CN103509164B - Lignin base reinforcing resin and preparation method thereof - Google Patents
Lignin base reinforcing resin and preparation method thereof Download PDFInfo
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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 field of organic polymer compound, the preparation method being specifically related to a kind of biomass-based reinforced resin and the product obtained.
Background technology
Resol is also bakelite, also known as 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, preparation method's mainly polycondensation under catalysts conditions by phenol and formaldehyde of current resol, through neutralization, wash and make, but due to phenol in above-mentioned reaction process and formaldehyde reaction incomplete, can remain phenol and formaldehyde completely in resol, free phenol and free aldehyde are discharged in air and can affect atmospheric environment and HUMAN HEALTH.
Xylogen, also known as lignin, is a ubiquitous class fragrant superpolymer in plant materials, containing various active functional groups such as aromatic base, phenolic hydroxyl group, alcoholic extract hydroxyl group, carbonyl, methoxyl group, carboxyl and conjugated double bonds in lignin molecule.Xylogen and Mierocrystalline cellulose, hemicellulose are bonded together the primary structure forming plant, and have the effect of strengthening wood fibre, it is next in number only to Mierocrystalline cellulose, are the organic polymer that vegitabilia second is abundant.Xylogen content is in wood 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 reduces volume worn, and have good Efficient Adhesive Promotion.
At present, the most of reaction raw materials of lignin modification resol is phenol, xylogen, catalyzer and aldehyde, its preparation process discloses a kind of preparation method of lignin modification resol performed polymer for patent: CN201210557028.6 below, be specially: by lignin compound 100 parts, phenolic compound 10-200 part and an acidic catalyst mixing, be heated to 180 DEG C-350 DEG C reactions, obtain mixed reaction solution; Mixed with formaldehyde by described mixed reaction solution, obtain lignin phenol formaldehyde resin performed polymer after polycondensation reflection, wherein the mol ratio of formaldehyde and phenolic compound is 0.1-0.8:1.
CN03113395.9 discloses and is a kind ofly used as the hbs lignin derivative of 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, dissolve with ω=10% aqueous sodium hydroxide solution 40g, be diluted with water to 1000ml, be heated to 95 DEG C, slowly drip 0.3mol or 0.6mol formaldehyde respectively, isothermal reaction 2h, the aqueous sulfuric acid 98g adding ω=5% after completion of the reaction make to obtain after dry 12h in lignin deposit, filtration, washing, 60 DEG C of baking ovens and refer to containing the few HBS xylogen I of formaldehyde amount with containing the HBS xylogen II modification tree that formaldehyde amount is many.
But itself and rubber compatibility problem govern the industrial application of xylogen all the time, improving xylogen rubber compatibility is the key solving 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 the one of essential oil, is terpenes mixture, and main component is firpene, can be obtained from the processing of rosin, pine torch or sulphate process pine pulp gas phlegma.
Terebinthine main component is sesquiterpene, the method for turps for improvement of resol is confirmed, and it is mainly the contraposition of the phenolic hydroxyl group in resol or faces position and be connected with a terpenes molecule, and this step is hydrocarbylation or alkylation.
Terpene phenolic resin, softening temperature 130 ~ 150 DEG C.Containing polar group, there is bonding force strong, nontoxic odorless, ageing-resistant, resistance to diluted acid, diluted alkaline, heat-resisting, fast light, the superperformances such as electrical insulating property is strong are good to intermiscibilities such as synthetic rubber, SBS resin, SIS resins.
(the Su Tao etc. such as Su Tao, high softening-point terpene phenolic resin is prepared with turps or Heavy turpentine, chemistry of forest product and industry, in September, 1998, 18 volumes (3): 39-47) disclose the method preparing terpene phenolic resin and be: 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 of band tightness system, reflux exchanger and thermometer, add concentrated hydrochloric acid 0.5mL, be heated with stirring to water reflux temperature 100 DEG C, after certain hour, material is divided into water and resin two, complete the synthesis of resol, then vitriol oil 0.4mL is added, be that about 1:1-1:2 adds turps or Heavy turpentine by phenol and terpenes molecular ratio, a water trap is inserted between flask and reflux exchanger, the water distillated during to get rid of and to heat up, be warming up to the boiling point of reactant, can take the circumstances into consideration to add sulfuric acid after temperature reaches 170 DEG C, reactant is continue reflection for some time after 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 manufacturing rosin modified phenolic resin with rosin, after dissolving by rosin, with the magnesium oxide of significant quantity and alkali metal lithium compound for 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 heat up dehydration afterwards, fractionates out byproduct turps, use glycerine esterification again, of light color, that softening temperature is high, oil soluble is good rosin products can be obtained.
