CN116178976A - Preparation method of modified lignin and application of modified lignin in natural rubber - Google Patents
Preparation method of modified lignin and application of modified lignin in natural rubber Download PDFInfo
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- CN116178976A CN116178976A CN202310143353.6A CN202310143353A CN116178976A CN 116178976 A CN116178976 A CN 116178976A CN 202310143353 A CN202310143353 A CN 202310143353A CN 116178976 A CN116178976 A CN 116178976A
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- lignin
- process oil
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- 229920005610 lignin Polymers 0.000 title claims abstract description 74
- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 13
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 13
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000010734 process oil Substances 0.000 claims abstract description 17
- 229920001971 elastomer Polymers 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 239000002199 base oil Substances 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000010902 jet-milling Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000010057 rubber processing Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- -1 methoxy, hydroxyl Chemical group 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compounds Of Unknown Constitution (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A method for improving lignin dispersion in natural rubber, comprising the specific steps of: (1) The grain diameter of lignin is controlled to be D50 less than 10 mu m and D100 is controlled to be 70 mu m after being crushed; (2) Blending a certain amount of rubber auxiliary agent process oil and a certain amount of lignin at a certain temperature for a certain time until the process oil and the lignin are in a uniform paste state, so as to obtain modified lignin; wherein, the mass portions of the lignin and the process oil are as follows: 10-40 parts of lignin and 10-30 parts of process oil. The method adopted by the invention can overcome the difficulty that lignin series products have poor dispersing effect in natural rubber, is simple and easy to obtain, and fully utilizes the difficulty existing in the physical and chemical performance result processing process among materials.
Description
Technical Field
The invention relates to the field of rubber processing, in particular to a preparation method of modified lignin and application of the modified lignin in natural rubber.
Background
Lignin is a non-crystalline, highly branched three-dimensional network aromatic ring-containing phenolic biopolymer, and lignin is widely present in higher plant cells. In nature, it is a renewable natural polymer in the second place of world reserves, next to cellulose. It is estimated that about 5 x 10 can be produced annually worldwide 8 -36×10 8 Tons. In the plant body, lignin, cellulose, hemicellulose and the like form a supermolecular system together, and the lignin is bonded with the cellulose to strengthen the mechanical strength of the plant body. The lignin has a complex structure, and although the complete structure of the natural lignin is not known so far, many years of researches show that the lignin contains more active groups such as aromatic groups, alcoholic hydroxyl groups, carboxyl groups, methoxy groups, conjugated double bonds and the like and has certain chemical activity; the lignin can react with materials such as rubber, plastics and the like in a grafting, crosslinking and other manners, and hydroxyl active groups in the lignin can form aromatic hydrogen bonds with pi electron clouds of conjugated double bonds in the rubber; the oxygen atoms in the methoxy, hydroxyl, carbonyl and other groups do not share electron pairs, so that lignin-metal chelate can be formed with metal ions in a coordination bond mode, and a crosslinking network structure is constructed by utilizing the reactivity of lignin molecules, so that the lignin plays a role in reinforcing and plasticizing.
The lignin has the above multiple functional groups and has relatively large molecular polarity, so that the lignin is difficult to disperse in natural rubber, and even if the particle size is small, the lignin can not be effectively dispersed within a specified processing time due to the agglomeration phenomenon in the processing process, so that the functions of the lignin can not be reflected. In view of the above problems, the present invention solves the problem that lignin cannot be in natural rubber in an effective manner.
Disclosure of Invention
In order to solve the problems, the invention provides a method for improving the dispersion of lignin in natural rubber, which comprises the following specific steps:
(1) The grain diameter of lignin is controlled to be D50 less than 10 mu m and D100 is controlled to be 70 mu m after being crushed;
(2) Blending a certain amount of rubber auxiliary agent process oil and a certain amount of lignin at a certain temperature for a certain time until the process oil and the lignin are in a uniform paste state, so as to obtain modified lignin;
wherein, the mass portions of the lignin and the process oil are as follows: 10-40 parts of lignin and 10-30 parts of process oil.
