CN103509164A - Lignin base reinforcing resin and preparation method thereof - Google Patents
Lignin base reinforcing resin and preparation method thereof Download PDFInfo
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- CN103509164A CN103509164A CN201310310819.3A CN201310310819A CN103509164A CN 103509164 A CN103509164 A CN 103509164A CN 201310310819 A CN201310310819 A CN 201310310819A CN 103509164 A CN103509164 A CN 103509164A
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Abstract
The invention relates to a lignin base reinforcing resin and a preparation method thereof. The lignin base reinforcing resin comprises the following components: phenolic compounds, an acidic catalyst, lignin, turpentine and aldehyde compounds. According to the invention, through combination of lignin with phenolic resin and the participation of turpentine, the reinforcing resin has good compatibility with rubber, so as to improve the machining performance of rubber. Practice has proved that the rubber added with the resin has obvious hardening reinforcement effect and thickening effect, and the yield of resin is increased by 10-45%, so as to greatly reduce the cost of resin.
Description
Technical field
The present invention relates to organic high molecular compound field, be specifically related to a kind of preparation method of biomass-based reinforced resin and the product obtaining.
Background technology
Resol is also bakelite, claim again bakelite, there is good acid resistance, mechanical property, resistance toheat, be widely used in the industries such as anticorrosion engineering, sizing agent, fire retardant material, grinding wheel manufacture, the preparation method of resol is mainly polycondensation under catalyzer condition by phenol and formaldehyde at present, through neutralizing, washing, make, but because phenol and formaldehyde reaction in above-mentioned reaction process are incomplete, the residual phenol completely of meeting and formaldehyde in resol, free phenol and free aldehyde are discharged in air can affect atmospheric environment and HUMAN HEALTH.
Xylogen claims again lignin, is a ubiquitous class fragrant superpolymer in plant materials, contains the various active functional groups such as aromatic base, phenolic hydroxyl group, alcoholic extract hydroxyl group, carbonyl, methoxyl group, carboxyl and conjugated double bond in lignin molecule.Xylogen and Mierocrystalline cellulose, hemicellulose are bonded together the primary structure that forms plant, have the effect of strengthening wood fibre, and it is next in number only to the abundant organic polymer of Mierocrystalline cellulose ，Wei vegitabilia second.The content of xylogen in timber is generally 20-40%, and in Gramineae plant, xylogen is generally low than timber to content, is 15-25%.
Xylogen is applied to rubber industry, as a kind of natural strengthening agent, has done a large amount of reports both at home and abroad, such as: sulfonated lignin are as rubber modifier, and it can effectively reduce heat-dissipating, obviously reduce volume abrasion, and have good Efficient Adhesive Promotion.
At present, the most of reaction raw materials of lignin modification resol are phenol, xylogen, catalyzer and aldehyde, it is the preparation method that example: CN201210557028.6 discloses a kind of lignin modification resol performed polymer that its preparation process be take patent below, be specially: 100 parts of lignin compounds, phenolic compound 10-200 part and an acidic catalyst are mixed, be heated to 180 ℃ of-350 ℃ of reactions, obtain mixed reaction solution; Described mixed reaction solution is mixed with formaldehyde, after polycondensation reflection, obtain lignin phenol formaldehyde resin performed polymer, wherein the mol ratio of formaldehyde and phenolic compound is 0.1-0.8:1.
CN03113395.9 discloses a kind of hbs lignin derivative as modified rubber auxiliary agent, and its raw material is high-boiling alcohol lignin, utilize its active group and aldehydes, phenols, halogenation or with other monomer-grafted formation derivatives.Embodiment is: the high xylogen that boils of 100g, with ω=10% aqueous sodium hydroxide solution 40g, dissolve, be diluted with water to 1000ml, be heated to 95 ℃, slowly drip respectively 0.3mol or 0.6mol formaldehyde, isothermal reaction 2h, adds the aqueous sulfuric acid 98g of ω=5% to make after dry 12h, to make containing the few HBS xylogen I of formaldehyde amount with containing the many HBS xylogen II modifications of formaldehyde amount and set and refer in xylogen precipitation, filtration, washing, 60 ℃ of baking ovens after completion of the reaction.
