CN104530639B - Phenolaldehyde moulding compound of lignin modification and preparation method thereof - Google Patents
Phenolaldehyde moulding compound of lignin modification and preparation method thereof Download PDFInfo
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- CN104530639B CN104530639B CN201410818075.0A CN201410818075A CN104530639B CN 104530639 B CN104530639 B CN 104530639B CN 201410818075 A CN201410818075 A CN 201410818075A CN 104530639 B CN104530639 B CN 104530639B
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Abstract
Phenolaldehyde moulding compound of lignin modification and preparation method thereof, other auxiliary agents such as lignin modification thermoplastic phenolic resin and curing agent, filler, releasing agent and pigment are blended uniformly, open type plastic purificating set carries out semi-curing process, obtain the sheet brittle prod with fine glossiness, cross 200 mesh after crushed and obtain moulding compound.Described lignin-base phenolaldehyde moulding compound product bending strength >=70MPa, notch impact strength >=1.3kJ/m2, unnotched impact strength >=4kJ/m2, heat distortion temperature >=140 DEG C.
Description
Technical field
Phenolaldehyde moulding compound that the present invention relates to lignin modification and preparation method thereof, the wood specifically produced about bio-fuel industry
Quality preparation method in thermoplastic phenolic resin and phenolaldehyde moulding compound thereof.
Background technology
Phenolaldehyde moulding compound is a kind of heat resistance with excellence and the material of preferable cost performance, and its main component is phenolic resin.
Phenolic resin by phenolic compound and aldehyde compound under catalyst action the phenolic resin of polycondensation due to cheap, resistance to
Ablation hot, resistance to, fire-retardant, burning fuming is few etc. is widely used in adhesive, coating, moulding compound, laminated plastic, foamed plastics
And ion exchange resin etc..The production of phenolic resin and use can consume bulk petroleum chemical products, and bring one to environment
Determine the pollution of degree, affect the whole ecosystem.Nowadays for producing the phenol of the main petrochemicals of phenolic resin, formaldehyde
Price improve constantly, cause China's phenolic resin relevant industries profit drastically to decline, have a strong impact on the development of phenolic resin industry.
Lignin (lignin) is the non-oil resource that nature uniquely can provide renewable aryl compound, be in plant kingdom only
The second abundant natural polymer inferior to cellulose.Lignin molecule has numerous different types of active group, and having concurrently can be again
Life, degradable, the advantage such as nontoxic.Enzymolysis xylogen (Enzymatic Hydrolysis Lignin is called for short EHL) is by plant
Stalk fermentation prepares the Novel wooden quality extracted in the residue of alcohol fuel.At present, most enzymolysis xylogen is used for burning,
Not only its composition is not utilized effectively, and pollutes environment, and China produces maize straw 6.7 hundred million tons, every 1 ton of jade now per year
Rice stalk fermentation prepares the residue of alcohol fuel can obtain the lignin of about 300 kilograms, the most efficiently utilizes enzymolysis xylogen
Be possible not only to the resource rational utilization done, again can petroleum replacing chemical products, protect environment.In the present invention used wooden usually
Come from the agricultural wastes such as corncob, maize straw and produce the residue of fuel.Cheng Xian etc. use organic solvent extraction with inorganization
Method separation and Extraction from the residue of microorganism enzymolysis corn stalk that product process obtains enzymolysis xylogen, and prepares bio-modification
Hot melt type phenolic resin, such a process increases production cost.
Lignin application study in phenolic resin, reporting for work more is the application in based Wood Adhesives, at thermoplastic phenolic
Application in resin rarely has reports for work.Matuana have studied different types of lignin and substitutes phenolic resin；Peng and Khharade
Have studied lignin mechanical behavior in phenolic resin, and have studied lignin, phenol and formaldehyde addition with Modern Methods
The resinous molecular structure that polycondensation obtains；Wang Dizhen uses the preparation of methylolation technique study lignin thermoplastic phenolic resin, by
Relatively big (compared with the molecular weight of phenol and thermoplastic phenolic resin) in lignin molecule amount, the therefore reactivity phase of lignin
To relatively low, and methylolation does not increase the number of active site, simply the active site on lignin phenyl ring is become methylol.
