CN106008867A - Preparation method for lignin-modified phenolic tackifying resin for rubber - Google Patents
Preparation method for lignin-modified phenolic tackifying resin for rubber Download PDFInfo
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- CN106008867A CN106008867A CN201610346065.0A CN201610346065A CN106008867A CN 106008867 A CN106008867 A CN 106008867A CN 201610346065 A CN201610346065 A CN 201610346065A CN 106008867 A CN106008867 A CN 106008867A
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- lignin
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- tackifying resins
- phenolic tackifying
- acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
Abstract
The invention discloses a preparation method for lignin-modified phenolic tackifying resin for rubber. The method is implemented by the following two steps: (1) degrading lignin: after chemical degradation treatment, the molecular chain of lignin is shortened, the molecular weight is reduced and the reaction activity is improved; (2) directly adding corresponding amounts of phenol, formaldehyde and a catalyst into a system after degradation is finished, performing addition polycondensation at certain temperature, and removing water and unreacted micromolecular monomers in the system to obtain the lignin-modified phenolic tackifying resin with a softening point of 80 to 110 DEG C and an acid value of 10 to 30mgKOH/g for the rubber after reaction is finished. The resin can be used for implementing matching processing of the rubber and improving bonding performance between rubber layers; the cost of the phenolic tackifying resin for the rubber can be reduced, and in addition, a high-added-value manner is also provided for the application of rich pulp papermaking waste of China to the field of high molecular materials.
Description
Technical field
The present invention relates to the preparation method of a kind of modified rubber phenolic tackifying resins, wooden particularly to one
The preparation method of element modified rubber phenolic tackifying resins.
Background technology
The main component of phenolic tackifying resins is phenolic resin, by petrochemical industry based raw material phenol and formaldehyde addition polycondensation
Become.The production of phenolic resin and use can bring a certain degree of pollution to environment, affect whole ecological environment.
In the production of phenolic resin, produce substantial amounts of waste water, waste water is mainly phenols and aldehyde material, by former
Material phenol and formaldehyde produce, if phenol wastewater is the most treated takes up the post of meaning discharge, to the mankind, Fish and farming
Thing all can bring serious harm, and the place of phenol wastewater comprehends and is greatly increased product cost.Along with human environment
Consciousness and the enhancing day by day of crisis of resource, the most effectively comprehensively utilize biomass resource and replace petrochemical material system
Standby phenolic resin oneself mentioned strategic height by many countries and take in.
Lignin is the natural polyphenol compounds being widely present in plant, by lignum-vitae base, Syringa oblata Lindl. base
Form with para hydroxybenzene propane three basic structures unit, answered by carbon oxygen-ether linkage and having of C-C bond formation
Miscellaneous spacial framework.At nature, lignin regenerates with the speed of 50,000,000,000 tons every year, pulping and paper-making
Industry sub-argument to go out 1.4 hundred million tons of celluloses every year from plant, obtains the lignin by-product of 50,000,000 tons simultaneously
Product.Due to the similarity of lignin Yu phenol structure, both at home and abroad to lignin should be used as in phenolic resin
Numerous studies, and having made some progress, but overwhelming majority literature research lignin is by various modifications
Afterwards for based Wood Adhesives aspect, the research in phenolic tackifying resins field is the fewest.
The rubber phenolic tackifying resins sold in the market exists that permanent tack is poor, expensive etc. to be lacked
Point, constantly expands in the face of rubber processing market, and urgent need to solve this difficult problem.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of lignin modification rubber phenolic tackifying resins, solve
Certainly there is permanent tack pollution environment poor, expensive, raw materials used in existing rubber phenolic tackifying resins
And non-renewable problem.