Preferably, the process oil is one or more of aromatic base oils, paraffinic base oils, naphthenic base oils, more preferably aromatic base oils.
Preferably, the process oil is mixed with lignin at a temperature of 20-60 ℃.
Preferably, the lignin pulverizing method comprises one of mechanical pulverization, jet milling and ball milling.
The invention also provides a modified lignin, which is prepared by the preparation method.
The invention also provides application of the modified lignin in the field of natural rubber, and the dispersibility of the lignin in a rubber matrix can be improved.
Compared with the prior art, the invention has the following advantages:
1. the method overcomes the difficulty that lignin series products have poor dispersing effect in natural rubber, is simple and easy to obtain, and fully utilizes the difficulty existing in the physical and chemical performance result processing process between materials.
2. The dust generated by lignin in rubber processing can be reduced after the process oil is mixed with lignin.
3. The papermaking waste liquid is recycled, so that the concept of green development at present is met, and the environmental protection pressure is relieved.
4. The invention reduces the cost investment.
Drawings
FIG. 1 is a schematic view showing the effect of dispersing the modified lignin obtained in example 1 in natural rubber;
fig. 2 is a schematic view showing the effect of dispersing lignin in natural rubber obtained in comparative example 1.
Detailed Description
The invention will be further illustrated with reference to the following examples, although the scope of the invention is not limited thereto.
Example 1
(1) Pulverizing lignin until the particle diameter reaches D50 less than 10 μm, and keeping D100 at 70 μm for later use;
(2) Mixing 20 parts of weighed lignin and 15 parts of aromatic hydrocarbon base oil together, using a stirring rod to perform primary mixing and stirring, and heating a kneader to 20 ℃ to perform kneading to obtain modified lignin.
Example 2
(1) Pulverizing lignin until the particle diameter reaches D50 less than 10 μm, and keeping D100 at 70 μm for later use;
(2) Mixing 40 parts of weighed lignin with 20 parts of paraffin oil, using a stirring rod to perform primary mixing and stirring, and heating a kneader to 40 ℃ to perform kneading to obtain modified lignin.
Example 3
(1) Pulverizing lignin until the particle diameter reaches D50 less than 10 μm, and keeping D100 at 70 μm for later use;
(2) Mixing 10 parts of weighed lignin and 30 parts of naphthenic oil together, using a stirring rod to perform primary mixing and stirring, and heating a kneader to 60 ℃ to perform kneading to obtain modified lignin.
Comparative example 1
The raw materials were used in the same amounts as in example 1, but the mixing equipment was directly added during rubber processing, and no premixing was performed.
Effect of the invention
The example uses the process recipe:
raw materials: 100 parts of nitrile rubber, 2 parts of stearic acid, 5 parts of zinc oxide, 1.8 parts of insoluble vulcanization, 1.5 parts of accelerator TBBS, 5 parts of carbon black N55035 and 5 parts of modified lignin.
The application process comprises the following steps:
(1) Setting an internal mixer at 30 ℃ and at the rotating speed of 50r/min, adding rubber into the internal mixer for banburying for 1min after the temperature is stable, and adding carbon black, modified lignin, stearic acid and zinc oxide for banburying for 8min for discharging;
(2) Setting the temperature of an open mill at 90 ℃, and milling the mixed rubber with the open mill for 3min, and then setting the thickness of the mixed rubber to be 2mm for blanking;
(3) Placing the rubber compound for 4 hours, setting the temperature of an open mill to be 100 ℃, putting the rubber compound into the open mill, boiling for 1min, adding insoluble vulcanization and accelerator TBBS, boiling for 3min, ensuring uniform mixing of materials by continuous side cutting during the process, and then setting the thickness to be 2mm and feeding the sheets;
(4) The vulcanization process is carried out at 150 ℃ for 50min under 10mpa, and the thickness of the sample is controlled to be 2mm.
