CN104877178A - Method for preparing aging-resistance rubber by utilization of halloysite slow-release anti-aging agent - Google Patents

Method for preparing aging-resistance rubber by utilization of halloysite slow-release anti-aging agent Download PDF

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CN104877178A
CN104877178A CN201510128852.3A CN201510128852A CN104877178A CN 104877178 A CN104877178 A CN 104877178A CN 201510128852 A CN201510128852 A CN 201510128852A CN 104877178 A CN104877178 A CN 104877178A
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halloysite
aging agent
aging
rubber
halloysite nanotubes
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CN104877178B (en
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王文才
张立群
付烨
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention discloses a method for preparing aging-resistance rubber by the utilization of a halloysite slow-release anti-aging agent. According to the method, a natural nanotube structure of halloysite is used as a carrier, and an anti-aging agent preparation functional filler is loaded inside the halloysite tube by a vacuum physical absorption method, and the functional filler and rubber are compounded to prepare an aging-resistance rubber composite material with excellent mechanical property. By slow release of the halloysite nanotube by the anti-aging agent, functional long-acting performance and controllability of the composite material are realized. The method provided by the invention is simple to operate and has low time consumption. The prepared composite material has excellent mechanical performance and ageing resistance.

Description

A kind of method utilizing halloysite slowly-releasing anti-aging agent to prepare ageing-resistant rubber
Technical field
The invention belongs to and prepare functional composite material field, be specifically related to a kind of method utilizing halloysite slowly-releasing anti-aging agent to prepare ageing-resistant rubber, particularly by the method for the halloysite nanotubes of physical vacuum absorption preparation load anti-aging agent.
Background technology
Elastomer material, in processing, in storage and use procedure, causes progressively degenerating of its physicochemical property and mechanical property, finally loses use value owing to being subject to the comprehensive action of internal and external factor aging.Main manifestations for chapping, be clamminess, harden, soften, efflorescence, variable color, mildew etc.Most importantly thermo-oxidative ageing in elastomer material aging techniques, is typically employed in matrix material for thermo-oxidative ageing and adds antioxidant and oxygen/ozone reacts thus slows down the aging of elastomer material.But micromolecular anti-aging agent can move and be enriched in elastomeric article surface generation " bloom " phenomenon between elastomerics macromolecules cross-linking network, therefore in elastomer formulations, the number of anti-aging agent has strict restriction, and the highest interpolation number of anti-aging agent not of the same race is different.This patent can, the functional preparation loads such as anti-aging agent are carried out effective modification to possess the functional elastomer of the performance such as ageing-resistant method in order to preparation in natural halloysite nanotubes tube chamber and to it, be mainly example with antioxidant 4010NA by being specifically related to a kind of.
Halloysite (Al 2o 32SiO 22H 2o) be a kind of natural nano tubular material, its structure can be considered the multi-walled pipes by the curling 15-20 layer of kaolin, and internal diameter is 10-15nm, and external diameter is 50-70nm, and length is 1-1.5 μm.Halloysite nanotubes outside surface is SiO 2, tube chamber inside is Al 2o 3, density is 2.53g/cm 3, specific surface area is 60-70m 2/ g.Be different from the laminar clay material such as polynite, kaolin, wilkinite, halloysite a large advantage for being scattered in well in water and polar polymer without the need to peeling off, its dispersiveness in low polar polymer and even melt polypropylene is also fine simultaneously.Such as, but in order to make halloysite still can good distribution need to carry out surface modification to it in rubber, silane surface is coupling agent modified.Due to the length-to-diameter ratio that it is higher, halloysite nanotubes is used as to add number well below particulate filler when matrix material prepared by filler.At halloysite nanotubes tube chamber internal burden functional preparation, as functional in imparting halloysites such as sanitas, fire retardant, microbiotic, can for the preparation of functional composite material.The load volume of halloysite nanotubes is 10-15wt%, in solution the time of releasing of load preparation be several hours to several days not etc., be some months in polymeric matrix to the several years not etc.
Nearly two over 100 years, and people are devoted to research filler and strengthen elastic composite, can improve modulus and the intensity of rubber on the one hand, can reduce costs on the other hand.Because the height of natural clay nanoparticle strengthens efficiency and low filling ratio, make natural clay nanoparticle cause very big concern as the research of filler, wherein bar-shaped and tubulose clay nanoparticle as polygorskite, attapulgite, halloysite is used for Reinforced Rubber can direct combination without the need to peeling off.Therefore, in halloysite nanotubes, loading functional preparation utilizes its slow releasing function to make it be extremely innovative as functional filler in order to matrix materials such as Reinforced Rubber.
