CN109867826B - Preparation method of modified diatomite - Google Patents
Preparation method of modified diatomite Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- diatomite
- preparation
- phenolic resin
- rubber
- ball milling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000005011 phenolic resin Substances 0.000 claims description 25
- 229920001568 phenolic resin Polymers 0.000 claims description 22
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 21
- 239000005909 Kieselgur Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims 1
- 244000043261 Hevea brasiliensis Species 0.000 abstract description 36
- 229920003052 natural elastomer Polymers 0.000 abstract description 36
- 229920001194 natural rubber Polymers 0.000 abstract description 36
- 229920001971 elastomer Polymers 0.000 abstract description 17
- 239000005060 rubber Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 32
- 238000002156 mixing Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 239000011787 zinc oxide Substances 0.000 description 16
- 239000012763 reinforcing filler Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 235000021355 Stearic acid Nutrition 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 230000003712 anti-aging effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
- 238000010057 rubber processing Methods 0.000 description 8
- 239000008117 stearic acid Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920001169 thermoplastic Polymers 0.000 description 6
- 239000004416 thermosoftening plastic Substances 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- -1 phenolic resin modified diatomite Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000206761 Bacillariophyta Species 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical group C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
本发明公开了一种硅藻土的改性制备方法，属于橡胶材料领域。该方法具有原料便宜、易得，加工设备简单、操作方便、加工过程中不污染环境，与未改性硅藻土相比，改性后的硅藻土与天然橡胶基体具有较好的结合能力，可提高天然橡胶的力学性能。The invention discloses a modified preparation method of diatomite, which belongs to the field of rubber materials. The method has the advantages of cheap and easy-to-obtain raw materials, simple processing equipment, convenient operation, and no environmental pollution during processing. Compared with unmodified diatomite, the modified diatomite has better binding ability to the natural rubber matrix. , which can improve the mechanical properties of 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)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811655235.9A CN109867826B (en) | 2018-12-30 | 2018-12-30 | Preparation method of modified diatomite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811655235.9A CN109867826B (en) | 2018-12-30 | 2018-12-30 | Preparation method of modified diatomite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109867826A CN109867826A (en) | 2019-06-11 |
| CN109867826B true CN109867826B (en) | 2021-03-30 |
Family
ID=66917407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811655235.9A Active CN109867826B (en) | 2018-12-30 | 2018-12-30 | Preparation method of modified diatomite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109867826B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111518415B (en) * | 2020-04-26 | 2022-01-14 | 远东电缆有限公司 | Modified diatomite synergistic flame-retardant polyolefin material and preparation method thereof |
| CN115572419B (en) * | 2022-12-09 | 2023-04-18 | 广东粤港澳大湾区黄埔材料研究院 | Wet mixing rubber material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045111A (en) * | 1989-02-24 | 1990-09-05 | 戴运生 | The weighting agent of diatomite as high molecular material |
| JP5584990B2 (en) * | 2009-03-31 | 2014-09-10 | 日本ゼオン株式会社 | Method for producing modified silica, resin composition for insulating material, and film for insulating film |
| 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 |
| CN108359137A (en) * | 2017-12-29 | 2018-08-03 | 柳州市海达新型材料科技有限公司 | A kind of preparation method of low bulk modified talc powder |
-
2018
- 2018-12-30 CN CN201811655235.9A patent/CN109867826B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109867826A (en) | 2019-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102786726B (en) | High performance XNBR vulcanized rubber containing graphene oxide and its preparation method | |
| CN100457812C (en) | Process for preparing attapulgite and natural rubber nano composite material | |
| CN109867826B (en) | Preparation method of modified diatomite | |
| CN107337815B (en) | A kind of preparation method of silicon carbon black/natural rubber composite material | |
| Ginting et al. | Mechanical properties and mophology natural rubber blend with bentonit and carbon black | |
| CN101508801B (en) | Method for preparing oil-filled styrene butadiene rubber SBR1712/attapulgite stone nano-composite material | |
| US20170121511A1 (en) | A process to prepare high-quality natural rubber silica masterbatch by liquid phase mixing | |
| CN110628140B (en) | Wear-resistant runway granular material and preparation method thereof | |
| CN116855000A (en) | Preparation method of graphene/carbon black with different particle sizes and synergistically vulcanized modified natural rubber long-life load tire | |
| CN105694144A (en) | A preparing method of a nitrile butadiene rubber/attapulgite/hydrotalcite composite material | |
| WO2016014037A1 (en) | A process to prepare high-quality natural rubber-silica masterbatch by liquid phase mixing | |
| CN118374068B (en) | Preparation method and application of diatomite and zinc oxide composite high-density rubber material | |
| CN110452419A (en) | A kind of surface grafting has the preparation method of the nano silica of liquid rubber | |
| CN101875733B (en) | Preparation method of kaolin/styrene-butadiene rubber composite material for soft rubber sole | |
| CN110564026B (en) | A kind of preparation method of high wear-resistant rain boots | |
| CN114407266A (en) | Preparation method of carbon black/natural latex composite material | |
| CN114437446A (en) | Preparation method of dummy rib material suitable for collision test of Chinese people | |
| CN104650303B (en) | Preparation method of modified oil-extended high-performance powdered styrene-butadiene rubber | |
| CN104650421B (en) | Preparation method of rice hull ash modified styrene butadiene rubber | |
| CN104650414B (en) | Preparation method of rice hull ash modified powder butadiene-acrylonitrile polymer | |
| CN105461974A (en) | Modified attapulgite for rubber reinforcing, and preparation method thereof | |
| CN109608706A (en) | A kind of preparation method of graphene rubber composite material | |
| CN103113632A (en) | Method for preparing composite material of reaction type egg shell powder and natural rubber | |
| CN114907590A (en) | A synthetic rubber wet masterbatch and its preparation method and application | |
| KR102753270B1 (en) | Method for manufacturing wet master batch elastomer compositon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |