CN109867826B - Preparation method of modified diatomite - Google Patents
Preparation method of modified diatomite Download PDFInfo
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- CN109867826B CN109867826B CN201811655235.9A CN201811655235A CN109867826B CN 109867826 B CN109867826 B CN 109867826B CN 201811655235 A CN201811655235 A CN 201811655235A CN 109867826 B CN109867826 B CN 109867826B
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Abstract
The invention discloses a modification preparation method of diatomite, and belongs to the field of rubber materials. The method has the advantages of cheap and easily-obtained raw materials, simple processing equipment, convenient operation and no environmental pollution in the processing process, and compared with unmodified diatomite, the modified diatomite has better binding capacity with a natural rubber matrix and can improve the mechanical property of the natural rubber.
Description
Technical Field
The invention relates to the field of rubber fillers, in particular to a preparation method of modified diatomite, which is used in the field of natural rubber reinforcing fillers.
Background
Diatomite is a biological mineral material formed by depositing and mineralizing remains of unicellular lower aquatic plants diatom in sea and river for millions of years. The diatomite has the advantages of unique orderly arranged microporous structure, a large number of tiny holes and channels, high porosity, large pore volume, light weight, small bulk density, large specific surface area, low heat conductivity coefficient and the like, and the diatomite is widely distributed in China, abundant in resources, convenient to purify and low in price; therefore, the diatomite is used as a rubber filler by utilizing the special structures and properties of micron-sized shapes and natural nano-pores of the diatomite, and has good reinforcing effect (slow shrinkage and the like, performance comparison research of white carbon black and diatomite filled butyl rubber, 2016 (3): 150-154 in the rubber industry). However, since diatomaceous earth has a hydrophilic surface and is poor in compatibility with a rubber matrix, and tends to agglomerate in rubber and is difficult to exert its reinforcing effect, surface modification treatment has been required (Ma Xiao et al, treatment of diatomaceous earth and its application to rubber, rubber science 2014 (10): 14-18). The modification method reported at present mainly adopts wet mixing small molecular modifiers such as silane coupling agents, surfactants and the like, such as Wuweili and the like (a new diatomite-filled rubber nano composite material research, high molecular report, 2017, (11): 54-59) reports that silane coupling agents Si69 are adopted to modify diatoms to replace white carbon black to reinforce filled fluororubber, ethylene propylene diene monomer rubber and acrylate rubber; pengze et al (patent No. 101914229A, a process for preparing diatomite/natural rubber composite) propose that diatomite is modified by silane coupling agent and dispersed in natural latex by emulsion blending method, then surface modifier is added, and after coagulating agent coagulation and drying, a diatomite/natural rubber composite is prepared for preparing medical natural latex products.
The thermoplastic phenolic resin has good compatibility with styrene butadiene rubber, natural rubber and the like, and hydroxymethyl contained in the thermoplastic phenolic resin has strong reactivity, so that the thermoplastic phenolic resin can be used as a tackifier, a reinforcing agent and a softener of rubber, the processing temperature can be reduced, and the safety and the quality uniformity of rubber material mixing can be ensured. Therefore, the thermoplastic phenolic resin modified diatomite can increase the compatibility of the diatomite with natural rubber, styrene butadiene rubber and the like, play a role in reinforcing the diatomite in the rubber and improve the physical and mechanical properties of the rubber.
Drawings
FIGS. 1 and 2 are scanning electron micrographs of unmodified diatomaceous earth and phenolic resin-modified diatomaceous earth, respectively. The diatomite is in a disc-shaped structure, and more micropores exist on the surface; when the surface of diatomaceous earth is modified with a phenolic resin, the discoid structure disappears.
Disclosure of Invention
The invention mainly solves the technical problems that the compatibility between diatomite and a natural rubber matrix is poor, the diatomite is difficult to disperse in rubber, easy to agglomerate and difficult to exert the reinforcing effect.
