CN115490880A - Preparation method and application of modified lignin - Google Patents
Preparation method and application of modified lignin Download PDFInfo
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- CN115490880A CN115490880A CN202211237234.9A CN202211237234A CN115490880A CN 115490880 A CN115490880 A CN 115490880A CN 202211237234 A CN202211237234 A CN 202211237234A CN 115490880 A CN115490880 A CN 115490880A
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- lignin
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- 229920005610 lignin Polymers 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 24
- 238000012986 modification Methods 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 20
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 6
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract 8
- 238000006243 chemical reaction Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010063 rubber manufacturing process Methods 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 26
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000003014 reinforcing effect Effects 0.000 abstract description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 abstract 2
- 238000005303 weighing Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- -1 methoxyl groups Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 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
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Compounds Of Unknown Constitution (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to modified lignin, which comprises the following raw materials in parts by mass: 100 parts of lignin, 1-20 parts of a modification auxiliary agent A and 2-8 parts of a modification auxiliary agent B, wherein the modification auxiliary agent A comprises one or more of phenol, dimethylphenol, methylphenol, terephthalic acid and bisphenol A; the modification auxiliary agent 2 comprises one or more of melamine, toluene Diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). The invention also provides a preparation method of the modified lignin and application of the modified lignin in the field of rubber. The modified lignin prepared by the method is easy to crosslink with a rubber macromolecular chain, the tensile strength and the tearing strength of a rubber matrix are improved, and the reinforcing effect of lignin on the rubber matrix can be improved to a great extent.
Description
Technical Field
The invention relates to a preparation method and application of modified lignin, belonging to the technical field of material chemistry.
Background
The lignin is a non-crystalline, highly branched three-dimensional network phenol biological macromolecule containing aromatic rings. Lignin is widely present in higher plant cells, is the second renewable natural high-molecular polymer in the world in nature, and is second only to cellulose. It is estimated that about 5X 10 can be generated each year globally 8 -36×10 8 Ton. In plant body, lignin, cellulose, hemicellulose and the like form a supermolecular system together, and the ligninCellulose binds cellulose, enhancing the mechanical strength of the plant. The lignin has a complex structure, and although the complete structure of natural lignin is not known up to now, years of research show that lignin contains more active groups, such as aromatic groups, alcoholic hydroxyl groups, carboxyl groups, methoxyl groups, conjugated double bonds and the like, and has certain chemical activity. The lignin can be subjected to reactions such as grafting, crosslinking and the like with materials such as rubber, plastics and the like, 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 methoxyl, hydroxyl, carbonyl and other groups do not share electron pairs to form lignin-metal chelate in a coordination bond mode with metal ions, and a cross-linked network structure is built by utilizing the reaction activity of lignin molecules, so that the lignin plays a role in reinforcing and plasticizing.
Although lignin has a plurality of functional groups, the lignin has little reinforcing effect on rubber and can influence the strength of rubber products under certain conditions. Therefore, the lignin is modified by the hard-segment auxiliary agent, and the modified auxiliary agent has higher activity and is easy to crosslink the rubber macromolecular chains, so that the reinforcing effect of the lignin on the rubber matrix can be improved to a great extent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to modify lignin by using a hard segment auxiliary agent (modification auxiliary agent A), the modified lignin is easy to crosslink with a rubber macromolecular chain, and the reinforcing effect of the lignin on a rubber matrix can be improved to a great extent.
The technical scheme provided by the invention is as follows:
the modified lignin comprises the following raw materials in parts by mass: 100 parts of lignin, 1-20 parts of a modifying assistant A and 2-8 parts of a modifying assistant B;
the modification auxiliary agent A comprises one or more of phenol, dimethylphenol, methylphenol, terephthalic acid and bisphenol A;
the modification auxiliary agent B comprises one or more of melamine, toluene Diisocynate (TDI) and diphenylmethane diisocyanate (MDI).
A preparation method of modified lignin mainly comprises the following preparation steps:
step 1: dissolving lignin in an alkaline agent, adjusting the pH value to 8-13, and heating to a reaction temperature T1;
step 2: adding a modified auxiliary agent A to react for a certain time t1;
and 3, step 3: cooling to 50-60 ℃, adding an acidic solution, adjusting the system to be an acidic environment, adding a modification auxiliary agent B, and heating to the temperature T2 for reaction for a period of time T2;
and 4, step 4: washing, drying and crushing to obtain the modified lignin.
