, it is usual for thermo-oxidative ageing
React to slow down the aging of elastomeric material with oxygen/ozone using addition antioxidant in the composite.But
The age resistor of small molecule, which can move between elastomer macromolecules cross-linking network and be enriched in elastomeric article surface, produces " spray
The number of age resistor has strict restriction in frost " phenomenon, therefore elastomer formulations, and the highest addition number of age resistor not of the same race is not
Together.This patent will relate specifically to one kind can the functional preparations such as age resistor being supported in natural halloysite nanotubes tube chamber and
The effectively modified method to prepare the functional elastomer for possessing the performance such as ageing-resistant is carried out to it, mainly with antioxidant 4010NA
For example.
Galapectite (Al2O3·2SiO2·2H2O it is) a kind of natural nano tubular material, its structure can be considered by kaolin
The multi-walled pipes of the 15-20 layers of curling, internal diameter is 10-15nm, and external diameter is 50-70nm, and length is 1-1.5 μm.Galapectite is received
Mitron outer surface is SiO2, tube chamber inside is Al2O3, density is 2.53g/cm3, specific surface area is 60-70m2/g.It is de- different from covering
The laminar clay materials such as soil, kaolin, bentonite, galapectite once big advantage be without peel off can be well dispersed in water and
In polar polymer, while its dispersiveness in low polar polymer or even melt polypropylene is also fine.But in order that angstrom
Lip river stone remains to fine dispersion in rubber to be needed to carry out it surface modification, and such as silane surface is coupling agent modified.Due to its compared with
High draw ratio, addition number is well below particulate filler when halloysite nanotubes prepare composite as filler.In an angstrom Lip river
Loading functional preparation in stone nanotube tube chamber, such as preservative, fire retardant, antibiotic assign galapectite feature, can
For preparing functional composite material.The load volume of halloysite nanotubes is the release of load preparation in 10-15wt%, solution
Time be a few houres by several days, in polymeric matrix be some months to several years.
Nearly two over 100 years, and people are directed to research filler enhancing elastic composite, on the one hand can improve rubber
Modulus and intensity, on the other hand can reduce cost.Due to the high enhancing efficiency of natural clay nano-particle and low filling rate, make
Natural clay nano-particle causes very big concern as the research of filler, wherein bar-shaped and tubulose clay nanoparticle such as slope thread
Stone, attapulgite, galapectite can direct combinations without peeling off for strengthening rubber.Therefore, work(is loaded in halloysite nanotubes
It is extremely innovative to strengthen the composites such as rubber that energy preparation makes it as functional filler by the use of its slow releasing function.
The content of the invention
It is an object of the invention to solve it is existing prepare present in rubber composite technology it is not enough, and provide using angstrom
The method that Lip river stone sustained release age resistor prepares ageing-resistant rubber.Method provided by the present invention is easy to operate, time-consuming short, prepared
Ageing-resistant rubber mechanical performance and ageing-resistant performance are good.
Functional preparation, as matrix, galapectite nanometer is supported on using vacuum suction by the present invention using halloysite nanotubes
After in tube chamber, by the halloysite nanotubes of loading functional preparation and polymer matrix bluk recombination, processing machinery work(of good performance
Energy property polymer/halloysite composite material, is comprised the following steps that：
1) after by halloysite nanotubes matrix, ultrasonic wave is scattered in acetone soln, it is 2~50g/L's to be placed on concentration
In age resistor solution, 5~60min of vacuum is kept in vacuum chamber, then keeps 5~30min at ambient pressure, repeat the circulation three times with
After upper, sample is washed with deionized, after 50 DEG C of oven for drying, obtains loading the halloysite nanotubes of age resistor；
2) by step 1) prepare load age resistor halloysite nanotubes with 20~100phr ratio with it is rubber combined
Elastomeric compound is prepared, then sulfidization molding, the rubber composite of the halloysite nanotubes filling of load age resistor is made.
Further, step 1) in halloysite nanotubes matrix be natural halloysite nanotubes.
Step 2) in rubber matrix can be replaced other polymers, including plastics, resin, coating and adhesive etc..
Wherein, step 1) described in method be all suitable for for all functional preparations, including but not limited to medicine, albumen
Matter, metal and its oxide particle etc..The solvent of scattered galapectite is consistent with the solvent of function equipment formulation soln, does not limit
In acetone, water, ethanol, ethyl acetate or toluene are can be replaced, age resistor replaces medicine, protein, metal or metal oxide
Particle.