Summary of the invention
The object of the invention is to solve and existingly prepare the deficiency existed in rubber composite technology, and the method utilizing halloysite slowly-releasing anti-aging agent to prepare ageing-resistant rubber is provided.Method provided by the present invention is easy and simple to handle, consuming time short, prepared ageing-resistant rubber mechanical property and ageing-resistant performance good.
The present invention adopts halloysite nanotubes as matrix, utilize vacuum suck by after functional preparation load is in halloysite nanotubes chamber, by the halloysite nanotubes of loading functional preparation and polymer-based carbon volume recombination, processing machinery functional polymer/halloysite composite material of good performance, concrete steps are as follows:
1) after by halloysite nanotubes matrix, in acetone soln, ultrasonic wave is disperseed, being placed on concentration is in the anti-aging agent solution of 2 ~ 50g/L, vacuum 5 ~ 60min is kept at vacuum chamber, keep 5 ~ 30min at ambient pressure again, after repeating this circulation more than three times, use deionized water wash sample, after 50 DEG C of oven for drying, obtain the halloysite nanotubes of load anti-aging agent;
2) by step 1) halloysite nanotubes of load anti-aging agent prepared is with the ratio of 20 ~ 100phr and rubber combinedly prepare rubber unvulcanizate, then sulfidization molding, the rubber composite that the halloysite nanotubes of obtained load anti-aging agent is filled.
Further, step 1) in the matrix of halloysite nanotubes be natural halloysite nanotubes.
Step 2) in rubber matrix can be replaced other polymkeric substance, comprise plastics, resin, coating and tackiness agent etc.
Wherein, step 1) described in method all applicable for all functional preparations, include but not limited to medicine, protein, metal and oxide particle thereof etc.The solvent of dispersion halloysite is consistent with the solvent of function equipment formulation soln, is not limited to acetone, can be replaced water, ethanol, ethyl acetate or toluene, and anti-aging agent replaces medicine, protein, metal or metal oxide particle.
Principle of the present invention is: utilize vacuum suck effect to make anti-aging agent solution be full of halloysite nanotubes inside, and by washing drying process, the anti-aging agent load in solution, in halloysite nanotubes chamber, obtains the halloysite nanotubes of functionalization.By the halloysite nanotubes of load anti-aging agent and rubber matrix compound, anti-aging agent is from halloysite nanotubes two ends slow releasing to rubber matrix, realize improving the object that aging inhibitor dosage does not cause again bloom, halloysite nanotubes plays again the effect of enhancing to rubber matrix simultaneously.
Prepare compared with ageing-resistant rubber technology with existing, the inventive method has following beneficial effect:
1) halloysite nanotubes that the present invention can prepare the various functional preparation of load is used as functional stuffing, and easy and simple to handle, and consuming time short, cost is low.
2) halloysite nanotubes of the loading functional preparation prepared by the present invention is used for enhancing by polymer without the need to peeling off as schistose clay, and the interpolation number needed for more granular Nano filling wants the much smaller glue sense that can keep product.
3) the controllable sustained-release effect of the halloysite nanotubes of the loading functional preparation prepared by the present invention can increase the functional preparation consumption in rubber compounding and then improve the functional of rubber under the prerequisite not causing bloom.
4) composition of the present invention to functional preparation does not limit, and the load of functional preparation can not affect the physical and mechanical properties of halloysite.
Accompanying drawing explanation
Fig. 1 prepares loading functional preparation halloysite nanotubes schema.
Thermogravimetric analysis (TGA) curve of the halloysite nanotubes of Fig. 2 embodiment 1 load antioxidant 4010NA.
The anti-aging agent release profiles of the halloysite of Fig. 3 embodiment 1 load antioxidant 4010NA.
The microscopic appearance of Fig. 4 embodiment 1 halloysite/butadiene-styrene rubber matrix material, wherein cross sectional scanning electron microscope (SEM) photo of (a) halloysite/butadiene-styrene rubber matrix material, ultrathin section(ing) transmission electron microscope (TEM) photo of (b) halloysite/butadiene-styrene rubber matrix material.
The mechanical property of halloysite in Fig. 5 embodiment 1/butadiene-styrene rubber matrix material (SBR#1) aging front and back, the mechanical property of halloysite/butadiene-styrene rubber matrix material (SBR#2 ~ 4) aging front and back in comparative example 3 ~ 5.