In order to achieve the above object, the present invention is achieved by the following technical solutions:
The present invention provides the preparation method of a kind of lignin modification rubber phenolic tackifying resins, and the method includes
Following steps: 1) degraded of lignin: add catalyst in the reactor, by lignin in the basic conditions
Processing through thermally and chemically auxiliary agent and carry out lignin degradation, the PH controlling reaction system with catalyst regulation is
7-12, temperature is 50-100 DEG C, obtains lignin degradation products, and the thermally and chemically auxiliary agent used is in warm
The lower cracking of effect discharges oxygen containing strong free radical (hydroxyl radical free radical), makes the carbon of connected wood quality construction unit
Carbon bond and ehter bond rupture, and molecular weight reduces, structures alone (guaiacyl, Syringa oblata Lindl. base and to hydroxyl
Phenylpropyl alcohol alkane) content increase, therefore reactivity improves, it is possible to achieve effective replacement of Pyrogentisinic Acid；2) phenolic aldehyde
Prepared by tackifying resin: to step 1) lignin degradation products adds phenol, formaldehyde and acidic catalyst, use
Acidic catalyst regulation pH to 0-2, reaction temperature is 90-110 DEG C, and sampling observes polyreaction degree to viscous
When degree reaches target viscosities, open the moisture in vacuum removal reaction system and little molecule unreacted monomer, tree
After fat softening point is up to standard, acid number to the resin adding nertralizer regulation resin reaches discharging after target acid number, with
The lignin degrading phenol of 10%～45% mass parts (substitute) and phenol, formaldehyde carry out reaction and obtain lignin and change
Property rubber phenolic tackifying resins.
Preferably, step 1) lignin degraded in add catalyst be hydrochloric acid, sulphuric acid, sodium hydroxide,
One or both mixture in potassium hydroxide, calcium oxide, magnesium oxide or zinc oxide.
Preferably, step 1) lignin degraded in the thermally and chemically auxiliary agent used be inorganic molecules or organic
Little molecule.
Preferably, step 1) inorganic molecules thermally and chemically auxiliary agent be hydrogen peroxide, Ammonium persulfate., potassium peroxydisulfate,
Sodium sulfite；Organic molecule thermally and chemically auxiliary agent is tert-butyl hydroperoxide, azodiisobutyronitrile, peroxide
Change benzoyl.
Preferably, step 2) in acidic catalyst be hydrochloric acid, sulphuric acid, oxalic acid, benzenesulfonic acid or to toluene sulphur
One or more mixture in acid.
Preferably, step 2) nertralizer used is inorganic base, inorganic salt or organic base.
Preferably, one or more during inorganic base nertralizer is sodium hydroxide, potassium hydroxide, calcium hydroxide；
Inorganic salt nertralizer is one or more in sodium bicarbonate, ammonium hydrogen carbonate, potassium bicarbonate, calcium bicarbonate；
Organic base nertralizer is open-chain crown ether, ethamine, ethanolamine, ethylenediamine, dimethylamine, trimethylamine, three second
Amine, 1,3-propane diamine, 1,2-propane diamine, tripropyl amine (TPA), triethanolamine, butylamine, isobutyl amine, tert-butylamine,
Hexylamine, octylame, aniline, benzylamine, cyclohexylamine, pyridine, hexamethylenetetramine, para-aminophenol, 8-hydroxyl
One or more in base quinoline, diphenylamines.
Preferably, step 2) in react total phenolic aldehyde mol ratio be 1:0.7-1:0.9.
Preferably, step 2) in react total phenolic aldehyde mol ratio be 1:0.85.
Preferably, lignin modification rubber phenolic tackifying resins softening point be 80-110 DEG C, acid number be
10-30mgKOH/g。
Preferably, lignin be wood hydrolysis industry, dilute acid hydrolysis lignin in paper industry garbage,
Concentrated acid hydrolysis lignin, sulfate-reducing conditions, alkali lignin, lignosulfonates, enzymolysis xylogen or its
Any one or a few mixture in derivant.