CN88101794.9(publication number is 1034932A) relate to the method manufacturing light oil soluble terpene phenolic resin, namely under an acidic catalyst effect, phenol and formaldehyde condensation is made by adding, then hydrocarbonylation is carried out with terpenes, temperature of reaction is 95-210 DEG C, when temperature of reaction reaches 160-210 DEG C, add appropriate discoloring agent, and distill out low boiling component.Described alkylating agent is gum turpentine.
Resol because space steric effect, with turps level of response is very low or the reaction times is long.
Therefore, need to provide one can accelerate the turps reaction times shorter, and the resin of resin and rubber compatibility can be improved.
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 lignin synthesis reinforcement resol, and introduce turps, to reach the consistency good with rubber, thus reach the effect of reinforcement.
Another object of the present invention is the reinforced resin that the described preparation method of proposition obtains.
The concrete technical scheme realizing 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;
0.5-5%, 5-50%, 5-30% of the quality of described an acidic catalyst, xylogen and terebinthine consumption difference phenolic compound, be 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, preferred 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 the complicated phenol polymer of one formed by four kinds of alcohol monomers (to tonquinol, lubanol, 5-hydroxyl lubanol, sinapyl alcohol).Wherein, sulfonated lignin, also known as sulfonated lignin, is the byproduct of sulphite process papermaking wood pulp, is linear polymer; Alkali lignin is the xylogen extracted from plant tissue with alkali; The acidolysis such as sulfuric acid, hydrochloric acid xylogen is acidolysis xylogen; High-boiling alcohol lignin is the xylogen extracted from plant by high alcohol method of boiling.Preferred bases xylogen.
Described aldehyde compound is one or more in formaldehyde, acetaldehyde, furfural, paraformaldehyde, preferred formaldehyde.
Described turps is light oil or superfine turps.
Present invention also offers a kind of method preparing lignin-base reinforced resin, the method comprises the following steps:
1) phenolic compound, an acidic catalyst and xylogen are mixed, 100-300 DEG C of pre-treatment 2-4h;
2) in step 1) gained intermediate, turps is added, at temperature 120-150 DEG C, reaction 1.5-2.5h;
3) to step 2) add aldehyde compound in gained reaction mixture, at temperature 100-110 DEG C, carry out the condensation reaction of 2-3h.
In described method:
Described step 1) in, phenolic compound, catalyzer and xylogen be 100-300 DEG C of pre-treatment 2-4h in encloses container, is preferably 120-260 DEG C, 3-4h.
After described step 3) has been reacted, also comprise dehydration and vacuum step.
Present invention also offers the index of above-mentioned lignin-base reinforced resin: molecular weight is 1200-1800, free phenol is 0.2-1.0%, and at recording 800 DEG C with urotropine with mass ratio 2:8 mixing abrasive dust, Residual carbon is for 50-60%.
Present invention also offers above-mentioned lignin-base reinforced resin and prepare the application in 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 | Start mixing at 90rpm/90 DEG C |
| 0'' | Rubber |
| 30'' | Add 2/3 filler |
| 1'30'' | Add residue 1/3 filler |
| 2' | Cleaning |
| 3' | Refuel and vulcanization accelerator outside small powder |
| 4' | Cleaning |
| 5' | Binder removal |
| Bottom sheet on a mill until, at room temperature parks 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 |
| Thin-pass three times on a mill until, bottom sheet |
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, thus improve the machining property of rubber, facts have proved, with the addition of the rubber item of this resin, Hardening reinforcing effect is obvious, and having Efficient Adhesive Promotion, resin yield improves 10 ~ 45%, greatly reduces resin cost.
2, lignin-base reinforced resin provided by the invention is by adding xylogen and turps, obvious to the reinforcing effect of triangular rubber core, significantly improve the tear resistance of rubber and hardness, aging resistance has a clear superiority in, thus improves the machining property of rubber.
Embodiment
Following examples for illustration of 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, adds oxalic acid 5g, after stirring, add xylogen 30g, be heated to 130 DEG C, isothermal reaction 4h, be cooled to 80 DEG C, drop into turps 13g, be warming up to 120 DEG C of reaction 2h; Be cooled to 90 DEG C, drip the formaldehyde 68g(0.84mol that massfraction is 37%); After dropwising, be warming up to 100 DEG C of back flow reaction 2h; Heat up dehydration to 160 DEG C, and being evacuated to relative vacuum degree is-0.098Mpa, sloughs free phenol, obtained rosin products.