Halloysite prepared by Fig. 6 embodiment 1/butadiene-styrene rubber matrix material SBR#1 and the halloysite prepared by comparative example 6/butadiene-styrene rubber matrix material SBR#5 is statically placed in blank sheet of paper upper 12 day and 30 days respectively at ambient temperature, removes the photo (Fig. 6 (a)) of blank sheet of paper after sample.Halloysite prepared by embodiment 1/butadiene-styrene rubber matrix material SBR#1 and the halloysite prepared by comparative example 6/butadiene-styrene rubber matrix material SBR#5 records surface nitrogen constituent content result (Fig. 6 (b)) via surface-element analysis (XPS) after 90 DEG C of standing certain hours.
Embodiment
Embodiment by halloysite nanotubes matrix in acetone soln ultrasonic wave dispersion after, being placed on concentration is in the anti-aging agent solution of 2 ~ 50g/L, vacuum 5 ~ 60min is kept at vacuum chamber, keep 5 ~ 30min at ambient pressure again, after repeating this circulation three times, use deionized water wash sample, after 50 DEG C of oven for drying, obtain the halloysite nanotubes of load anti-aging agent; But the present invention is not limited to anti-aging agent.
Embodiment 1
1) by flow process shown in Fig. 1, by isopyknic massfraction be 5% halloysite acetone dispersion liquor and massfraction be 10% antioxidant 4010NA acetone soln mixes, the feed ratio of halloysite and anti-aging agent is 1:2, stir 5min with the stir speed (S.S.) of 60 turns/min, mixed solution is kept vacuum 30min at vacuum chamber, then keeps 15min at ambient pressure, repeat this process three times, centrifugation obtains the halloysite of load antioxidant 4010NA, with deionized water wash three times, at 50 DEG C of oven dryings.
2) UV-vis absorption spectrum is utilized to study the halloysite nanotubes anti-aging agent dispose procedure of load antioxidant 4010NA, the halloysite of 50mg load anti-aging agent is placed in 1mL deionized water or hexanaphthene stirs certain hour, each solvent supplementary new after centrifugation solution, utilizes ultraviolet-visible absorption spectroscopy to analyze supernatant liquid.
3) get the halloysite nanotubes of 20g load antioxidant 4010NA, adopt following formula to prepare halloysite/butadiene-styrene rubber matrix material SBR#1.
Note: cure conditions is 150 DEG C × 7min.
4) obtained halloysite/butadiene-styrene rubber matrix material is carried out thermo-oxidative ageing, the aging condition of employing is 90 DEG C and 120 DEG C of difference aging 1 day, 3 days and 7 days.
In the present embodiment, the thermal gravimetric analysis curve of the halloysite of halloysite, antioxidant 4010NA, load antioxidant 4010NA is shown in Fig. 2, and the halloysite of load antioxidant 4010NA is shown in Fig. 3 with the release profiles in hexanaphthene in deionized water.
Fig. 4 (a) and Fig. 4 (b) is shown in respectively by halloysite/butadiene-styrene rubber matrix material cross-sectional scanning electron microscope (SEM) photo obtained in the present embodiment and ultrathin section(ing) transmission electron microscope (TEM) photo, and the mechanical property of halloysite/aging front and back of butadiene-styrene rubber matrix material is shown in SBR#1 in Fig. 5.
From Fig. 2, the weight loss of the halloysite of halloysite, antioxidant 4010NA, load antioxidant 4010NA calculates the charge capacity of anti-aging agent in halloysite tube chamber is 8.1wt.%.From Fig. 3, the halloysite of load antioxidant 4010NA can prove that antioxidant 4010NA is controlled in halloysite tube chamber in deionized water and slowly release with the release profiles in hexanaphthene, as shown in the figure, release rate in hexanaphthene is far away higher than release rate in deionized water, and this is due to the high-dissolvability of antioxidant 4010NA in hexanaphthene.But release rate is still acceptable faster in hexanaphthene, on the one hand because anti-aging system needs anti-aging agent to possess certain starting point concentration, in rubber composite, halloysite nanotubes surface is reduced the release rate of the inner anti-aging agent of official jargon greatly by rubber polymer polymeric PTC materials on the other hand.As can be seen from Figure 4, the dispersiveness of halloysite nanotubes in rubber matrix of load anti-aging agent is very good, substantially reach monodispersed level, effective Reinforced Rubber matrix, and halloysite nanotubes pattern keeps good in Fragmentation Phenomena in Rubber processing process.