Advantages of the present invention and having the beneficial effects that: the present invention provides a kind of lignin modification rubber phenolic aldehyde to increase
The preparation method of viscosity resin, with the lignin degrading phenol of 10%-45% mass parts (substitute) be raw material with phenol,
Formaldehyde reaction obtains lignin modification rubber phenolic tackifying resins, and the present invention can make rubber phenolic tackifying
Resin cost is substantially reduced, and lignin can substitute phenol 10%-45%, and formaldehyde consumption reduces the most accordingly simultaneously；
Paper pulp papermaking waste liquid and agriculture and forestry organic waste material for China's abundant open a high added value approach, add agriculture
The people take in, and reduce environmental pollution, reduce the dependency of phenolic resin industry Pyrogentisinic Acid；Lignin portion
Substitute phenol and prepare rubber phenolic tackifying resins, and can operate with industrialization continuity production, improve enterprise
Economic benefit.
Resin prepared by the present invention and the compatibility of rubber are improved, permanent tack, make full use of China rich
Rich cheap renewable biomass resource papermaking waste lignin, not only reduces cost but also protect environment,
And consecutive production suitable for industrialized, it is the product of a kind of good market prospects.
Detailed description of the invention
Below in conjunction with embodiment, the detailed description of the invention of the present invention is further described.Following example are only
For technical scheme is clearly described, and can not limit the scope of the invention with this.
The present invention is the preparation method of a kind of lignin modification rubber phenolic tackifying resins, the method include with
Lower step: 1) degraded of lignin: add catalyst in the reactor, by lignin warp in the basic conditions
Overheated and chemical assistant processes and carries out lignin degradation, and the PH controlling reaction system with catalyst regulation is 7-12,
Temperature is 50-100 DEG C, obtains lignin degradation products；2) prepared by phenolic tackifying resins: 60 DEG C of conditions
Under, to step 1) lignin degradation products adds phenol, formaldehyde and acidic catalyst, use acidic catalyst
Regulation pH to 0-2, reaction temperature is 90-110 DEG C, and sampling is observed polyreaction degree and reached target to viscosity
During viscosity, opening the moisture in vacuum removal reaction system and little molecule unreacted monomer, resin softening point reaches
After mark, acid number to the resin adding nertralizer regulation resin reaches discharging after target acid number.Gained lignin changes
Property rubber with phenolic tackifying resins softening point 80-110 DEG C, acid number is at 10-30mgKOH/g.
Embodiment 1
40g alkali lignin (20wt% substitutes phenol) disperses in 40g water, and hydro-oxidation aqueous solutions of potassium adjusts pH
To 10, being warming up to 80 degree, be slowly added to 1g tert-butyl hydroperoxide (70wt% aqueous solution), reaction 2 is little
Time；Adjustment temperature, to 60 DEG C, adds whole phenol and formaldehyde (phenolic aldehyde mol ratio 1:0.8), adjusts with oxalic acid
Joint pH to 1.5, is warming up to 100 degree of back flow reaction to viscositys and reaches target viscosity, open vacuum removal moisture
Suitable with unreacted small-molecule substance to softening point, add a small amount of triethanolamine regulation resinous acid value, discharging.
End product softening point 85 DEG C, acid number 23mgKOH/g.
Embodiment 2
40g alkali lignin (20wt% substitutes phenol) disperses in 40g water, and hydro-oxidation aqueous solutions of potassium adjusts pH
To 10.5, being warming up to 75 DEG C, be slowly added to 5g ammonium persulfate aqueous solution (20wt% aqueous solution), reaction 2 is little
Time；Adjustment temperature, to 60 DEG C, adds whole phenol and formaldehyde (phenolic aldehyde mol ratio 1:0.85), with to first
Benzenesulfonic acid regulation pH to 1.2, is warming up to 100 degree of back flow reaction to viscositys and reaches target viscosity, open vacuum
Removing moisture and unreacted small-molecule substance are suitable to softening point, add a small amount of ethylenediamine regulation resinous acid value,
Discharging.End product softening point 97 DEG C, acid number 26mgKOH/g.
Embodiment 3
60g alkali lignin (30wt% substitutes phenol) disperses in 60g water, is warming up to 50 DEG C, hydro-oxidation
Sodium regulation pH to 8.5, is slowly added to 6g hydrogen peroxide (30wt% aqueous solution), reacts 1 hour；Adjust temperature
To 60 DEG C, add whole phenol and formaldehyde (phenolic aldehyde mol ratio 1:0.78), regulate pH with p-methyl benzenesulfonic acid
To 1.0, it is warming up to 100 degree of back flow reaction to viscositys and reaches target viscosity, open vacuum removal moisture and the most anti-
Answer small-molecule substance suitable to softening point, add a small amount of open-chain crown ether regulation resinous acid value, discharging.Finally
Product softening point 94 DEG C, acid number 20mgKOH/g.