The reactivity of lignin only has 1/10th of phenol to have document to show, therefore in the studies above, lignin should mainly as filler
With, and non-real react with phenol formaldehyde (PF).This patent uses phenolate method liquefaction degradation biological fire-bote quality, due to this next
The lignin active function groups in source is preferably retained, containing more micromolecule phenolic in catabolite, permissible
It is effectively realized effective replacement of lignin Pyrogentisinic Acid.
Summary of the invention
Solve the technical problem that: the present invention provides the phenolic aldehyde of the lignin modification of a kind of environmental protection, low cost and good combination property
Moulding compound and preparation method thereof, preparation method is simple, efficiently utilizes the residue that biomass fuel preparation process produces, and promotes
Bio-fuel industrial expansion.
Technical scheme: the preparation method of the phenolaldehyde moulding compound of lignin modification, lignin, under acidic catalyst, is molten with phenol
Agent carries out phenolate degraded, complete addition liquid formaldehyde of degrading, and reacts 2-3h at a temperature of 80-100 DEG C, and then air-distillation removes
Moisture and phenol, obtain the lignin modification thermoplastic phenolic resin of black fragility；This lignin modification thermoplastic phenolic resin and
Phenolic resin presses WT lignin modification thermoplastic phenolic resin/(WT lignin modification thermoplastic phenolic resin+WT common thermoplastic's phenolic resinThe mass ratio of)=20%-100%
It is blended uniformly with curing agent, filler, releasing agent and pigment after mixing, specifically comprises lignin phenol formaldehyde resin+phenolic resin
137 parts, 22 parts of curing agent, filler 125 parts, 3 parts of magnesia, calcium hydroxide 4.2 parts, stearic acid 3.1 parts, three fly powder 7.8
Part, 5 parts of water, ink black 2.9 parts and talcum powder 7.8 parts, then carry out semi-curing process on open type plastic purificating set, and low temperature rolls
40-60 DEG C of axle, high temperature roller bearing 140-180 DEG C, roll spacing 1.5-2.5mm, time 2-5min, obtain sheet brittle prod, through powder
Cross 200 mesh after broken and obtain the phenolaldehyde moulding compound of lignin modification.
Lignin used is enzymolysis xylogen, hydrolytic lignin or the alkali lignin produced during biological fuel industry produces.
Acidic catalyst used is hydrochloric acid or oxalic acid.
Curing agent used is methenamine, paraformaldehyde or thermosetting resin.
Filler used is wood powder or bamboo powder.
Low temperature roller bearing preferably 50 DEG C used；High temperature roller bearing preferably 150 DEG C；The preferred 1.5-2mm of roll spacing, time preferred 2-3min.
Lignin modification thermoplastic phenolic resin used and phenolic resin press WT lignin modification thermoplastic phenolic resin/(WT lignin modification thermoplastic phenolic resin Fat+WT common thermoplastic's phenolic resin)=60%.
The phenolaldehyde moulding compound of the lignin modification that described method prepares, the phenolaldehyde moulding compound bending of described lignin modification is strong
Degree >=70MPa, notch impact strength >=1.3kJ/m2, unnotched impact strength >=4kJ/m2, heat distortion temperature >=140 DEG C.
Described lignin modification thermoplastic phenolic resin is prepared as follows:
Phenol, acid catalyst and lignin being mixed, lignin is 1:(1-4 with the mass ratio of phenol), by changing acid catalysis
The pH value of the addition above-mentioned reaction system of regulation of agent, to 1-3, is heated to 90 DEG C-160 DEG C, reacts 1-3h, be subsequently adding first
Aldehyde, phenol is 1:(0.81-0.87 with the mol ratio of aldehyde), forming reaction system, regulation reaction temperature, to 90 DEG C-200 DEG C, is reacted
2-4h, first normal pressure reduces pressure again, the moisture in system and the phenol of residual, formaldehyde is steamed, obtains lignin modification phenolic resin.