Preferably, the alkaline agent in step 1 is sodium hydroxide solution; the reaction temperature T1 is 80-100 ℃.
Preferably, the reaction time t1 in step 2 is 1-2h.
Preferably, the acidic solution in step 3 comprises hydrochloric acid and/or acetic acid; the pH of the acidic environment is 3-6.
Preferably, the reaction temperature T2 in the step 3 is 70-90 ℃; the reaction time t2 is 2-3h.
Preferably, the lignin in the step 4 has a pH of 6-8 after being washed with water.
Preferably, the particle size of the lignin prepared by the steps is as follows: d50 is less than or equal to 2 microns, and D100 is less than or equal to 10 microns.
The invention also provides application of the modified lignin as a rubber reinforcing agent in the rubber field.
In the invention, the modification auxiliary agent A is a hard segment substance, and the hardness of lignin can be improved due to the addition of the modification auxiliary agent A into the lignin, so that the reinforcement of a rubber matrix is also improved; the modification auxiliary agent B is a functional substance, and can increase the reactivity of lignin and polysulfide, disulfide or monosulfur bonds. After modification, the double bond and the sulfur bond can be opened by the functional group in the lignin, and then the lignin is connected and associated to the rubber matrix, so that the reinforcing effect of the lignin on the rubber is enhanced.
Compared with the prior art, the invention has the following advantages:
1. the modification auxiliary agent used in the invention has high unsaturation degree, and hydroxyl ions and hydrogen ions in the solvent can play a catalytic role, thereby being beneficial to the reaction of the auxiliary agent and the lignin macromolecules.
2. The modified auxiliary agent used in the invention has higher activity, and the prepared modified lignin as a rubber reinforcing agent is easy to crosslink with a rubber macromolecular chain, so that the reinforcing effect of a rubber matrix can be improved to a great extent.
3. The papermaking waste liquid is recycled, the current green development concept is met, and the environmental protection pressure is relieved.
4. The invention uses the alkalinity of the papermaking waste liquid as the catalyst, thereby reducing the cost input.
Detailed Description
The invention is further illustrated with reference to the following examples, without limiting the scope of the invention thereto.
Example 1
A preparation method of modified lignin mainly comprises the following preparation steps:
step 1, weighing 100 parts of lignin sample, adding the lignin sample into a reaction kettle, adding sodium hydroxide solution to completely dissolve the lignin, adjusting the pH to 8, starting stirring and heating to 90 ℃;
step 2, weighing 1 part of dimethyl phenol, adding into a reaction kettle, and reacting for 1.5h;
step 3, cooling to 55 ℃, adding hydrochloric acid to adjust the pH of the reaction environment to 3, adding 8 parts of TDI, heating to 80 ℃, and reacting for 3 hours;
and 4, after the reaction is finished, washing for 3 times by using deionized water until the pH value is 6, drying and then crushing.
Example 2
A preparation method of modified lignin mainly comprises the following preparation steps:
step 1, weighing 100 parts of lignin sample, adding the lignin sample into a reaction kettle, adding sodium hydroxide solution to completely dissolve the lignin, adjusting the pH value to 10, starting stirring, and heating to 100 ℃;
step 2, weighing 10 parts of phenol, adding into a reaction kettle, and reacting for 2 hours;
step 3, cooling to 60 ℃, adding hydrochloric acid, adjusting the pH value of the reaction environment to 4, adding 5 parts of melamine, heating to 70 ℃, and reacting for 2.5 hours;
and 4, after the reaction is finished, washing for 3 times by using deionized water until the pH value is 8, drying and then crushing.
Example 3
A preparation method of modified lignin mainly comprises the following preparation steps:
step 1, weighing 100 parts of lignin sample, adding the lignin sample into a reaction kettle, adding sodium hydroxide solution to completely dissolve the lignin, adjusting the pH to 13, starting stirring and heating to 80 ℃;
step 2, weighing 10 parts of methyl phenol and 10 parts of terephthalic acid, adding into a reaction kettle, and reacting for 1 hour;
step 3, cooling to 50 ℃, adding hydrochloric acid, adjusting the pH value of the reaction environment to 6, adding 2 parts of MDI, heating to 90 ℃, and reacting for 2 hours;
and 4, after the reaction is finished, washing for 3 times by using deionized water until the pH value is 6.5, drying, and then crushing.