Embodiment 4
60g enzymolysis xylogen (30wt% substitutes phenol) disperses in 60g water, is warming up to 65 DEG C, adds hydrogen-oxygen
Change aqueous solutions of potassium and adjust pH to 9, be slowly added dropwise the acetone soln (10wt%) of 5g azodiisobutyronitrile, react 2
Hour；Adjustment temperature, to 60 DEG C, adds whole phenol and formaldehyde (phenolic aldehyde mol ratio 1:0.85), with grass
Acid for adjusting pH, to 0.8, is warming up to 105 degree of back flow reaction to viscositys and reaches target viscosity, open vacuum removal
Moisture and unreacted small-molecule substance are suitable to softening point, add a small amount of open-chain crown ether regulation resinous acid value,
Discharging.End product softening point 104 DEG C, acid number 17mgKOH/g.
Embodiment 5
80g lignosulfonates (40wt% substitutes phenol) disperse in 80g water, are warming up to 50 DEG C, hydrogenation
Sodium oxide regulation pH to 11, is slowly added to 8g hydrogen peroxide (30wt% aqueous solution), reacts 2 hours；Adjust
Temperature, to 60 DEG C, adds whole phenol and formaldehyde (phenolic aldehyde mol ratio 1:0.85), adjusts with p-methyl benzenesulfonic acid
Joint pH to 1.2, is warming up to 106 degree of back flow reaction to viscositys and reaches target viscosity, open vacuum removal moisture
Suitable with unreacted small-molecule substance to softening point, add a small amount of open-chain crown ether regulation resinous acid value, discharging.
End product softening point 107 DEG C, acid number 17mgKOH/g.
Embodiment 6
40g sulfate-reducing conditions (20wt% substitutes phenol) is dispersed in 40g water, hydro-oxidation sodium water solution
Regulation pH to 9.8, is warming up to 70 DEG C, hydro-oxidation sodium regulation pH to 11, is slowly added to 1 tert-butyl group mistake
Hydrogen oxide (30wt% aqueous solution), reacts 2 hours；Adjustment temperature, to 60 DEG C, adds whole phenol and first
Aldehyde (phenolic aldehyde mol ratio 1:0.80), with sulfur acid for adjusting pH to 1.0, is warming up to 100 degree of back flow reaction to glutinous
Degree reaches target viscosity, opens vacuum removal moisture and unreacted small-molecule substance suitable to softening point, adds
A small amount of open-chain crown ether regulation resinous acid value, discharging.End product softening point 91 DEG C, acid number 21mgKOH/g.
Comparing embodiment
As a example by using the resin in embodiment 2, and commercially available phenolic tackifying resins performance indications contrast, property
Energy index such as following table:
As can be seen from the above table, the lignin modification rubber tackifying resin that prepared by the present invention increases with commercially available phenolic aldehyde
Viscosity resin performance indications softening point and acid number are the most closely, it is ensured that the lignin modification rubber of preparation increases
Viscosity resin application effect in rubber.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Within bright spirit and principle, any modification, equivalent substitution and improvement etc. made, should be included in this
Within bright protection domain.
Claims (10)
1. the preparation method of a lignin modification rubber phenolic tackifying resins, it is characterised in that the method
Comprise the following steps: 1) degraded of lignin: add catalyst in the reactor, by lignin at alkalescence bar
Process through thermally and chemically auxiliary agent under part and carry out lignin degradation, control the PH of reaction system with catalyst regulation
For 7-12, temperature is 50-100 DEG C, obtains lignin degradation products；2) prepared by phenolic tackifying resins: to
Step 1) lignin degradation products adds phenol, formaldehyde and acidic catalyst, regulate with acidic catalyst
PH to 0-2, reaction temperature is 90-110 DEG C, and sampling is observed polyreaction degree and reached target viscosities to viscosity
Time, open the moisture in vacuum removal reaction system and little molecule unreacted monomer, after resin softening point is up to standard,
Acid number to the resin adding nertralizer regulation resin reaches discharging after target acid number.