This resin index: gel chromatography records molecular weight (Mw) 1439, and vapor phase process records free phenol 0.71, at recording 800 DEG C with urotropine with mass ratio 2:8 mixing abrasive dust, Residual carbon is for 54.6%.
Embodiment 2: lignin-base reinforced resin
100g phenol (1.06mol) is dropped in four-hole boiling flask, under reflux state, adds tosic acid 3g, after stirring, add xylogen 15g, be heated to 150 DEG C, isothermal reaction 3h; Be cooled to 80 DEG C, drop into turps 15g, be warming up to 135 DEG C of reaction 2h; Be cooled to 90 DEG C, drip the formaldehyde 65g(0.80mol that massfraction is 37%); After dropwising, be warming up to 100 DEG C of back flow reaction 2.5h; Be cooled to 80 DEG C, add barium hydroxide 5.49g with in and tosic acid; Be warming up to 160 DEG C of dehydrations, being evacuated to relative vacuum degree is-0.098Mpa, sloughs free phenol, obtained rosin products.
This resin index: gel chromatography records molecular weight (Mw) 1583, and vapor phase process records free phenol 0.67, at recording 800 DEG C with urotropine with mass ratio 2:8 mixing abrasive dust, Residual carbon is for 55.3%.
Embodiment 3: lignin-base reinforced resin
150g phenol (1.60mol) is dropped in four-hole boiling flask, under reflux state, adds oxalic acid 5g, after stirring, add xylogen 20g, be heated to 150 DEG C, isothermal reaction 2h; Be cooled to 80 DEG C, drop into turps 15g, be warming up to 135 DEG C of reaction 2h; Be cooled to 90 DEG C, drip the formaldehyde 65g(0.80mol that massfraction is 37%); After dropwising, be warming up to 100 DEG C of back flow reaction 2.5h; Heat up dehydration to 160 DEG C, and being evacuated to relative vacuum degree is-0.098Mpa, sloughs free phenol, obtained rosin products.
This resin index: gel chromatography records molecular weight (Mw) 1594, and vapor phase process records free phenol 0.48, at recording 800 DEG C with urotropine with mass ratio 2:8 mixing abrasive dust, Residual carbon is for 56.6%.
Embodiment 4: lignin-base reinforced resin
150g phenol (1.60mol) is dropped in four-hole boiling flask, under reflux state, adds tosic acid 5.25g, after stirring, add xylogen 60g, be heated to 160 DEG C, isothermal reaction 3h; Be cooled to 80 DEG C, drop into turps 30g, be warming up to 150 DEG C of reaction 2h; Be cooled to 90 DEG C, drip the formaldehyde 75g(0.925mol that massfraction is 37%); After dropwising, be warming up to 100 DEG C of back flow reaction 2h; Be cooled to 80 DEG C, add in barium hydroxide 9.61g and tosic acid; Heat up dehydration to 160 DEG C, and being evacuated to relative vacuum degree is-0.098Mpa, sloughs free phenol, obtained rosin products.
This resin index: gel chromatography records molecular weight (Mw) 1590, and vapor phase process records free phenol 0.85, at recording 800 DEG C with urotropine with mass ratio 2:8 mixing abrasive dust, Residual carbon is for 54.2%.
Lignin-base reinforced resin obtained in above embodiment 1-4 is for the preparation of rubber product, and use triangular rubber core technical recipe shown in table 1, adopt two-part calendering process sample preparation shown in table 2, the performance test results of gained rubber product is as shown in table 3:
Table 1: the two-part calendering process formula preparing rubber
Table 2: the two-part calendering process preparing rubber
| First paragraph | Start mixing at 90rpm/90 DEG C |
| 0'' | Rubber |
| 30'' | Add 2/3 filler |
| 1'30'' | Add residue 1/3 filler |
| 2' | Cleaning |
| 3' | Refuel and vulcanization accelerator outside small powder |
| 4' | Cleaning |
| 5' | Binder removal |
| Bottom sheet on a mill until, at room temperature parks 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 |
| Thin-pass three times on a mill until, bottom sheet |
Table 3: with embodiment gained resin for component obtains the performance perameter of rubber
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, adds tosic acid 2g, be cooled to 80 DEG C, drop into turps 13g, be warming up to 120 DEG C of reaction 2h; Be cooled to 90 DEG C, drip the formaldehyde 60g that massfraction is 37%; After dropwising, be warming up to 100 DEG C of back flow reaction 2.5h; Be cooled to 80 DEG C, add barium hydroxide 3.66g with in and tosic acid; Be warming up to 160 DEG C of dehydrations, being evacuated to relative vacuum degree is-0.098Mpa, sloughs free phenol, obtained 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, adds tosic acid 2g, after stirring, add xylogen 20g, be heated to 150 DEG C, isothermal reaction 3h; Be cooled to 90 DEG C, drip the formaldehyde 60g that massfraction is 37%; After dropwising, be warming up to 100 DEG C of back flow reaction 2.5h; Be cooled to 80 DEG C, add barium hydroxide 3.66g with in and tosic acid; Be warming up to 160 DEG C of dehydrations, being evacuated to relative vacuum degree is-0.098Mpa, sloughs free phenol, obtained 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
Resol is not added in comparative example 1 rubber compounding;
Add resol in comparative example 2 rubber compounding, resol wherein with the addition of turps;
Add resol in comparative example 3 rubber compounding, resol wherein through lignin modification, but does not add turps;
Add in embodiment 1 rubber compounding and with the addition of xylogen and terebinthine resol.