The principle of the present invention is：Make age resistor solution full of inside halloysite nanotubes using vacuum suction effect, lead to
The age resistor crossed in washing drying process, solution is supported on halloysite nanotubes intracavitary, obtains the halloysite nanotubes of functionalization.
The halloysite nanotubes for loading age resistor are combined with rubber matrix, age resistor is released slowly to rubber from halloysite nanotubes two ends
In matrix body, realize and improve the purpose that aging inhibitor dosage does not cause bloom again, while halloysite nanotubes rise to rubber matrix again
To enhanced effect.
With it is existing prepare ageing-resistant rubber technology compared with, the inventive method has the advantages that：
1) halloysite nanotubes of the invention that can prepare load various functions preparation are used as functional stuffing, and easy to operate,
Time-consuming short, cost is low.
2) halloysite nanotubes of the loading functional preparation prepared by the present invention are viscous without photo shape for enhancing by polymer
Soil is equally peeled off, and the addition number needed for more granular Nano filling is much smaller can keep the glue sense of product.
3) the controllable sustained-release effect of the halloysite nanotubes of the loading functional preparation prepared by the present invention can not cause
Increase the functional preparation consumption in rubber compounding on the premise of bloom and then improve the feature of rubber.
4) present invention is not limited the composition of functional preparation, and the load of functional preparation does not interfere with the physical machine of galapectite
Tool performance.
Brief description of the drawings
Fig. 1 prepares loading functional preparation halloysite nanotubes flow chart.
Thermogravimetric analysis (TGA) curve of the halloysite nanotubes of the load antioxidant 4010NA of Fig. 2 embodiments 1.
The age resistor release profiles of the galapectite of the load antioxidant 4010NA of Fig. 3 embodiments 1.
The microscopic appearance of 1 galapectite of Fig. 4 embodiments/butadiene-styrene rubber composite, wherein (a) galapectite/butadiene-styrene rubber composite wood
Cross sectional scanning electron microscope (SEM) photo of material, the ultra-thin section transmitted electron of (b) galapectite/butadiene-styrene rubber composite shows
Micro mirror (TEM) photo.
Mechanical performance in Fig. 5 embodiments 1 before and after galapectite/butadiene-styrene rubber composite (SBR#1) aging, comparative example 3~5
Mechanical performance before and after middle galapectite/butadiene-styrene rubber composite (SBR#2~4) aging.
The galapectite prepared by galapectite/butadiene-styrene rubber composite SBR#1 and comparative example 6 prepared by Fig. 6 embodiments 1/
Butadiene-styrene rubber composite SBR#5 is statically placed on blank sheet of paper 12 days and 30 days at ambient temperature respectively, removes the photograph of blank sheet of paper after sample
Piece (Fig. 6 (a)).The galapectite prepared by galapectite/butadiene-styrene rubber composite SBR#1 and comparative example 6 prepared by embodiment 1/
Butadiene-styrene rubber composite SBR#5 stand certain time at 90 DEG C after analyze (XPS) via surface-element and measure surface nitrogen
Content results (Fig. 6 (b)).
Embodiment
Embodiment is after by halloysite nanotubes matrix, the ultrasonic wave in acetone soln is scattered, be placed on concentration for 2~
In 50g/L age resistor solution, 5~60min of vacuum is kept in vacuum chamber, then keeps 5~30min at ambient pressure, this is repeated and follows
After ring three times, sample is washed with deionized, after 50 DEG C of oven for drying, obtains loading the halloysite nanotubes of age resistor；But
The present invention is not limited to age resistor.
Embodiment 1
1) flow as shown in Figure 1, with mass fraction be by the galapectite acetone dispersion liquor that isometric mass fraction is 5%
The rate of charge of 10% antioxidant 4010NA acetone soln mixing, galapectite and age resistor is 1:2, with 60 turns/min stirring speed
Rate stirs 5min, and mixed liquor is kept into vacuum 30min in vacuum chamber, then keeps 15min at ambient pressure, repeats the process three times,
The galapectite of load antioxidant 4010NA is centrifugally separating to obtain, is washed with deionized three times, in 50 DEG C of oven dryings.