The invention aims to provide a novel rubber filler diatomite modification preparation method, which comprises the steps of carrying out ball milling on thermoplastic phenolic resin and diatomite in a ball mill, and enabling hydroxymethyl in the thermoplastic phenolic resin and silicon hydroxyl on the surface of the diatomite to be mutually combined through mechanical force action so as to modify the surface of the diatomite, improve the dispersibility and compatibility of the diatomite in a natural rubber matrix, improve the bonding force with the rubber matrix and further achieve the effect of enhancing the natural rubber.
The preparation method of the modified diatomite provided by the invention has the advantages of simple processing equipment, convenience in operation, no environmental pollution in the processing process, good reinforcing effect of the modified diatomite on natural rubber, high product cost performance and good market application prospect. The specific embodiment adopted by the invention is as follows:
the invention is further described with reference to specific embodiments, without limiting the scope of protection. Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Embodiment 1
(1) Firstly, drying the diatomite in an oven at 105 ℃ for 3 hours, weighing 50g of diatomite after cooling, and putting the diatomite into a ball milling tank. Ball milling is carried out on a planetary ball mill, the rotating speed is adjusted to be 200 r/min, the time is 10 hours, and a sample is taken out.
(2) The unmodified diatomite sample is used as a natural rubber reinforcing filler, and is subjected to plastication, mixing, tabletting, vulcanization and cutting to obtain a standard sample piece for mechanical property test. The basic formula of the rubber processing is as follows: natural Rubber (NR), 100 parts; zinc oxide (ZnO-80), 6.25; stearic acid, 1.5; 2.5 parts of sulfur; accelerator NS (NS-80), 1.25; anti-aging agent 4020, 1.5; 30 parts of unmodified diatomite.
(2) From the mechanical property test results (see table 1), it can be seen that the elongation at break is 749.72%, which is increased by 306.42%, and the tensile strength at break is 23.84MPa, which is increased by 1.96MPa, compared with the unmodified natural diatomite.
Embodiment 2
(1) Firstly, drying the diatomite in an oven at 105 ℃ for 3 hours, weighing 50g of diatomite after cooling, and weighing 1g of phenolic resin (according to m)Phenolic resin∶mDiatomiteMixing the two at a ratio of 1: 50, and placing the mixture into a ball milling tank. Ball milling is carried out on a planetary ball mill, the rotating speed is adjusted to be 200 r/min, the time is 10 hours, and a sample is taken out.
(2) The modified diatomite sample is used as a natural rubber reinforcing filler, and is subjected to plastication, mixing, tabletting, vulcanization and cutting to obtain a standard sample piece for mechanical property test. The basic formula of the rubber processing is as follows: natural Rubber (NR), 100 parts; zinc oxide (ZnO-80), 6.25; stearic acid, 1.5; 2.5 parts of sulfur; accelerator NS (NS-80), 1.25; anti-aging agent 4020, 1.5; 30 parts of modified diatomite.
(3) From the mechanical property test results (see table 1), it can be seen that the elongation at break is 749.72%, which is increased by 306.42%, and the tensile strength at break is 23.84MPa, which is increased by 1.96MPa, compared with the unmodified natural diatomite.
Embodiment 3
(1) Diatomaceous earth was first placed in an oven at 105 deg.CDrying for 3 hr, cooling, weighing 50g diatomaceous earth, and weighing 1.67g phenolic resin (according to m)Phenolic resin∶mDiatomite1: 30), mixing the two, and putting the mixture into a ball milling tank. Ball milling is carried out on a planetary ball mill, the rotating speed is adjusted to be 200 r/min, the time is 10 hours, and a sample is taken out.
(2) The modified diatomite sample is used as a natural rubber reinforcing filler, and is subjected to plastication, mixing, tabletting, vulcanization and cutting to obtain a standard sample piece for mechanical property test. The basic formula of the rubber processing is as follows: natural Rubber (NR), 100 parts; zinc oxide (ZnO-80), 6.25; stearic acid, 1.5; 2.5 parts of sulfur; accelerator NS (NS-80), 1.25; anti-aging agent 4020, 1.5; 30 parts of modified diatomite.