Halloysite/butadiene-styrene rubber matrix material aging front and back mechanical property obtained in the present embodiment is shown in SBR#1 in Fig. 5, can see through 90 DEG C after aging 7 days, the tensile strength of halloysite/butadiene-styrene rubber and elongation at break are substantially unchanged, hardness (Shao A) raises slightly, illustrate that the ageing-resistant performance of this rubber has long-lasting, this is the slow releasing function of the halloysite due to load anti-aging agent; And through 120 DEG C after aging 1 day, 3 days, the tensile strength of halloysite/butadiene-styrene rubber, elongation at break and hardness (Shao A), also without considerable change, illustrate that the ageing-resistant performance of this rubber is very excellent.
Embodiment 2
Process, with embodiment 1, changes the feed ratio of halloysite in step 1 and anti-aging agent into 4:1,2:1 and 1:1, can obtain the halloysite nanotubes of load antioxidant 4010NA.
In the present embodiment, the thermal gravimetric analysis curve of the halloysite of load antioxidant 4010NA prepared by different feed ratio is shown in Fig. 2, as calculated, the load factor of the halloysite of the load anti-aging agent of feed ratio 4:1,2:1 and 1:1 is respectively 0.8wt.%, 1.5wt.%, 3.8wt.%.
Comparative example 3
1) get 20g halloysite, adopt following formula to prepare halloysite/butadiene-styrene rubber matrix material SBR#2.
Note: cure conditions is 150 DEG C × 17min.
2) obtained halloysite/butadiene-styrene rubber matrix material SBR#2 is carried out thermo-oxidative ageing, the aging condition of employing is 90 DEG C and 120 DEG C of difference aging 1 day, 3 days and 7 days.
Halloysite/butadiene-styrene rubber matrix material SBR#2 aging front and back mechanical property obtained in this comparative example is shown in SBR#2 in Fig. 5.
Comparative example 4
1) following formula is adopted to prepare halloysite/butadiene-styrene rubber matrix material SBR#3.
Note: cure conditions is 150 DEG C × 15min.
2) obtained halloysite/butadiene-styrene rubber matrix material SBR#3 is carried out thermo-oxidative ageing, the aging condition of employing is 90 DEG C and 120 DEG C of difference aging 1 day, 3 days and 7 days.
Halloysite/butadiene-styrene rubber matrix material SBR#3 aging front and back mechanical property obtained in this comparative example is shown in SBR#3 in Fig. 5.
Comparative example 5
1) get the halloysite 20g of load antioxidant 4010NA, adopt following formula to prepare halloysite/butadiene-styrene rubber matrix material SBR#4.
Note: cure conditions is 150 DEG C × 6min.
2) obtained halloysite/butadiene-styrene rubber matrix material SBR#4 is carried out thermo-oxidative ageing, the aging condition of employing is 90 DEG C and 120 DEG C of difference aging 1 day, 3 days and 7 days.
Halloysite/butadiene-styrene rubber matrix material SBR#4 aging front and back mechanical property obtained in this comparative example is shown in SBR#4 in Fig. 5.
Comparative example 1 and comparative example 3 ~ 5, halloysite prepared by comparative example 3 ~ 5/butadiene-styrene rubber matrix material (SBR#2 ~ SBR#4) mechanical property after thermo-oxidative ageing has obvious decline, and the mechanical property of halloysite/butadiene-styrene rubber matrix material SBR#1 prepared by embodiment 1 is without considerable change, especially aging 7 days through 120 DEG C, comparative example 3 and SBR#2 and the SBR#3 prepared by comparative example 4 hardening, break, and the SBR#1 prepared by embodiment 1 still keeps good elasticity and mechanical property, the enhancement of halloysite to butadiene-styrene rubber is described, the slow releasing function of the halloysite of load anti-aging agent can give ageing-resistant effect long-lasting and can by with free anti-aging agent and be used in and do not cause under the prerequisite of bloom significantly (several times and even ten several times) to increase the consumption of anti-aging agent.
Comparative example 6
1) following formula is adopted to prepare halloysite/butadiene-styrene rubber matrix material SBR#5.
Note: cure conditions is 150 DEG C × 11min.
2) by obtained halloysite/butadiene-styrene rubber matrix material SBR#5 respectively at room temperature (25 DEG C) and 90 DEG C of standing certain hours, the SBR#1 obtained with embodiment 1 contrasts bloom phenomenon.