2) the halloysite nanotubes age resistor release of load antioxidant 4010NA is studied using UV-vis absorption spectrum
Process, the 50mg galapectites for loading age resistor are placed in 1mL deionized waters or hexamethylene and stir certain time, every time by from
New solvent is supplemented after heart separation solution, supernatant liquor is analyzed using ultraviolet-visible absorption spectroscopy.
3) take 20g to load the halloysite nanotubes of antioxidant 4010NA, galapectite/butadiene-styrene rubber is prepared using formula as below multiple
Condensation material SBR#1.
Note：Conditions of vulcanization is 150 DEG C × 7min.
4) obtained galapectite/butadiene-styrene rubber composite is subjected to thermo-oxidative ageing, the aging condition used is 90 DEG C and 120
DEG C difference aging 1 day, 3 days and 7 days.
Galapectite, antioxidant 4010NA, the thermal gravimetric analysis curve of the galapectite of load antioxidant 4010NA in the present embodiment
See Fig. 2, the galapectite of load antioxidant 4010NA is shown in Fig. 3 with the release profiles in hexamethylene in deionized water.
In the present embodiment obtained galapectite/butadiene-styrene rubber composite cross-sectional scanning electron microscope (SEM) photo and
Ultra-thin section transmission electron microscope (TEM) photo is shown in Fig. 4 (a) and Fig. 4 (b), galapectite/butadiene-styrene rubber composite aging respectively
Front and rear mechanical performance is shown in SBR#1 in Fig. 5.
Galapectite, antioxidant 4010NA, the weight loss for the galapectite for loading antioxidant 4010NA are calculated and obtained angstrom from Fig. 2
The load capacity of Lip river madreporic canal intracavitary age resistor is 8.1wt.%.From Fig. 3, the galapectite of antioxidant 4010NA is loaded in deionized water
It can prove that antioxidant 4010NA is controllable out of galapectite tube chamber with the release profiles in hexamethylene to slowly release, such as figure institute
Show, the rate of release in hexamethylene is significantly larger than rate of release in deionized water, this is due to that antioxidant 4010NA exists
High-dissolvability in hexamethylene.But faster rate of release is still acceptable in hexamethylene, on the one hand because anti-ageing
Change system needs age resistor to possess certain initial concentration, on the other hand the halloysite nanotubes surface quilt in rubber composite
Rubber polymer polymeric PTC materials substantially reduce the rate of release of age resistor inside official jargon.Figure 4, it is seen that load is anti-old
Dispersiveness of the halloysite nanotubes of agent in rubber matrix is very good, basically reaches monodispersed level, effectively strengthens rubber
Matrix, and halloysite nanotubes pattern keeps good without Fragmentation Phenomena during rubber processing.
Mechanical performance is shown in SBR#1 in Fig. 5 before and after obtained galapectite/butadiene-styrene rubber composite aging in the present embodiment,
It can be seen that after 90 DEG C of agings 7 days, the tensile strength and elongation at break of galapectite/butadiene-styrene rubber are substantially unchanged, hardness
(Shao A) is slightly elevated, illustrates the ageing-resistant performance of the rubber and has long-term effect, and this is due to the slow of the galapectite of load age resistor
Release effect；And after 120 DEG C of agings 1 day, 3 days, tensile strength, elongation at break and the hardness (Shao A) of galapectite/butadiene-styrene rubber
Also without significant change, illustrate that the ageing-resistant performance of the rubber is very excellent.
Embodiment 2
Process be the same as Example 1,4 are changed to by the rate of charge of galapectite in step 1 and age resistor:1、2:1 and 1:1, it can obtain
To the halloysite nanotubes of load antioxidant 4010NA.
The thermal gravimetric analysis curve of the galapectite of load antioxidant 4010NA prepared by different rate of charges is shown in figure in the present embodiment
2, it is computed, rate of charge 4:1、2:1 and 1:The load factor of the galapectite of 1 load age resistor is respectively 0.8wt.%,
1.5wt.%, 3.8wt.%.
Comparative example 3
1) 20g galapectites are taken, galapectite/butadiene-styrene rubber composite SBR#2 is prepared using formula as below.
Note：Conditions of vulcanization is 150 DEG C × 17min.