(3) From the mechanical property test results (see table 1), it can be seen that the elongation at break is 561.42%, which is increased by 118.12%, and the tensile strength at break is 24.50MPa, which is increased by 2.62MPa, compared with the unmodified natural diatomite.
Embodiment 4
(1) Diatomaceous earth is first dried in an oven at 105 ℃ for 3 hours, after cooling 50g of diatomaceous earth are weighed out, and 2.5g of phenolic resin (in terms of m) are weighed outPhenolic resin∶mDiatomite1: 20), mixing the two, and putting the mixture into a ball milling tank. Ball milling is carried out on a planetary ball mill, the rotating speed is adjusted to be 200 r/min, the time is 12 hours, and a sample is taken out.
(2) The modified diatomite sample is used as a natural rubber reinforcing filler, and is subjected to plastication, mixing, tabletting, vulcanization and cutting to obtain a standard sample piece for mechanical property test. The basic formula of the rubber processing is as follows: natural Rubber (NR), 100 parts; zinc oxide (ZnO-80), 6.25; stearic acid, 1.5; 2.5 parts of sulfur; accelerator NS (NS-80), 1.25; anti-aging agent 4020, 1.5; 30 parts of modified diatomite.
(3) From the mechanical property test results (see table 1), it can be seen that compared with the unmodified natural diatomite, the elongation at break is 710.46%, which is improved by 267.16%, and the tensile strength at break is 24.92MPa, which is improved by 3.04 MPa.
Embodiment 5
(1) Firstly, diatomite is dried in an oven at 105 ℃ for 3 hours, and 50g of diatomite is weighed after coolingSoil, and 2.63g of phenolic resin (in terms of m) were weighed outPhenolic resin∶mDiatomite1: 19), mixing the two, and putting the mixture into a ball milling tank. Ball milling is carried out on a planetary ball mill, the rotating speed is adjusted to be 220 r/m, the time is 10 hours, and a sample is taken out.
(2) The modified diatomite sample is used as a natural rubber reinforcing filler, and is subjected to plastication, mixing, tabletting, vulcanization and cutting to obtain a standard sample piece for mechanical property test. The basic formula of the rubber processing is as follows: natural Rubber (NR), 100 parts; zinc oxide (ZnO-80), 6.25; stearic acid, 1.5; 2.5 parts of sulfur; accelerator NS (NS-80), 1.25; anti-aging agent 4020, 1.5; 30 parts of modified diatomite.
(3) From the mechanical property test results (see table 1), it can be seen that compared with the unmodified natural diatomite, the elongation at break is 624.26%, which is improved by 180.96%, and the tensile strength at break is 25.20MPa, which is improved by 3.32 MPa.
Embodiment 6
(1) The diatomaceous earth is dried in an oven at 105 ℃ for 3 hours, 50g of diatomaceous earth is weighed after cooling, and 0.63g of phenolic resin (in terms of m) is weighedPhenolic resin∶mDiatomite1: 80), mixing the two, and putting the mixture into a ball milling tank. Ball milling is carried out on a planetary ball mill, the rotating speed is adjusted to be 220 r/m, the time is 10 hours, and a sample is taken out.
(2) The modified diatomite sample is used as a natural rubber reinforcing filler, and is subjected to plastication, mixing, tabletting, vulcanization and cutting to obtain a standard sample piece for mechanical property test. The basic formula of the rubber processing is as follows: natural Rubber (NR), 100 parts; zinc oxide (ZnO-80), 6.25; stearic acid, 1.5; 2.5 parts of sulfur; accelerator NS (NS-80), 1.25; anti-aging agent 4020, 1.5; 30 parts of modified diatomite.
(3) From the mechanical property test results (see table 1), it can be seen that compared with the unmodified natural diatomite, the elongation at break is 642.62%, which is improved by 199.32%, and the tensile strength at break is 23.41MPa, which is improved by 1.53 MPa.