Halloysite prepared by embodiment 1/butadiene-styrene rubber matrix material SBR#1 and the halloysite prepared by comparative example 6/butadiene-styrene rubber matrix material SBR#5 is statically placed in blank sheet of paper upper 12 day and 30 days respectively at ambient temperature, and after removing sample, Fig. 6 (a) is shown in by the photo of blank sheet of paper.Halloysite prepared by embodiment 1/butadiene-styrene rubber matrix material SBR#1 and the halloysite prepared by comparative example 6/butadiene-styrene rubber matrix material SBR#5 recording surface nitrogen constituent content via surface-element analysis (XPS) and the results are shown in Figure 6 (b) after 90 DEG C of standing certain hours.
Halloysite prepared by embodiment 1/butadiene-styrene rubber matrix material SBR#1 and the halloysite prepared by comparative example 6/butadiene-styrene rubber matrix material SBR#5 is statically placed in blank sheet of paper upper 12 day and 30 days respectively at ambient temperature, what after removing sample, blank sheet of paper remains is anti-aging agent, the depth of color has reacted the spray volume of anti-aging agent, display is placed SBR#1 sample position blank sheet of paper for 12 days afterwards and is substantially placed SBR#5 sample position blank sheet of paper without colour-change and become brown color in Fig. 6 (a), and within 30 days, place SBR#1 sample position blank sheet of paper afterwards and still place SBR#5 sample position brown color without obvious colour-change and deepen, illustrate that " nano container " due to halloysite also can not cause bloom even if act on the anti-aging agent adding higher amount.The surface nitrogen constituent content that via surface-element analysis (XPS) record of halloysite prepared by embodiment 1/butadiene-styrene rubber matrix material SBR#1 and the halloysite prepared by comparative example 6/butadiene-styrene rubber matrix material SBR#5 after 90 DEG C of standing certain hours has reacted the amount of sample surfaces anti-aging agent, from Fig. 6 (b), the content of sample surfaces nitrogen element and the amount of anti-aging agent increase gradually and the content of the nitrogen element of SBR#5 sample surfaces far away higher than SBR#1 sample surfaces, describe quantitatively and anti-aging agent load is effectively controlled bloom phenomenon in halloysite tube chamber.

Claims (4)

1. utilize halloysite slowly-releasing anti-aging agent to prepare a method for ageing-resistant rubber, it is characterized in that, comprise the following steps:
1) after by halloysite nanotubes matrix, in acetone soln, ultrasonic wave is disperseed, being placed on concentration is in the anti-aging agent solution of 2 ~ 50g/L, vacuum 5 ~ 60min is kept at vacuum chamber, keep 5 ~ 30min at ambient pressure again, after repeating this circulation more than three times, use deionized water wash sample, after 50 DEG C of oven for drying, obtain the halloysite nanotubes of load anti-aging agent;
2) by step 1) halloysite nanotubes of load anti-aging agent prepared is with the ratio of 20 ~ 100phr and rubber combinedly prepare rubber unvulcanizate, then sulfidization molding, the rubber composite that the halloysite nanotubes of obtained load anti-aging agent is filled.
2. in accordance with the method for claim 1, it is characterized in that, step 1) in the matrix of halloysite nanotubes be natural halloysite nanotubes.
3. in accordance with the method for claim 1, it is characterized in that, step 2) in rubber replace with plastics, resin, coating or tackiness agent.
4. in accordance with the method for claim 1, it is characterized in that, acetone soln replaces with water, ethanol, ethyl acetate or toluene, and anti-aging agent replaces medicine, protein, metal or metal oxide particle.
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CN106084353A (en) * 2016-06-21 2016-11-09 北京化工大学 A kind of method utilizing CNT slow release age resistor to prepare ageing-resistant functional rubber
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
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CN109593304A (en) * 2018-12-27 2019-04-09 安徽百通高科塑业有限公司 A kind of preparation method of coal mine PVC pipe
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CN112175239A (en) * 2019-07-03 2021-01-05 北京化工大学 Long-acting and controllable composite anti-aging agent and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN106010394A (en) * 2016-06-02 2016-10-12 国际竹藤中心 Preparation method of slow-release type multifunctional adhesive
CN106084353A (en) * 2016-06-21 2016-11-09 北京化工大学 A kind of method utilizing CNT slow release age resistor to prepare ageing-resistant functional rubber
CN110156919A (en) * 2018-02-10 2019-08-23 北京化工大学 A kind of rubber antioxidant and preparation method thereof
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
CN109593304A (en) * 2018-12-27 2019-04-09 安徽百通高科塑业有限公司 A kind of preparation method of coal mine PVC pipe
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
CN112175239A (en) * 2019-07-03 2021-01-05 北京化工大学 Long-acting and controllable composite anti-aging agent and preparation method and application thereof
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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