The preparation method of a kind of lignin modification rubber phenolic tackifying resins the most according to claim 1,
It is characterized in that, described step 1) catalyst that adds in the degraded of lignin is hydrochloric acid, sulphuric acid, hydroxide
One or both mixture in sodium, potassium hydroxide, calcium oxide, magnesium oxide or zinc oxide.
The preparation method of a kind of lignin modification rubber phenolic tackifying resins the most according to claim 1,
It is characterized in that, described step 1) the thermally and chemically auxiliary agent used in the degraded of lignin be inorganic molecules or
Organic molecule.
The preparation method of a kind of lignin modification rubber phenolic tackifying resins the most according to claim 3,
It is characterized in that, described step 1) inorganic molecules thermally and chemically auxiliary agent is hydrogen peroxide, Ammonium persulfate., over cure
Acid potassium, sodium sulfite；Organic molecule thermally and chemically auxiliary agent be tert-butyl hydroperoxide, azodiisobutyronitrile,
Benzoyl peroxide.
The preparation method of a kind of lignin modification rubber phenolic tackifying resins the most according to claim 1,
It is characterized in that, described step 2) in acidic catalyst be hydrochloric acid, sulphuric acid, oxalic acid, benzenesulfonic acid or to first
One or more mixture in benzenesulfonic acid.
The preparation method of a kind of lignin modification rubber phenolic tackifying resins the most according to claim 1,
It is characterized in that, described step 2) nertralizer used is inorganic base, inorganic salt or organic base.
The preparation method of a kind of lignin modification rubber phenolic tackifying resins the most according to claim 6,
It is characterized in that, described inorganic base nertralizer is the one in sodium hydroxide, potassium hydroxide, calcium hydroxide
Or it is several；Inorganic salt nertralizer is the one in sodium bicarbonate, ammonium hydrogen carbonate, potassium bicarbonate, calcium bicarbonate
Or it is several；Organic base nertralizer is open-chain crown ether, ethamine, ethanolamine, ethylenediamine, dimethylamine, front three
Amine, triethylamine, 1,3-propane diamine, 1,2-propane diamine, tripropyl amine (TPA), triethanolamine, butylamine, isobutyl amine,
Tert-butylamine, hexylamine, octylame, aniline, benzylamine, cyclohexylamine, pyridine, hexamethylenetetramine, p-aminophenyl
One or more in phenol, 8-hydroxyquinoline, diphenylamines.
The preparation method of a kind of lignin modification rubber phenolic tackifying resins the most according to claim 1,
It is characterized in that, described step 2) in react total phenolic aldehyde mol ratio be 1:0.7-1:0.9.
The preparation method of a kind of lignin modification rubber phenolic tackifying resins the most according to claim 8,
It is characterized in that, described step 2) in react total phenolic aldehyde mol ratio be 1:0.85.
The preparation side of a kind of lignin modification rubber phenolic tackifying resins the most according to claim 1
Method, it is characterised in that described lignin modification rubber phenolic tackifying resins softening point is 80-110 DEG C, acid
Value is 10-30mgKOH/g.
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Cited By (1)
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| CN111491768A (en) * | 2017-12-22 | 2020-08-04 | 斯道拉恩索公司 | Modified wood product and method for producing said product |
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| 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 |
| CN103626642A (en) * | 2013-11-28 | 2014-03-12 | 上海应用技术学院 | Method for preparing vanillin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111491768A (en) * | 2017-12-22 | 2020-08-04 | 斯道拉恩索公司 | Modified wood product and method for producing said product |
| US11504877B2 (en) | 2017-12-22 | 2022-11-22 | Stora Enso Oyj | Modified wood product and a process for producing said product |
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Application publication date: 20161012 |