Method for preparing nano attapulgite and phenolic aerogel and method for preparing abrasion-resistant vehicle tire

Abstract

A method for preparing an aerogel comprising nano attapulgite and phenolic aldehyde and a method for preparing abrasion-resistant vehicle tire. 80-100 weight distributions of rubber, 3-8 weight distributions of SiO.sub.2.nH.sub.2O, 3-6 weight distributions of an anti-aging agent, 3-4 weight distributions of a heat stabilizer, 3-5 weight distributions of a compatibilizing agent, and 3-12 weight distributions of the aerogel comprising the nano attapulgite and the phenolic aldehyde is selected as a raw material of the abrasion-resistant rubber material to prepare rubber composite material for the abrasion-resistant vehicle tire.

Claims

1. A method for preparing an aerogel comprising nano attapulgite and phenolic aldehyde, comprising: (1) dispersing bisphenol A, tetraethylenepentamine, and paraformaldehyde in 1,4-dioxane, stirring in an ice bath for 0.8-1.2 hours, heating to room temperature, continually stirring for 4-12 hours to obtain a monomer BA-TEPA, wherein a structural formula of the monomer BA-TEPA is as follows: ##STR00004## (2) dispersing original attapulgite in ultrapure water, stirring for 0.8-1.2 hours, then adding oxalic acid, hydrothermally processing at 120-160° C. for 2-8 hours, then thermally processing at 80-140° C. for 10-40 hours, washing to neutrality to obtain nano attapulgite; (3) sonicating to disperse the nano attapulgite prepared in step (2) in a 50/50 (vol/vol) water-ethanol solution, then adding chitosan and acetic acid, stirring for 20-25 hours, then adding the monomer BA-TEPA prepared in step (1), stirring to even, then adding formaldehyde, stirring for 2-4 minutes, then leaving to stand to form a gel, and finally aging the gel to form a wet gel; and (4) after substituting the wet gel prepared in step (3) with a solvent with a volume ratio of ethanol and water of 1-3:100 for 3-4 days, freeze-drying to obtain the aerogel comprising the nano attapulgite and the phenolic aldehyde.

2. The method according to claim 1, wherein a ratio of the bisphenol A, the tetraethylenepentamine, the paraformaldehyde, and the 1,4-dioxane is 1 mol-4 mol: 1 mol-4 mol: 4 mol-16 mol: 100 mL-500 mL.

3. The method according to claim 1, wherein: a mass ratio of the original attapulgite and the ultrapure water is 1:5 to 1:30, and the adding oxalic acid comprises adding the oxalic acid to a final concentration of 0.5-5 Mol/L.

4. The method according to claim 1, wherein a mass ratio of the nano attapulgite and the monomer BA-TEPA is 0.05-0.5:0.05-0.5.

5. The method according to claim 4, wherein a ratio of the nano attapulgite, the water-ethanol solution, and the formaldehyde is 0.05 g-0.5 g: 9 mL-11 mL:50μ-500 μL.

6. The method according to claim 1, wherein the aging the gel to form the wet gel comprises aging the gel at 20-70° C. for 6-30 hours.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 illustrates a proton nuclear magnetic resonance spectrum of a BA-TEPA monomer of Embodiment 1 of the present disclosure.

(2) FIG. 2 illustrates an infrared spectrum of the BA-TEPA monomer of Embodiment 1 of the present disclosure.

(3) FIG. 3 illustrates a scanning electron micrograph (SEM) of nano attapulgite of Embodiment 1 of the present disclosure.

(4) FIG. 4 illustrates stress-strain compression curves of chitosan and phenolic aerogel prepared in a control example 1 and the nano attapulgite and phenolic aerogel prepared in Embodiment 1 of the present disclosure, wherein curve a represents a stress-strain compression curve of the chitosan and the phenolic aerogel prepared in the control example 1, and curve b represents a compressive stress-strain curve of the nano attapulgite and the phenolic aerogel prepared in Embodiment 1.

(5) FIG. 5 illustrates thermogravimetric curves of nano-attapulgite and chitosan aerogel prepared in a control example 2 and the nano attapulgite and the phenolic aerogel prepared in Embodiment 1 of the present disclosure, wherein curve al represents a thermogravimetric curve of the nano-attapulgite and the chitosan aerogel prepared in the control example 2, and curve b1 represents a thermogravimetric curve of the nano attapulgite and the phenolic aerogel prepared in Embodiment 1.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(6) The technical solution of the present disclosure will be further described as follows in combination with the accompanying embodiments and drawings.

Embodiment 1

(7) (1) Preparation of a monomer BA-TEPA (i.e., phenolic monomer BA-TEPA):bisphenol A, tetraethylenepentamine (TEPA), and paraformaldehyde are dispersed (e.g., dissolved) in 100 mL of 1,4-dioxane, mechanically stirred in ice bath for 1 hour, heated to room temperature (e.g., 20-25° C.), and continually mechanically stirred for 8 hours to obtain a uniform yellow viscous fluid. Referring to FIGS. 1 and 2, which is the monomer BA-TEPA, a structural formula is as follows:

(8) ##STR00002##

(9) A dose ratio of the bisphenol A, the tetraethylenepentamine, the paraformaldehyde, and the 1,4-dioxane is 1 mol: 1 mol: 4 mol: 100 mL. A reaction principle in which rubber is modified using the phenolic monomer BA-TEPA is as follows:

(10) ##STR00003##

(11) (2) Preparation of nano attapulgite: original attapulgite is dispersed in ultrapure water with a mass ratio of 1:20 and stirred for 1 hour, 1M (mol/L) of oxalic acid is added, hydrothermally processed at 140° C. for 6 hours, and then thermally processed at 120° C. for 24 hours or then thermally processed at 120° C. for 24 hours and washed to neutrality. Referring to FIG. 3, the nano attapulgite is then obtained.