But itself and rubber compatibility problem are restricting the industrial application of xylogen all the time, improving xylogen rubber compatibility is the key that solves this problem.Approach one, extends mixing time; Approach two, lignin modification, comprise: formaldehyde, diatomite (CN200910043023.X, lignin-modified diatomite, the mass ratio of diatomite and xylogen is 10:1-1:10), kaolin is (as CN200910043022.5, lignin-modified kaolin, the mass ratio of kaolin and xylogen is 10:1-1:10), the modified lignin resin such as wilkinite (CN200910304645.3), latex.Though above two kinds of approach can solve consistency, but extending mixing time will increase tooling cost, and not be very large to performance impact; And go up at double through the xylogen cost of modification, cause its industrial application stranded because considering cost.
Turps (turpentine), is a kind of of essential oil, is terpenes mixture, and main component is firpene, can make from rosin, pine torch or the processing of sulphate process pine pulp gas phlegma.
Terebinthine main component is sesquiterpene, and the method by turps for improvement of resol is confirmed, and it is mainly the contraposition of the phenolic hydroxyl group in resol or faces position and is connected with a terpenes molecule, and this step is hydrocarbylation or alkylation.
Terpene phenolic resin, 130～150 ℃ of softening temperatures.Contain polar group, there is bonding force strong, nontoxic odorless, ageing-resistant, resistance to diluted acid, diluted alkaline, heat-resisting, fast light, the superperformance such as electrical insulating property is strong is good to intermiscibilities such as synthetic rubber, SBS resin, SIS resins.
(the Su Tao etc. such as Su Tao, with turps or Heavy turpentine, prepare high softening-point terpene phenolic resin, chemistry of forest product and industry, in September, 1998, 18 volumes (3): 39-47) having disclosed the method for preparing terpene phenolic resin is: the mol ratio of phenolic aldehyde is 1:0.75-0.9, melting phenol (1mol) and formaldehyde are added in there-necked flask, flask is furnished with the mechanical stirring with tightness system, reflux exchanger and thermometer, add concentrated hydrochloric acid 0.5mL, be heated with stirring to 100 ℃ of water reflux temperatures, after certain hour, material is divided into two of water and resins, complete the synthetic of resol, then add vitriol oil 0.4mL, by phenol and terpenes molecular ratio, be that 1:1-1:2 left and right adds turps or Heavy turpentine, between flask and reflux exchanger, insert a water trap, the water distillating while heating up to get rid of, be warming up to the boiling point of reactant, after reaching 170 ℃, temperature can take the circumstances into consideration to add sulfuric acid, reactant continues reflection for some time after being homogeneous phase, alkylation stage carries out a moon 3-10h, (turps needs 3-6h, Heavy turpentine needs 5-10h).
CN93105520.2 (publication number is CN1077462A) discloses the method for manufacturing rosin modified phenolic resin with rosin, be about to after rosin dissolving, magnesium oxide and the alkali metal lithium compound of significant quantity of take is catalyzer, directly and phenol and formaldehyde consolute generation condensation, addition reaction, the mole ratio of the present invention and formaldehyde is 1:1.2-2.0, and the dehydration that heats up afterwards, fractionates out byproduct turps, use again glycerine esterification, can obtain rosin products of light color, that softening temperature is high, oil soluble is good.
CN88101794.9(publication number is 1034932A) relate to the method for manufacturing light oil soluble terpene phenolic resin, under an acidic catalyst effect, by adding, make phenol and formaldehyde condensation, then with terpenes, carry out hydrocarbonylation, temperature of reaction is 95-210 ℃, when temperature of reaction reaches 160-210 ℃, add appropriate discoloring agent, and distill out low boiling component.Described alkylating agent is gum turpentine.
Resol is because of space steric effect, with turps level of response is very low or the reaction times is long.
Therefore, need to provide that a kind of to accelerate the turps reaction times shorter, and can improve the resin of resin and rubber compatibility.
Summary of the invention
For the deficiencies in the prior art part, the object of this invention is to provide a kind of lignin-base reinforced resin.By xylogen, synthesize reinforcement resol, and introduce turps, to reach the consistency good with rubber, thereby reach the effect of reinforcement.
Another object of the present invention is to propose the reinforced resin that described preparation method obtains.