Beneficial effect: the shortage increasingly of fossil energy promotes the fast development of bio-fuel, but bio-fuel cost is relative at present
Higher, to promote relatively difficult, the value added applications of the biological combustion byproducts of research advantageously reduces the production cost of such enterprise,
Promote the sound development of China's bio-fuel.The present invention substitutes phenol with the product section that lignin phenol liquefaction obtains and formaldehyde is
Base stock, reacts under catalyst action, obtains having low cost, the phenolic aldehyde of hypotoxicity (free phenol content reduction)
Naval stores.Lignin phenol liquefaction products mainly contains the little molecule of phenolic hydroxyl group, and relative to the big molecule of lignin, it has
Reactivity is high, and reaction speed is fast, the feature that production efficiency is high.Oxalic acid is weak organic acid, uses oxalic acid as catalyst, system
Standby high adjacent position phenolic resin, can improve the curing rate of resin, for the thermoplastic phenolic resin containing lignin, especially have
Benefit the solidification of product.Scarcity day by day due to petroleum resources so that the research to lignin both at home and abroad becomes focus, but right
The research being applied to moulding compound in bio-fuel lignin is not the most reported, the present invention has widened the raw material sources preparing moulding compound.
Detailed description of the invention
Following example further illustrate present disclosure, but should not be construed as limitation of the present invention.Without departing substantially from the present invention
In the case of spirit and essence, the amendment that the inventive method, step or condition are made and replacement, belong to the scope of the present invention.
If not specializing, the conventional means that technological means used in embodiment is well known to those skilled in the art.
Normal pressure of the present invention refers to an atmospheric pressure.
Embodiment 1
The preparation of enzymatic hydrolysis (EH) lignin modified thermoplastic phenolic resin
100 grams of phenol, enzymolysis xylogen (the 30% of phenol quality) and hydrochloric acid (the 5% of phenol quality) are added reactor
In, reaction temperature 95 DEG C, reaction time 2h, add formaldehyde (phenolic aldehyde mol ratio is 1:0.85), reaction temperature is 90 DEG C-110 DEG C,
Reaction time 2h, first normal pressure reduces pressure and sloughs moisture and residue phenol, prepares enzymatic hydrolysis (EH) lignin modified phenolic resin.Common thermoplastic
Property preparation method of phenolic resin is identical.
The preparation of enzymolysis xylogen base phenolaldehyde moulding compound
By above-mentioned enzymatic hydrolysis (EH) lignin modified thermoplastic phenolic resin with common thermoplastic's phenolic resin with 20%, 40%, 60%, 80%,
100% is blended, and is blended uniformly with other auxiliary agents such as curing agent, filler, releasing agent and pigment, and concrete formula is Lignin phenolic tree
Fat+phenolic resin 137 parts, methenamine 22 parts, wood powder 125 parts, 3 parts of magnesia, calcium hydroxide 4.2 parts, tristearin
Acid 3.1 parts, three fly 7.8 parts of powder, 5 parts of water, ink black 2.9 parts and talcum powder 7.8 parts, open type plastic purificating set carries out half
Maturation process, low temperature roller bearing 40 DEG C, high temperature roller bearing 145 DEG C, roll spacing 1.5, time 2.5min.Obtain that there is fine glossiness
Sheet brittle prod, crosses 200 mesh stand-by after crushed.
Embodiment 2
The preparation of hydrolytic lignin modified thermoplastic phenolic resin
100 grams of phenol, hydrolytic lignin (the 40% of phenol quality) and oxalic acid (the 5% of phenol quality) are added reactor
In, reaction temperature 100 DEG C, reaction time 1.5h, add formaldehyde (phenolic aldehyde mol ratio is 1:0.85), reaction temperature is 90 DEG C-110 DEG C,
Reaction time 2.5h, first normal pressure reduces pressure and sloughs moisture and residue phenol, prepares hydrolytic lignin phenol-formaldehyde resin modified.Ordinary hot
Plastic phenolic process for preparing resins is identical.
The preparation of hydrolytic lignin base phenolaldehyde moulding compound
By said hydrolyzed lignin modification thermoplastic phenolic resin with common thermoplastic's phenolic resin with 20%, 40%, 60%, 80%,
100% is blended, and is blended uniformly with other auxiliary agents such as curing agent, filler, releasing agent and pigment, and concrete formula is Lignin phenolic tree
Fat+phenolic resin 137 parts, paraformaldehyde 22 parts, 125 parts of bamboo powder, 3 parts of magnesia, calcium hydroxide 4.2 parts, tristearin
Acid 3.1 parts, three fly 7.8 parts of powder, 5 parts of water, ink black 2.9 parts and talcum powder 7.8 parts, open type plastic purificating set carries out half
Maturation process, low temperature roller bearing 40-60 DEG C；High temperature roller bearing 14-180 DEG C；Roll spacing 1.5-2.5mm, time 2-5min.Had
The sheet brittle prod of glossiness very well, crosses 200 mesh stand-by after crushed.