(12) (3) Preparation of aerogel: 0.25 g of the nano attapulgite is sonicated to be dispersed in 10 mL of 50/50 (vol/vol) water-ethanol solution, 1 wt % (weight percent) chitosan and 1 volume % (volume percent) acetic acid are added and stirred for 24 hours, 0.05 g of the phenolic monomer BA-TEPA is then added and uniformly stirred, 100 μL of formaldehyde is then added, stirred for 3 minutes, and then left to stand to form a gel. The gel is finally aged at 60° C. for 8 hours to form a nano attapulgite-phenolic wet gel.

(13) (4) After the nano attapulgite-phenolic wet gel is substituted with an ethanol-water solvent with a volume ratio of 1:100 for 3 days and freeze-dried at −30° C. to maintain original gel space structure, and the aerogel comprising the nano attapulgite and the phenolic aldehyde is finally obtained.

(14) 3-12 weight distributions of the aerogel comprising the nano attapulgite and the phenolic aldehyde prepared in this embodiment, 80-100 weight distributions of rubber, 3-8 weight distributions of a white carbon black (SiO.sub.2.nH.sub.2O), 3-6 weight distributions of an anti-aging agent, 3-4 weight distributions of a heat stabilizer, and 3-5 weight distributions of a compatibilizing agent are mixed in an internal mixer, continually mixed, materials are then discharge to a cutting machine, a sheet is obtained by three processes, which including calendering, extruding, and molding, an abrasion-resistant rubber material for preparing an abrasion-resistant vehicle tire is obtained, and the abrasion-resistant rubber material defines a certain shape.

Control Example 1

(15) In this control example, a chitosan-phenolic aerogel is prepared. This control example differs from Embodiment 1 in that: the step (2) is omitted, and 1 wt % (weight percent) chitosan and 1 volume % (volume percent) acetic acid are added and stirred for 24 hours. 0.05 g of the phenolic monomer BA-TEPA is then added and well stirred, 100 μL of formaldehyde is added and stirred for 3 minutes and then left to stand to form a gel. The gel is finally aged at 60° C. for 8 hours to form a chitosan-phenolic wet gel.

(16) A preparation of a rubber material in this control example is the same as Embodiment 1.

Control Example 2

(17) In this control example, a nano attapulgite-chitosan aerogel is prepared. This control example differs from Embodiment 1 in that: in step (3), 0.25 g of nano attapulgite is sonicated to be dispersed in a water-ethanol solution (V.sub.H2O/V.sub.EtOH=1:1), 1 wt % (weight percent) chitosan and 1 volume % (volume percent) acetic acid are added and stirred for 24 hours, 100 μL of formaldehyde is then added, stirred for 3 minutes, and left to stand to form a gel. The gel is finally aged at 60° C. for 8 hours to form a wet gel.

(18) A preparation of a rubber material in this control example is the same as Embodiment 1.

(19) An abrasion test condition of the abrasion-resistant rubber material prepared in Embodiment 1 and Control example 2 is as follows: sandpaper with a thickness of 120 A, a slip velocity of 10 m/min, a slip ratio of 5%, a load of 75 N, and a time of 15 minutes. Test data is shown in the following table:

(20) TABLE-US-00001 Average abrasion Abrasion weight (g) Specific volume Sample Sample 1 Sample 2 Sample 3 Average gravity (cm.sup.3) Control 41.4887 − 40.4075 − 40.9765 − 0.113 1.126 0.102 example 2 41.3951 = 40.2730 = 40.8654 =  0.0936  0.1345  0.1111 Embodiment 1 41.8475 − 40.9355 − 40.9588 − 0.100 1.109 0.089 41.7365 = 40.8265 = 40.8782 =  0.1110  0.1090  0.0806

(21) Referring to FIG. 4, a curve a and a curve b are respectively compressive stress-strain curves of the aerogel comprising the nano attapulgite and the phenolic aldehyde prepared in Embodiment 1 and the chitosan-phenolic aerogel prepared in Control example 1, which indicates that the aerogel comprising the nano attapulgite and the phenolic aldehyde prepared in Embodiment 1 has better mechanical properties.

(22) Referring to FIG. 5, a curve al and a curve b1 are respectively thermogravimetric curves of the chitosan-phenolic aerogel prepared in Embodiment 1 and the nano attapulgite-chitosan aerogel prepared in Control example 2. Carbon-residue contents are respectively 63.4% and 43.5%, which indicates that the aerogel comprising the nano attapulgite and the phenolic aldehyde prepared in Embodiment 1 has a better flame-retardant effect.

(23) It can be known from the above results that the abrasion-resistant rubber material prepared in the embodiment of the present disclosure can be used to prepare a heavy-duty vehicle tire.

(24) The aforementioned embodiments are merely some embodiments of the present disclosure, and the scope of the disclosure is not limited thereto. Thus, it is intended that the present disclosure cover any modifications and variations of the presently presented embodiments provided they are made without departing from the appended claims and the specification of the present disclosure.