Except above difference, comparative example 2 is substantially identical with embodiment 1 with the preparation process of resol in comparative example 3.
In table 4, in the made rubber of comparative example 1,2,3 and embodiment 1, to form contrast known for the performance perameter of made rubber: by adding xylogen and turps, tear resistance and the hardness of rubber significantly improve, and aging resistance has a clear superiority in.
Experiment proves: lignin-base reinforced resin provided by the invention is by adding xylogen and turps, obvious to the reinforcing effect of triangular rubber core, significantly improve the tear resistance of rubber and hardness, aging resistance has a clear superiority in, thus improves the machining property of rubber.
Although above with general explanation, embodiment and test, the present invention is described in detail, and on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (11)
1. lignin-base reinforced resin is preparing the application on triangular rubber core rubber, lignin-base reinforced resin raw material contains following composition: phenolic compound, an acidic catalyst, xylogen, turps and aldehyde compound, the molar ratio of described phenolic compound, aldehyde compound is 1:0.5-0.8, and described an acidic catalyst, xylogen and terebinthine consumption are respectively 0.5-5%, 5-50%, 5-30% of the quality of phenolic compound.
2. application according to claim 1, is characterized in that, described an acidic catalyst, xylogen and terebinthine consumption are respectively 3-4.2%, 13-40%, 10-20% of the quality of phenolic compound.
3. application according to claim 1, is characterized in that, the molar ratio of described phenolic compound, aldehyde compound is 1:0.5-0.75.
4. the application according to any one of claim 1-3, is characterized in that, described phenolic compound is one or more in phenol, cresols, dihydroxyphenyl propane, Bisphenol F, Resorcinol or pyrocatechol; Described an acidic catalyst is one or more in oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid, thionamic acid; Described xylogen is sulfonated lignin, alkali lignin, acidolysis xylogen or high-boiling alcohol lignin; Described aldehyde compound is one or more in formaldehyde, acetaldehyde, furfural, paraformaldehyde; Described turps is light oil or superfine turps.
5. application according to claim 4, is characterized in that, described phenolic compound is phenol.
6. application according to claim 4, is characterized in that, described an acidic catalyst is oxalic acid or tosic acid.
7. application according to claim 4, is characterized in that, described aldehyde compound is formaldehyde.
8. the application according to any one of claim 1-3, the preparation method of lignin-base reinforced resin, comprises the following steps:
1) phenolic compound, an acidic catalyst and xylogen are mixed, 100-300 DEG C of pre-treatment 2-4h;
2) to step 1) add turps in gained intermediate, at temperature 120-150 DEG C, reaction 1.5-2.5h;
3) to step 2) add aldehyde compound in gained reaction mixture, at temperature 100-110 DEG C, carry out the condensation reaction of 2-3h.
9. application according to claim 8, is characterized in that, described step 1) in, phenolic compound, catalyzer and xylogen be 100-300 DEG C of pre-treatment 2-4h in encloses container.
10. application according to claim 9, is characterized in that, described step 1) in, phenolic compound, catalyzer and xylogen be 120-260 DEG C of pre-treatment 3-4h in encloses container.
11. application according to claim 8, is characterized in that, described step 3) reacted after, also comprise dehydration and vacuum step.
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| 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 |
| 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 |
| 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 |
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 |
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| 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 |
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Address after: 250204 Diaozhen Industrial Development Zone, Zhangqiu City, Shandong Province Patentee after: SHANDONG SHENGQUAN NEW MATERIAL CO., LTD. Address before: 250204 Industrial Development Zone, Diao Town, Zhangqiu City, Ji'nan, Shandong Patentee before: Shandong Shengquan Chemical Industry Co., Ltd. |