Embodiment 3
The preparation of alkali lignin modified thermoplastic phenolic resin
100 grams of phenol, alkali lignin (the 50% of phenol quality) and hydrochloric acid (the 6% of phenol quality) are added in reactor,
Reaction temperature 98 DEG C, reaction time 2.5h, add formaldehyde (phenolic aldehyde mol ratio is 1:0.85), reaction temperature is 95 DEG C-110 DEG C,
Reaction time 4h, first normal pressure reduces pressure and sloughs moisture and residue phenol, prepares alkali lignin modified phenolic resin.Common thermoplastic
Preparation method of phenolic resin is identical.
The preparation of alkali lignin base phenolaldehyde moulding compound
By above-mentioned alkali lignin modified thermoplastic phenolic resin with common thermoplastic's phenolic resin with 20%, 40%, 60%, 80%,
100% is blended, and is blended uniformly with other auxiliary agents such as curing agent, filler, releasing agent and pigment, and concrete formula is Lignin phenolic tree
Fat+phenolic resin 137 parts, paraformaldehyde 22 parts, 125 parts of bamboo powder, 3 parts of magnesia, calcium hydroxide 4.2 parts, tristearin
Acid 3.1 parts, three fly 7.8 parts of powder, 5 parts of water, ink black 2.9 parts and talcum powder 7.8 parts, open type plastic purificating set carries out half
Maturation process, low temperature roller bearing 40-60 DEG C；High temperature roller bearing 14-180 DEG C；Roll spacing 1.5-2.5mm, time 2-5min.Had
The sheet brittle prod of glossiness very well, crosses 200 mesh stand-by after crushed.
Embodiment 4
The preparation of enzymatic hydrolysis (EH) lignin modified thermoplastic phenolic resin
100 grams of phenol, enzymolysis xylogen (the 55% of phenol quality) and oxalic acid (the 6% of phenol quality) are added reactor
In, reaction temperature 105 DEG C, reaction time 3h, add formaldehyde (phenolic aldehyde mol ratio is 1:0.85), reaction temperature is 100 DEG C-110 DEG C,
Reaction time 4h, first normal pressure reduces pressure and sloughs moisture and residue phenol, prepares enzymatic hydrolysis (EH) lignin modified phenolic resin.Common thermoplastic
Property preparation method of phenolic resin is identical.
The preparation of enzymolysis xylogen base phenolaldehyde moulding compound
By above-mentioned enzymatic hydrolysis (EH) lignin modified thermoplastic phenolic resin with common thermoplastic's phenolic resin with 20%, 40%, 60%, 80%,
100% is blended, and is blended uniformly with other auxiliary agents such as curing agent, filler, releasing agent and pigment, and concrete formula is Lignin phenolic tree
Fat+phenolic resin 137 parts, thermosetting resin 22 parts, wood powder 125 parts, 3 parts of magnesia, calcium hydroxide 4.2 parts, hard
Resin acid 3.1 parts, three fly 7.8 parts of powder, 5 parts of water, ink black 2.9 parts and talcum powder 7.8 parts, open type plastic purificating set is carried out
Semi-curing process, low temperature roller bearing 40-60 DEG C；High temperature roller bearing 14-180 DEG C；Roll spacing 1.5-2.5mm, time 2-5min.Had
There is the sheet brittle prod of fine glossiness, cross 200 mesh after crushed stand-by.
Lignin-base phenolaldehyde moulding compound the performance test results table
Preparing resin conditions used by batten in form is: in lignin thermoplastic phenolic resin, lignin substitutes phenol amount 30%, wood
Quality thermoplastic phenolic resin accounts for the 60% of two kinds of resin qualities.