Embodiment 7
(1) Firstly, drying the diatomite in an oven at 105 ℃ for 3 hours, weighing 50g of diatomite after cooling, and weighing 1g of phenolic resin (according to m)Phenolic resin∶mDiatomite1: 50), mixing the two, and putting the mixture into a ball milling tank. Ball milling is carried out on a planetary ball mill, the rotating speed is adjusted to be 220 r/m, the time is 10 hours, and a sample is taken out.
(2) The modified diatomite sample is used as a natural rubber reinforcing filler, and is subjected to plastication, mixing, tabletting, vulcanization and cutting to obtain a standard sample piece for mechanical property test. The basic formula of the rubber processing is as follows: natural Rubber (NR), 100 parts; zinc oxide (ZnO-80), 6.25; stearic acid, 1.5; 2.5 parts of sulfur; accelerator NS (NS-80), 1.25; anti-aging agent 4020, 1.5; 40 parts of modified diatomite.
(3) From the mechanical property test results (see table 1), it can be seen that compared with the unmodified natural diatomite, the elongation at break is 577.83%, which is improved by 134.53%, and the tensile strength at break is 23.49MPa, which is improved by 1.61 MPa.
Embodiment 8
(1) Firstly, drying the diatomite in an oven at 105 ℃ for 3 hours, weighing 50g of diatomite after cooling, and weighing 1g of phenolic resin (according to m)Phenolic resin∶mDiatomite1: 50), mixing the two, and putting the mixture into a ball milling tank. Ball milling is carried out on a planetary ball mill, the rotating speed is adjusted to be 220 r/m, the time is 10 hours, and a sample is taken out.
(2) The modified diatomite sample is used as a natural rubber reinforcing filler, and is subjected to plastication, mixing, tabletting, vulcanization and cutting to obtain a standard sample piece for mechanical property test. The basic formula of the rubber processing is as follows: natural Rubber (NR), 100 parts; zinc oxide (ZnO-80), 6.25; stearic acid, 1.5; 2.5 parts of sulfur; accelerator NS (NS-80), 1.25; anti-aging agent 4020, 1.5; 15 parts of white carbon black and 15 parts of modified diatomite.
(3) From the mechanical property test results (see table 1), it can be seen that compared with the unmodified natural diatomite, the elongation at break is 568.24%, which is improved by 124.94%, and the tensile strength at break is 23.03MPa, which is improved by 1.15 MPa.
TABLE 1 mechanical Properties of diatomaceous earth-filled Natural rubber
Claims (5)
1. The preparation method of the modified diatomite is characterized by comprising the following steps:
(1) placing the weighed diatomite in an oven, heating to 102-120 ℃, and drying for 2-6 hours;
(2) mixing the dried diatomite with a certain amount of phenolic resin, putting the mixture into a ball milling tank, carrying out ball milling on a planetary ball mill, taking out a sample after the ball milling is finished, and packaging the sample for later use.
2. The method of claim 1, wherein the diatomaceous earth comprises natural diatomaceous earth or calcined diatomaceous earth, and has the following performance characteristics: the color is white, and the whiteness is over 80; the fineness is 200-600 meshes; the pH value is 8-10; the bulk density is 0.36-0.48g/cm3。
3. The process according to claim 1, wherein the phenol resin has the following properties: thermoplastic property, softening point of 95-112 deg.C, and water content less than 3%.
4. The process according to claim 1, wherein the phenol resin and the diatomaceous earth are used in the following proportions: m isPhenolic resin∶mDiatomite＝1∶12-100。
5. The preparation method according to claim 1, wherein the method comprises a normal temperature mechanical ball milling method at a rotation speed of 200 and 250 rpm for a ball milling time of 10-12 h.
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| CN102432785B (en) * | 2011-09-14 | 2013-06-12 | 武汉理工大学 | Method for preparing in-situ dispersion nano polybasic graft modified phenolic resin |
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