The concrete technical scheme that realizes above-mentioned purpose of the present invention is:
A kind of lignin-base reinforced resin provided by the invention, its raw material contains following composition: phenolic compound, an acidic catalyst, xylogen, turps and aldehyde compound.
Concrete, in its raw material:
The molar ratio of described phenolic compound, aldehyde compound is 1:0.5-0.8, is preferably 1:0.5-0.75;
Described an acidic catalyst, xylogen and terebinthine consumption be 0.5-5%, 5-50%, the 5-30% of the quality of phenolic compound respectively, is preferably 3-4.2%, 13-40%, 10-20%.
In above-mentioned lignin-base reinforced resin raw material:
Described phenolic compound is one or more in phenol, cresols, alkylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol or pyrocatechol, preferably phenol.
Described an acidic catalyst is one or more in oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid, thionamic acid, is preferably oxalic acid or tosic acid;
Described xylogen is sulfonated lignin, alkali lignin, acidolysis xylogen, acidolysis xylogen or high-boiling alcohol lignin etc.Xylogen is a kind of complicated phenol polymer being formed by four kinds of alcohol monomers (to tonquinol, lubanol, 5-hydroxyl lubanol, sinapyl alcohol).Wherein, sulfonated lignin claims again sulfonated lignin, is the byproduct of sulphite process papermaking wood pulp, is linear polymer; Alkali lignin is the xylogen extracting from plant tissue with alkali; The acidolysis such as sulfuric acid, hydrochloric acid xylogen is acidolysis xylogen; High-boiling alcohol lignin is the xylogen extracting from plant by the high alcohol method of boiling.Preferred bases xylogen.
Described aldehyde compound is one or more in formaldehyde, acetaldehyde, furfural, paraformaldehyde, preferably formaldehyde.
Described turps is light oil or superfine turps.
The present invention also provides a kind of method of preparing lignin-base reinforced resin, and the method comprises the following steps:
1) phenolic compound, an acidic catalyst and xylogen are mixed to 100-300 ℃ of pre-treatment 2-4h;
2) in step 1) gained intermediate, add turps, at temperature 120-150 ℃, reaction 1.5-2.5h;
3) to step 2) add aldehyde compound in gained reaction mixture, at temperature 100-110 ℃, carry out the condensation reaction of 2-3h.
In described method:
Described step 1), in, phenolic compound, catalyzer and xylogen be 100-300 ℃ of pre-treatment 2-4h in encloses container, is preferably 120-260 ℃, 3-4h.
After described step 3) has been reacted, also comprise dehydration and vacuumize step.
The present invention also provides the index of above-mentioned lignin-base reinforced resin: molecular weight is 1200-1800, and free phenol is 0.2-1.0%, and it is 50-60% that the mass ratio 2:8 mixing abrasive dust of take with urotropine records carbon residue rate at 800 ℃.
The present invention also provides the application of above-mentioned lignin-base reinforced resin in preparing rubber.
In described application, the formula of rubber is:
Described rubber adopts two-part calendering process, and this technique comprises the following steps:
| First paragraph | At 90rpm/90 ℃, start mixing |
| 0'' | Rubber |
| 30'' | Add 2/3 filler |
| 1'30'' | Add residue 1/3 filler |
| 2' | Cleaning |
| 3' | Small powder outside oiling and vulcanization accelerator |
| 4' | Cleaning |
| 5' | Binder removal |
| ? | At mill fluctuating plate, at room temperature park at least 2 hours |
| Second segment | 60rpm/60℃ |
| 0'' | First paragraph rubber master batch is dropped into Banbury mixer |
| 30" | Add vulcanization accelerator |
| 2' | Binder removal |
| ? | In mill, thin-pass is three times, lower |
Lignin-base reinforced resin provided by the invention and preparation method thereof has following beneficial effect:
1, the present invention is combined with resol by xylogen, in terebinthine presence, this reinforced resin can have good consistency with rubber, thereby the machining property of improving rubber, facts have proved, added the rubber item of this resin, Hardening reinforcing effect is obvious, and having Efficient Adhesive Promotion, resin yield has improved 10～45%, greatly reduces resin cost.