Claims (2)
1. the preparation method of the phenolaldehyde moulding compound of lignin modification, it is characterized in that by 100 grams of phenol, account for phenol quality 30% enzymolysis xylogen and account for phenol quality 5% hydrochloric acid add in reactor, reaction temperature 95 DEG C, reaction time 2h, adds formaldehyde, and phenolic aldehyde mol ratio is 1:0.85, reaction temperature is 90 DEG C-110 DEG C, reaction time 2h, first normal pressure reduces pressure and sloughs moisture and residue phenol, prepares enzymatic hydrolysis (EH) lignin modified phenolic resin；Common thermoplastic's preparation method of phenolic resin is identical；Above-mentioned enzymatic hydrolysis (EH) lignin modified thermoplastic phenolic resin is blended with 60% with common thermoplastic's phenolic resin, with curing agent, filler, other auxiliary agents such as releasing agent and pigment are blended uniformly, concrete formula is lignin phenol formaldehyde resin+phenolic resin 137 parts, methenamine 22 parts, wood powder 125 parts, 3 parts of magnesia, calcium hydroxide 4.2 parts, stearic acid 3.1 parts, three fly 7.8 parts of powder, 5 parts of water, ink black 2.9 parts and talcum powder 7.8 parts, open type plastic purificating set carries out semi-curing process, low temperature roller bearing 40 DEG C, high temperature roller bearing 145 DEG C, roll spacing 1.5, time 2.5min, obtain the sheet brittle prod with fine glossiness, cross 200 mesh after crushed stand-by.
2. the phenolaldehyde moulding compound of the lignin modification that method described in claim 1 prepares, it is characterised in that phenolaldehyde moulding compound bending strength 85MPa of described lignin modification, notch impact strength 1.4kJ/m2, unnotched impact strength 6.2kJ/m2, heat distortion temperature 175 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019202476A1 (en) * | 2018-04-20 | 2019-10-24 | Stora Enso Oyj | Process for preparing a bonding resin |
| WO2019202475A1 (en) * | 2018-04-20 | 2019-10-24 | Stora Enso Oyj | Process for preparing a bonding resin |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11193022B2 (en) | 2016-09-09 | 2021-12-07 | Idemitsu Kosan Co., Ltd. | Method for producing lignin-containing resin composition and lignin-containing resin molded article |
| CN106380887A (en) * | 2016-09-27 | 2017-02-08 | 中国林业科学研究院林产化学工业研究所 | Preparation method of lignin-base phenolic aldehyde molding compound |
| SE1850470A1 (en) * | 2018-04-20 | 2019-10-21 | Stora Enso Oyj | Adhesive formulation comprising lignin |
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| CN101891933A (en) * | 2010-08-13 | 2010-11-24 | 福州大学 | Method for preparing friction-resistant composite material by modifying solvent type lignin |
| CN102408740A (en) * | 2011-11-10 | 2012-04-11 | 程贤甦 | Molding compound modified by organosolv lignin or derivative thereof and preparation method thereof |
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Patent Citations (2)
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| CN101891933A (en) * | 2010-08-13 | 2010-11-24 | 福州大学 | Method for preparing friction-resistant composite material by modifying solvent type lignin |
| CN102408740A (en) * | 2011-11-10 | 2012-04-11 | 程贤甦 | Molding compound modified by organosolv lignin or derivative thereof and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019202476A1 (en) * | 2018-04-20 | 2019-10-24 | Stora Enso Oyj | Process for preparing a bonding resin |
| WO2019202475A1 (en) * | 2018-04-20 | 2019-10-24 | Stora Enso Oyj | Process for preparing a bonding resin |
| EP3781642A4 (en) * | 2018-04-20 | 2022-06-15 | Stora Enso Oyj | Process for preparing a bonding resin |
| EP4241949A3 (en) * | 2018-04-20 | 2023-11-08 | Stora Enso Oyj | Process for preparing a bonding resin |
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Denomination of invention: Lignin-modified phenolic molding compound and preparation method thereof Effective date of registration: 20220823 Granted publication date: 20160907 Pledgee: Bank of Nanjing Co.,Ltd. Xuzhou Branch Pledgor: Xuzhou Rooker Chemical Technology Co.,Ltd. Registration number: Y2022980013334 |