2) obtained galapectite/butadiene-styrene rubber composite SBR#2 is subjected to thermo-oxidative ageing, the aging condition used is 90 DEG C
With 120 DEG C of difference agings 1 day, 3 days and 7 days.
Mechanical performance is shown in Fig. 5 before and after obtained galapectite/butadiene-styrene rubber composite SBR#2 agings in this comparative example
SBR#2。
Comparative example 4
1) galapectite/butadiene-styrene rubber composite SBR#3 is prepared using formula as below.
Note：Conditions of vulcanization is 150 DEG C × 15min.
2) obtained galapectite/butadiene-styrene rubber composite SBR#3 is subjected to thermo-oxidative ageing, the aging condition used is 90 DEG C
With 120 DEG C of difference agings 1 day, 3 days and 7 days.
Mechanical performance is shown in Fig. 5 before and after obtained galapectite/butadiene-styrene rubber composite SBR#3 agings in this comparative example
SBR#3。
Comparative example 5
1) the galapectite 20g of load antioxidant 4010NA is taken, galapectite/butadiene-styrene rubber composite is prepared using formula as below
SBR#4。
Note：Conditions of vulcanization is 150 DEG C × 6min.
2) obtained galapectite/butadiene-styrene rubber composite SBR#4 is subjected to thermo-oxidative ageing, the aging condition used is 90 DEG C
With 120 DEG C of difference agings 1 day, 3 days and 7 days.
Mechanical performance is shown in Fig. 5 before and after obtained galapectite/butadiene-styrene rubber composite SBR#4 agings in this comparative example
SBR#4。
Comparative example 1 and comparative example 3~5, galapectite/butadiene-styrene rubber composite (SBR#2 prepared by comparative example 3~5
~SBR#4) mechanical performance has obvious decline after thermo-oxidative ageing, and galapectite/butylbenzene prepared by embodiment 1
Glue composite SBR#1 mechanical performance is without significant change, especially by 120 DEG C of agings 7 days, comparative example 3 and the institute of comparative example 4
The SBR#2 and SBR#3 of preparation are hardened, ruptured, and the SBR#1 prepared by embodiment 1 remains in that good elasticity and mechanicalness
Can, illustrate humidification of the galapectite to butadiene-styrene rubber, ageing-resistant work can be assigned by loading the slow releasing function of the galapectite of age resistor
With long-term effect and can by with free age resistor and used in not causing on the premise of bloom significantly (several times or even ten numbers
The consumption of increase age resistor again).
Comparative example 6
1) galapectite/butadiene-styrene rubber composite SBR#5 is prepared using formula as below.
Note：Conditions of vulcanization is 150 DEG C × 11min.
2) obtained galapectite/butadiene-styrene rubber composite SBR#5 is stood into a timing respectively at room temperature (25 DEG C) and 90 DEG C
Between, contrast bloom phenomenon with SBR#1 made from embodiment 1.
Galapectite/butylbenzene prepared by galapectite/butadiene-styrene rubber composite SBR#1 and comparative example 6 prepared by embodiment 1
Glue composite SBR#5 is statically placed on blank sheet of paper 12 days and 30 days at ambient temperature respectively, and the photo for removing blank sheet of paper after sample is shown in
Fig. 6 (a).Galapectite/butylbenzene prepared by galapectite/butadiene-styrene rubber composite SBR#1 and comparative example 6 prepared by embodiment 1
Glue composite SBR#5 stand certain time at 90 DEG C after analyze (XPS) via surface-element and measure surface nitrogen element content
As a result Fig. 6 (b) is seen.
Galapectite/butylbenzene prepared by galapectite/butadiene-styrene rubber composite SBR#1 and comparative example 6 prepared by embodiment 1
Glue composite SBR#5 is statically placed on blank sheet of paper 12 days and 30 days at ambient temperature respectively, removes what is remained after sample on blank sheet of paper
For age resistor, the depth of color has reacted the spray volume of age resistor, and it is white that the middle displays of Fig. 6 (a) place SBR#1 sample positions after 12 days
This places the change of SBR#5 sample positions blank sheet of paper without color change for brown color to paper substrate, and SBR#1 sample positions are placed after 30 days
Blank sheet of paper still places the intensification of SBR#5 sample positions brown color without obvious color change, illustrates " nano container " due to galapectite
Bloom will not also be caused even if the age resistor of addition higher amount by acting on.Galapectite/butadiene-styrene rubber composite prepared by embodiment 1
SBR#1 and galapectite/butadiene-styrene rubber composite SBR#5 prepared by comparative example 6 stand certain time at 90 DEG C after via table
The surface nitrogen element content that surface element analysis (XPS) is measured has reacted the amount of sample surfaces age resistor, from Fig. 6 (b), sample
The content of surface nitrogen is that the amount of age resistor gradually increases and the content of the nitrogen of SBR#5 sample surfaces is significantly larger than
SBR#1 sample surfaces, quantitatively illustrate age resistor being supported in galapectite tube chamber and efficiently controlled bloom phenomenon.