2, lignin-base reinforced resin provided by the invention is by adding xylogen and turps, reinforcing effect to triangular rubber core is obvious, the tear resistance of rubber and hardness are significantly improved, and aging resistance has a clear superiority in, thereby has improved the machining property of rubber.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1: lignin-base reinforced resin
120g phenol (1.28mol) is dropped in four-hole boiling flask, under reflux state, add oxalic acid 5g, add xylogen 30g after stirring, be heated to 130 ℃, isothermal reaction 4h, is cooled to 80 ℃, drops into turps 13g, is warming up to 120 ℃ of reaction 2h; Be cooled to 90 ℃, the formaldehyde 68g(0.84mol that dropping massfraction is 37%); After dropwising, be warming up to 100 ℃ of back flow reaction 2h; Intensification is dewatered to 160 ℃, is evacuated to relative vacuum degree to be-0.098Mpa, sloughs free phenol, makes rosin products.
This resin index: gel chromatography records molecular weight (Mw) 1439, and vapor phase process records free phenol 0.71, it is 54.6% that the mass ratio 2:8 mixing abrasive dust of take with urotropine records carbon residue rate at 800 ℃.
Embodiment 2: lignin-base reinforced resin
100g phenol (1.06mol) is dropped in four-hole boiling flask, under reflux state, add tosic acid 3g, after stirring, add xylogen 15g, be heated to 150 ℃, isothermal reaction 3h; Be cooled to 80 ℃, drop into turps 15g, be warming up to 135 ℃ of reaction 2h; Be cooled to 90 ℃, the formaldehyde 65g(0.80mol that dropping massfraction is 37%); After dropwising, be warming up to 100 ℃ of back flow reaction 2.5h; Be cooled to 80 ℃, add barium hydroxide 5.49g with in and tosic acid; Be warming up to 160 ℃ of dehydrations, be evacuated to relative vacuum degree for-0.098Mpa, slough free phenol, make rosin products.
This resin index: gel chromatography records molecular weight (Mw) 1583, and vapor phase process records free phenol 0.67, it is 55.3% that the mass ratio 2:8 mixing abrasive dust of take with urotropine records carbon residue rate at 800 ℃.
Embodiment 3: lignin-base reinforced resin
150g phenol (1.60mol) is dropped in four-hole boiling flask, under reflux state, add oxalic acid 5g, after stirring, add xylogen 20g, be heated to 150 ℃, isothermal reaction 2h; Be cooled to 80 ℃, drop into turps 15g, be warming up to 135 ℃ of reaction 2h; Be cooled to 90 ℃, the formaldehyde 65g(0.80mol that dropping massfraction is 37%); After dropwising, be warming up to 100 ℃ of back flow reaction 2.5h; Intensification is dewatered to 160 ℃, is evacuated to relative vacuum degree to be-0.098Mpa, sloughs free phenol, makes rosin products.
This resin index: gel chromatography records molecular weight (Mw) 1594, and vapor phase process records free phenol 0.48, it is 56.6% that the mass ratio 2:8 mixing abrasive dust of take with urotropine records carbon residue rate at 800 ℃.
Embodiment 4: lignin-base reinforced resin
150g phenol (1.60mol) is dropped in four-hole boiling flask, under reflux state, add tosic acid 5.25g, after stirring, add xylogen 60g, be heated to 160 ℃, isothermal reaction 3h; Be cooled to 80 ℃, drop into turps 30g, be warming up to 150 ℃ of reaction 2h; Be cooled to 90 ℃, the formaldehyde 75g(0.925mol that dropping massfraction is 37%); After dropwising, be warming up to 100 ℃ of back flow reaction 2h; Be cooled to 80 ℃, add in barium hydroxide 9.61g and tosic acid; Intensification is dewatered to 160 ℃, is evacuated to relative vacuum degree to be-0.098Mpa, sloughs free phenol, makes rosin products.
This resin index: gel chromatography records molecular weight (Mw) 1590, and vapor phase process records free phenol 0.85, it is 54.2% that the mass ratio 2:8 mixing abrasive dust of take with urotropine records carbon residue rate at 800 ℃.