Example 4
Step 1, weighing 100 parts of lignin sample, adding the lignin sample into a reaction kettle, adding sodium hydroxide solution to completely dissolve the lignin, adjusting the pH to 8, starting stirring and heating to 90 ℃;
step 2, weighing 1.3 parts of bisphenol A, adding into a reaction kettle, and reacting for 1.5 hours;
step 3, cooling to 55 ℃, adding hydrochloric acid, adjusting the pH value of the reaction environment to 3, adding 4 parts of melamine, heating to 80 ℃, and reacting for 3 hours;
and 4, after the reaction is finished, washing for 3 times by using deionized water until the pH value is 7.5, drying, and then crushing.
Example 5
Step 1, weighing 100 parts of lignin sample, adding the lignin sample into a reaction kettle, adding sodium hydroxide solution to completely dissolve the lignin, adjusting the pH value to 10, starting stirring and heating to 100 ℃;
step 2, weighing 5 parts of methyl phenol and 7 parts of dimethyl phenol, adding the mixture into a reaction kettle, and reacting for 2 hours;
step 3, cooling to 60 ℃, adding hydrochloric acid, adjusting the pH value of the reaction environment to 4, adding 2 parts of melamine and 5 parts of MDI, heating to 70 ℃, and reacting for 2.5 hours;
and 4, washing the reaction product for 3 times by using deionized water after the reaction is finished until the pH value is 7, drying the reaction product and then crushing the reaction product.
Comparative example 1
The comparative example is unmodified lignin.
Effects of the implementation
(1) Raw material formula for rubber preparation
The formula is as follows: 100 parts of natural rubber, 45 parts of carbon black, 10 parts of modified lignin/lignin, 2 parts of aromatic oil, 2 parts of stearic acid, 3 parts of zinc oxide, 1.5 parts of sulfur, 0.1 part of anti-coking agent and 1.4 parts of accelerator.
(2) Preparation method
The processing technology comprises the following steps:
1. adding natural rubber into an internal mixer for plastication for 1min at 40 ℃;
2. adding carbon black, lignin/modified lignin, and process oil, and mixing for 15min;
3. adding stearic acid and zinc oxide, mixing for 10min, and aging the materials on an open mill for 4h;
4. adding the rubber compound into an internal mixer, adding sulfur, an anti-scorching agent and an accelerator, mixing for 3min at the temperature of 80 ℃, setting the temperature of an open mill to be 60 ℃, performing thin-passing sizing on the mixed rubber material on the open mill, and then discharging and aging for at least 4h and at most 24h.
And (3) a vulcanization process: weighing a certain mass of rubber compound, and carrying out shaping vulcanization by using a mold with the thickness of 2mm, wherein the temperature of a vulcanizing machine is 140 ℃, the vulcanization time is 40min, and the pressure is 10MPa.
(3) Results of performance testing
The tensile strength and tear strength of the samples were tested according to GB/T528-2009 and GB/T529-2008, respectively.
The following are rubber property data for the examples and comparative examples.
Sample (I) | Tensile strength/MPa | Tear Strength/MPa |
Example 1 | 31.7 | 100 |
Example 2 | 31.0 | 121.2 |
Example 3 | 30.1 | 113.6 |
Example 4 | 30.9 | 123.4 |
Example 5 | 30.2 | 112.9 |
Comparative example 1 | 28.9 | 95 |
As can be seen from the above table, the tensile strength and tear strength of the rubber prepared by adding the modified lignin are significantly improved compared with the unmodified lignin.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. The modified lignin is characterized by comprising the following raw materials in parts by mass: 100 parts of lignin, 1-20 parts of a modification auxiliary agent A and 2-8 parts of a modification auxiliary agent B;
the modification auxiliary agent A comprises one or more of phenol, dimethylphenol, methylphenol, terephthalic acid and bisphenol A;
the modification auxiliary agent B comprises one or more of melamine, toluene Diisocynate (TDI) and diphenylmethane diisocyanate (MDI).