Claims (3)
1. a kind of method that utilization galapectite sustained release age resistor prepares ageing-resistant rubber, it is characterised in that comprise the following steps：
1) after by halloysite nanotubes matrix, ultrasonic wave is scattered in acetone soln, it is the anti-old of 2~50g/L to be placed on concentration
In agent solution, 5~60min of vacuum is kept in vacuum chamber, then keeps 5~30min at ambient pressure, the circulation more than three times is repeated
Afterwards, sample is washed with deionized, after 50 DEG C of oven for drying, obtains loading the halloysite nanotubes of age resistor；
2) by step 1) prepare load age resistor halloysite nanotubes with 20~100phr ratio with it is rubber combined prepare
Elastomeric compound, then sulfidization molding, is made the rubber composite of the halloysite nanotubes filling of load age resistor.
2. the matrix of the halloysite nanotubes in accordance with the method for claim 1, it is characterised in that step 1) is natural angstrom
Lip river stone nanotube.
3. a kind of method that utilization galapectite is sustained age resistor, it is characterised in that comprise the following steps：
1) after by halloysite nanotubes matrix, ultrasonic wave is scattered in acetone soln, it is the anti-old of 2~50g/L to be placed on concentration
In agent solution, 5~60min of vacuum is kept in vacuum chamber, then keeps 5~30min at ambient pressure, the circulation more than three times is repeated
Afterwards, sample is washed with deionized, after 50 DEG C of oven for drying, obtains loading the halloysite nanotubes of age resistor；
2) by step 1) prepare load age resistor halloysite nanotubes with 20~100phr ratio and plastics, resin, painting
Material or adhesive are compound, and the composite of the halloysite nanotubes filling of load age resistor is made.
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| CN106010394B (en) * | 2016-06-02 | 2018-11-30 | 国际竹藤中心 | A kind of preparation method of slow-release Multi-function adhesive |
| CN106084353B (en) * | 2016-06-21 | 2018-02-02 | 北京化工大学 | A kind of method for preparing ageing-resistant functional rubber using CNT sustained release age resistor |
| CN110156919B (en) * | 2018-02-10 | 2020-07-28 | 北京化工大学 | Rubber antioxidant and preparation method thereof |
| CN109206814A (en) * | 2018-07-03 | 2019-01-15 | 广东省石油与精细化工研究院 | A kind of 150 DEG C of interior thermoplastic elastomer (TPE)s of grade oxytolerant oil resistant automobile engine of heatproof and preparation method thereof |
| CN110734581A (en) * | 2018-07-18 | 2020-01-31 | 北京化工大学 | halloysite nanotube grafted with antioxidant as well as preparation method and application thereof |
| CN109320774A (en) * | 2018-10-16 | 2019-02-12 | 青岛科技大学 | A kind of method that natural astaxanthin and its esters are carried on filler proof rubber composite material aging |
| CN109593304B (en) * | 2018-12-27 | 2021-03-26 | 安徽百通高科塑业有限公司 | Preparation method of PVC (polyvinyl chloride) pipe for coal mine |
| CN112175239B (en) * | 2019-07-03 | 2022-02-11 | 北京化工大学 | Long-acting and controllable composite anti-aging agent and preparation method and application thereof |
| CN111333914A (en) * | 2020-04-29 | 2020-06-26 | 江西宝弘纳米科技有限公司 | Slow-release anti-aging agent and preparation method and application thereof |
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| CN103396592B (en) * | 2013-07-11 | 2015-09-16 | 华南理工大学 | Loading type rubber antioxidant and preparation method thereof and application |
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