The lignin-base reinforced resin making in above embodiment 1-4, for the preparation of rubber product, is used triangular rubber core technical recipe shown in table 1, adopts two-part calendering process sample preparation shown in table 2, and the performance test results of gained rubber product is as shown in table 3:
Table 1: the two-part calendering process formula of preparing rubber
Table 2: the two-part calendering process of preparing rubber
| First paragraph | At 90rpm/90 ℃, start mixing |
| 0'' | Rubber |
| 30'' | Add 2/3 filler |
| 1'30'' | Add residue 1/3 filler |
| 2' | Cleaning |
| 3' | Small powder outside oiling and vulcanization accelerator |
| 4' | Cleaning |
| 5' | Binder removal |
| ? | At mill fluctuating plate, at room temperature park at least 2 hours |
| Second segment | 60rpm/60℃ |
| 0'' | First paragraph rubber master batch is dropped into Banbury mixer |
| 30" | Add vulcanization accelerator |
| 2' | Binder removal |
| ? | In mill, thin-pass is three times, lower |
Table 3: the embodiment gained resin of take makes the performance perameter of rubber as component
Comparative example 1
Use triangular rubber core technical recipe (only not adding lignin-base reinforced resin and urotropine component) shown in table 1, adopt two-part calendering process sample preparation shown in table 2, obtain rubber product.
Comparative example 2
100g phenol is dropped in four-hole boiling flask, under reflux state, add tosic acid 2g, be cooled to 80 ℃, drop into turps 13g, be warming up to 120 ℃ of reaction 2h; Be cooled to 90 ℃, the formaldehyde 60g that dropping massfraction is 37%; After dropwising, be warming up to 100 ℃ of back flow reaction 2.5h; Be cooled to 80 ℃, add barium hydroxide 3.66g with in and tosic acid; Be warming up to 160 ℃ of dehydrations, be evacuated to relative vacuum degree for-0.098Mpa, slough free phenol, make rosin products.
Use triangular rubber core technical recipe shown in table 1, adopt two-part calendering process sample preparation shown in table 2, obtain rubber product.
Comparative example 3
100g phenol is dropped in four-hole boiling flask, under reflux state, add tosic acid 2g, after stirring, add xylogen 20g, be heated to 150 ℃, isothermal reaction 3h; Be cooled to 90 ℃, the formaldehyde 60g that dropping massfraction is 37%; After dropwising, be warming up to 100 ℃ of back flow reaction 2.5h; Be cooled to 80 ℃, add barium hydroxide 3.66g with in and tosic acid; Be warming up to 160 ℃ of dehydrations, be evacuated to relative vacuum degree for-0.098Mpa, slough free phenol, make rosin products.
Use mining area tyre surface technical recipe shown in table 1, adopt two-part calendering process sample preparation shown in table 2, obtain rubber product.
Table 4: made rubber performance parameter comparison in made rubber and embodiment 1 in comparative example
In comparative example 1 rubber compounding, do not add resol;
In comparative example 2 rubber compoundings, added resol, resol has wherein added turps;
In comparative example 3 rubber compoundings, added resol, resol process lignin modification wherein, but do not add turps;
In embodiment 1 rubber compounding, added and added xylogen and terebinthine resol.
Except above difference, basic identical in the preparation process of resol and embodiment 1 in comparative example 2 and comparative example 3.
In table 4, it is known that in comparative example 1,2,3 made rubber and embodiment 1, the performance perameter of made rubber forms contrast: by adding xylogen and turps, tear resistance and the hardness of rubber significantly improve, and aging resistance has a clear superiority in.
Experimental results show that: lignin-base reinforced resin provided by the invention is by adding xylogen and turps, reinforcing effect to triangular rubber core is obvious, the tear resistance of rubber and hardness are significantly improved, and aging resistance has a clear superiority in, thereby has improved the machining property of rubber.
Although, above used general explanation, embodiment and test, the present invention is described in detail, on basis of the present invention, can make some modifications or improvements it, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a lignin-base reinforced resin, its raw material contains following composition: phenolic compound, an acidic catalyst, xylogen, turps and aldehyde compound.
2. lignin-base reinforced resin according to claim 1, is characterized in that, the molar ratio of described phenolic compound, aldehyde compound is 1:0.5-0.8.
3. lignin-base reinforced resin according to claim 2, is characterized in that, the molar ratio of described phenolic compound, aldehyde compound is 1:0.5-0.75.
4. lignin-base reinforced resin according to claim 2, is characterized in that, described an acidic catalyst, xylogen and terebinthine consumption be 0.5-5%, 5-50%, the 5-30% of the quality of phenolic compound respectively.