2. The method for preparing modified lignin according to claim 1, wherein the preparation steps mainly comprise:
step 1: dissolving lignin in an alkaline agent, adjusting the pH value to 8-13, and heating to a reaction temperature T1;
step 2: adding a modified auxiliary agent A to react for a certain time t1;
and step 3: cooling to 50-60 ℃, adding an acidic solution, adjusting the system to be an acidic environment, adding a modification auxiliary agent B, heating to a reaction temperature T2, and reacting for a period of time T2;
and 4, step 4: washing, drying and crushing to obtain the modified lignin.
3. The method for preparing modified lignin according to claim 2, wherein the alkaline agent in step 1 is sodium hydroxide solution; the reaction temperature T1 is 80-100 ℃.
4. The method for preparing modified lignin according to claim 2, wherein the reaction time t1 in step 2 is 1-2h.
5. The method for preparing modified lignin according to claim 2, wherein the acidic solution in step 3 comprises hydrochloric acid, acetic acid and their solutions, and the pH of the acidic environment is 3-6.
6. The method for preparing modified lignin according to claim 2, wherein the reaction temperature T2 in step 3 is 70-90 ℃ and the reaction time T2 is 2-3h.
7. The method for preparing modified lignin according to claim 2, wherein the lignin in step 4 has a pH of 6-8 after being washed with water.
8. Use of a modified lignin prepared by the method of any one of claims 1 to 7 in a rubber manufacturing process.
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CN116178976A (en) * | 2023-02-21 | 2023-05-30 | 上海昶法新材料有限公司 | Preparation method of modified lignin and application of modified lignin in natural rubber |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103509164A (en) * | 2013-07-23 | 2014-01-15 | 山东圣泉化工股份有限公司 | Lignin base reinforcing resin and preparation method thereof |
CN104592530A (en) * | 2015-01-05 | 2015-05-06 | 广西民族大学 | Preparation method of phenolated lignin amine cationic emulsifier |
WO2015147165A1 (en) * | 2014-03-28 | 2015-10-01 | 住友ベークライト株式会社 | Phenol-modified lignin resin, method for producing same, resin composition, rubber composition, and cured product |
CN111548532A (en) * | 2020-06-19 | 2020-08-18 | 南京林业大学 | Biomass intumescent flame retardant, preparation method and special device thereof |
CN111793456A (en) * | 2020-07-20 | 2020-10-20 | 广西众人投资有限公司 | Lignin modified phenolic glue and preparation method thereof |
CN113372877A (en) * | 2021-07-19 | 2021-09-10 | 深圳市洪欣巨供应链有限公司 | Modified lignin-based adhesive and preparation method thereof |
CN115819689A (en) * | 2022-12-30 | 2023-03-21 | 上海昶法新材料有限公司 | Preparation method and application of modified lignin |
-
2022
- 2022-10-10 CN CN202211237234.9A patent/CN115490880B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103509164A (en) * | 2013-07-23 | 2014-01-15 | 山东圣泉化工股份有限公司 | Lignin base reinforcing resin and preparation method thereof |
WO2015147165A1 (en) * | 2014-03-28 | 2015-10-01 | 住友ベークライト株式会社 | Phenol-modified lignin resin, method for producing same, resin composition, rubber composition, and cured product |
CN104592530A (en) * | 2015-01-05 | 2015-05-06 | 广西民族大学 | Preparation method of phenolated lignin amine cationic emulsifier |
CN111548532A (en) * | 2020-06-19 | 2020-08-18 | 南京林业大学 | Biomass intumescent flame retardant, preparation method and special device thereof |
CN111793456A (en) * | 2020-07-20 | 2020-10-20 | 广西众人投资有限公司 | Lignin modified phenolic glue and preparation method thereof |
CN113372877A (en) * | 2021-07-19 | 2021-09-10 | 深圳市洪欣巨供应链有限公司 | Modified lignin-based adhesive and preparation method thereof |
CN115819689A (en) * | 2022-12-30 | 2023-03-21 | 上海昶法新材料有限公司 | Preparation method and application of modified lignin |
Non-Patent Citations (1)
Title |
---|
TON THAT MINH TAN: ""Cardanol-Lignin-Based Polyurethanes"", 《POLYMER INTERNATIONAL》, vol. 41, no. 1, pages 13 - 16 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116178976A (en) * | 2023-02-21 | 2023-05-30 | 上海昶法新材料有限公司 | Preparation method of modified lignin and application of modified lignin in natural rubber |
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