After the sample was applied, the cross-section of the vulcanized rubber was observed for dispersion, as shown in FIGS. 1-2. From the graph, in the embodiment 1, after rubber processing, the screenshot of the rubber interface does not find the existence of lignin particles, so that the dispersion effect is better; in comparative example 1, lignin particles were clearly present, and the dispersion effect was not ideal.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the modified lignin is characterized by comprising the following specific steps of:
(1) The grain diameter of lignin is controlled to be D50 less than 10 mu m and D100 is controlled to be 70 mu m after being crushed;
(2) Blending a certain amount of rubber auxiliary agent process oil and a certain amount of lignin at a certain temperature for a certain time until the process oil and the lignin are in a uniform paste state, so as to obtain modified lignin;
wherein, the mass parts of the process oil and lignin are as follows: 10-40 parts of lignin and 10-30 parts of process oil.
2. The method for preparing modified lignin according to claim 1, wherein the process oil is one or more of aromatic hydrocarbon base oil, paraffinic base oil and naphthenic base oil.
3. The method of claim 1, wherein in step (2), the mixing temperature of the process oil and lignin is 20-60 ℃.
4. The method of claim 1, wherein the lignin pulverizing method comprises one of mechanical pulverization, jet milling, and ball milling.
5. A modified lignin produced according to the production method according to any one of claims 1 to 4.
6. Use of a modified lignin according to claim 5 in natural rubber, wherein the modified lignin increases the dispersibility of lignin in the rubber matrix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310143353.6A CN116178976A (en) | 2023-02-21 | 2023-02-21 | Preparation method of modified lignin and application of modified lignin in natural rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310143353.6A CN116178976A (en) | 2023-02-21 | 2023-02-21 | Preparation method of modified lignin and application of modified lignin in natural rubber |
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| CN116178976A true CN116178976A (en) | 2023-05-30 |
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| CN202310143353.6A Pending CN116178976A (en) | 2023-02-21 | 2023-02-21 | Preparation method of modified lignin and application of modified lignin in natural rubber |
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB709991A (en) * | 1951-03-01 | 1954-06-02 | Dunlop Rubber Co | Improvements in compounding rubber |
| FR1132027A (en) * | 1955-05-20 | 1957-03-04 | Us Rubber Co | Incorporation of lignin in artificial rubber |
| CN1044477A (en) * | 1989-12-19 | 1990-08-08 | 华南理工大学 | Utilize the method for xylogen as rubber reinforcing filler |
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| CN104448585A (en) * | 2014-11-28 | 2015-03-25 | 青岛科技大学 | Technology for processing ethylene propylene diene monomer rubber/polypropylene/lignin composite material |
| WO2015056758A1 (en) * | 2013-10-16 | 2015-04-23 | 住友ベークライト株式会社 | Resin composition and rubber composition |
| CN109796603A (en) * | 2018-11-19 | 2019-05-24 | 青岛中科和源新材料有限公司 | A kind of rubber phase solvent and preparation method thereof |
| CN110408180A (en) * | 2019-08-19 | 2019-11-05 | 南京工业大学 | A kind of Biodegradable polyester material and preparation method thereof that lignin-starch composition master batch is compound |
| CN111763358A (en) * | 2019-04-02 | 2020-10-13 | 中国石油化工股份有限公司 | Rubber composition containing rubber modifier, vulcanized rubber, and preparation method and application thereof |
| JP2021011559A (en) * | 2019-07-09 | 2021-02-04 | 大阪瓦斯株式会社 | Rubber-like composition and method for producing the same |
| US20210371630A1 (en) * | 2019-01-04 | 2021-12-02 | Suzano Canada Inc. | Lignin-enhanced butyl rubbers |
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2023
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