5. lignin-base reinforced resin according to claim 4, is characterized in that, is 3-4.2%, 13-40%, 10-20%.
6. according to the lignin-base reinforced resin described in claim 1-5 any one, it is characterized in that, described phenolic compound is one or more in phenol, cresols, alkylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol or pyrocatechol, preferably phenol; Described an acidic catalyst is one or more in oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid, thionamic acid, is preferably oxalic acid or tosic acid; Described xylogen is sulfonated lignin, alkali lignin, acidolysis xylogen, acidolysis xylogen or high-boiling alcohol lignin; Described aldehyde compound is one or more in formaldehyde, acetaldehyde, furfural, paraformaldehyde, preferably formaldehyde; Described turps is light oil or superfine turps.
7. a method of preparing lignin-base reinforced resin described in claim 1-6 any one, is characterized in that, the method comprises the following steps:
1) phenolic compound, an acidic catalyst and xylogen are mixed to 100-300 ℃ of pre-treatment 2-4h;
2) in step 1) gained intermediate, add turps, at temperature 120-150 ℃, reaction 1.5-2.5h;
3) to step 2) add aldehyde compound in gained reaction mixture, at temperature 100-110 ℃, carry out the condensation reaction of 2-3h.
8. method according to claim 7, is characterized in that, described step 1) in, phenolic compound, catalyzer and xylogen be 100-300 ℃ of pre-treatment 2-4h in encloses container, is preferably 120-260 ℃, 3-4h.
9. method according to claim 7, is characterized in that, after described step 3) has been reacted, also comprises dehydration and vacuumizes step.
10. the application of the lignin-base reinforced resin described in claim 1-6 any one in preparing rubber.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105873970A (en) * | 2014-03-28 | 2016-08-17 | 住友电木株式会社 | Phenol-modified lignin resin, method for producing same, resin composition, rubber composition, and cured product |
| CN106008867A (en) * | 2016-05-24 | 2016-10-12 | 上海橡瑞新材料科技有限公司 | Preparation method for lignin-modified phenolic tackifying resin for rubber |
| CN115490880A (en) * | 2022-10-10 | 2022-12-20 | 上海昶法新材料有限公司 | Preparation method and application of modified lignin |
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| CN1034932A (en) * | 1988-03-25 | 1989-08-23 | 福建省龙岩地区林产工业公司 | The manufacture method of terpene phenolic resin |
| CN101725776A (en) * | 2009-12-11 | 2010-06-09 | 张仲伦 | Lignin reinforcing filled butadiene-acrylonitrile rubber hose |
| CN103319672A (en) * | 2013-06-27 | 2013-09-25 | 山东圣泉化工股份有限公司 | Tear resistant phenolic resin and preparation method thereof |
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2013
- 2013-07-23 CN CN201310310819.3A patent/CN103509164B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034932A (en) * | 1988-03-25 | 1989-08-23 | 福建省龙岩地区林产工业公司 | The manufacture method of terpene phenolic resin |
| CN101725776A (en) * | 2009-12-11 | 2010-06-09 | 张仲伦 | Lignin reinforcing filled butadiene-acrylonitrile rubber hose |
| CN103319672A (en) * | 2013-06-27 | 2013-09-25 | 山东圣泉化工股份有限公司 | Tear resistant phenolic resin and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105873970A (en) * | 2014-03-28 | 2016-08-17 | 住友电木株式会社 | Phenol-modified lignin resin, method for producing same, resin composition, rubber composition, and cured product |
| CN105873970B (en) * | 2014-03-28 | 2019-09-10 | 住友电木株式会社 | Phenol modified lignin resin resin and its manufacturing method and resin combination, rubber composition and solidfied material |
| CN106008867A (en) * | 2016-05-24 | 2016-10-12 | 上海橡瑞新材料科技有限公司 | Preparation method for lignin-modified phenolic tackifying resin for rubber |
| CN115490880A (en) * | 2022-10-10 | 2022-12-20 | 上海昶法新材料有限公司 | Preparation method and application of modified lignin |
| CN115490880B (en) * | 2022-10-10 | 2023-11-21 | 上海昶法新材料有限公司 | Preparation method and application of modified lignin |
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