CN1966545A - Enzymatic hydrolysis lignin epoxy resin material formula and its preparation method - Google Patents
Enzymatic hydrolysis lignin epoxy resin material formula and its preparation method Download PDFInfo
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Abstract
The invention provides a raw materials formula of enzymolysis lignin epoxy resin and its fabrication method. The formula includes enzymolysis lignin or its derivatives, bisphenol A-type compound, epichlorohydrin or its mixture with organic solvent, catalyst, curing agent, and filler. The preparation method includes adding enzymolysis lignin or its derivatives into epichlorohydrin solution or its mixture with organic solvent, stirring and adding catalyst, curing agent or the mixture of curing agent and filler, heating and reacting completely, vacuum-distilling to remove the excessive epichlorohydrin or organic solvent to obtain brown solid insoluble in water, washing, and drying to obtain enzymolysis lignin epoxy resin. The adopted enzymolysis lignin is the natural polymer material extracted from wood, bamboo and straw, which not only effectively use the biological resources, but also can replace petrochemical raw materials. The prepared enzymolysis lignin epoxy resin can be used for engineering materials, adhesives, coating or polymer materials modifier, which has a broad application prospect.
Description
Technical field
The present invention relates to biomass resource comprehensive utilization and Resins, epoxy production, more specifically relate to and utilize enzymolysis xylogen and derivative thereof preparation method as the lignin epoxide resin main raw material.
Background technology
In the research report of preparation Resins, epoxy, had in the past and used the precedent of sulfonated lignin as raw material, but sulfonated lignin are to extract to obtain from traditional papermaking " black liquor ", not only foreign matter content is very high, and great structural modification takes place in the natural lignin in the plant material after the boiling of alkali and sulphite, chemically reactive obviously reduces, preparation Resins, epoxy is essential through complicated acidifying, just can obtain lignin epoxide resin with epichlorohydrin reaction again after the modification processing of complexity such as phenolate modification and the purifying process, and can produce bigger disadvantageous effect the performance of Resins, epoxy.The high-boiling alcohol lignin that also has research and utilization high boiling solvent (hbs) method to prepare in addition prepares the novel method of Resins, epoxy, high-boiling alcohol lignin prepares Resins, epoxy has many improvement than using sulfonated lignin as raw material, but need use the higher height of the price alcohol that boils during high boiling solvent (hbs) method prepared xylogen, and high boiling solvent (hbs) reclaims and needs to consume more energy.
Summary of the invention
The present invention seeks to solve the problems referred to above that prior art exists, the preparation method of a kind of good product performance, production cost is low, processing method is easy enzymatic hydrolysis lignin epoxide resin is provided.
Composition of raw materials of the enzymatic hydrolysis lignin epoxide resin that provides of the present invention and preparation method thereof, its composition of raw materials is:
Enzymolysis xylogen or its derivative 5-80 part
Bisphenol A-type compound 0-85 part
Epoxy chloropropane or epoxy chloropropane and organic solvent mixed solution 10-95 part
Catalyzer 0.01-5 part
Solidifying agent 0.05-10 part
Weighting agent 0-80 part
Composition of raw materials of the enzymatic hydrolysis lignin epoxide resin that provides of the present invention and preparation method thereof, its described preparation process is: enzymolysis xylogen or its derivative are joined in the mixing solutions of epoxy chloropropane solution or epoxy chloropropane and organic solvent, fully stir to make it to dissolve fully or under heated condition, fully stir and make it to dissolve fully, wherein Heating temperature 50-120 ℃, add catalyzer again and add the mixture of solidifying agent or solidifying agent and weighting agent simultaneously, make it to react completely through heating, Heating temperature is 50-120 ℃, in pressure range is 5-20mmHg, time 0.5-3.0 hour, temperature 60-120 ℃ decompression steams under the condition decompression of end reaction thing is steamed excessive epoxy chloropropane or organic solvent, obtain water insoluble and the rubber-like brown solid, in temperature is 80-120 ℃, and the time is to obtain enzymatic hydrolysis lignin epoxide resin through the washing oven dry under 0.5-3.0 hour the drying condition.
The present invention has following advantage:
1. the enzymolysis xylogen of the present invention's employing is to adopt solvent method from wood chip, bamboo, the vegetation stalk fermentation prepares the natural macromolecular material that extraction obtains in the alcoholic acid residue, and lignin dissolution makes it separate with other solid residues among alkaline aqueous solution or organic solvent.Outside desolventizing, the preparation process of enzymolysis xylogen do not add other chemical agents, enzymolysis xylogen purity height, and ash oontent is than low tens times of traditional sulfonated lignin.
2. because enzymolysis xylogen is to adopt solvent method from wood chip, and bamboo, vegetation stalk fermentation prepare the natural macromolecular material that extraction obtains in the alcoholic acid residue, it has kept the chemically reactive of natural lignin preferably.Enzymolysis xylogen is a raw material, under certain conditions, enzymolysis xylogen and aldehydes, phenols, or halide reaction prepares derivative, also can form graft product with other high polymer monomer copolymerization, can be according to needs to different rings epoxy resins product properties, the enzymolysis xylogen derivative of selecting adequate types is a raw material.
3. enzymolysis xylogen and derivative thereof can improve the tensile strength of Resins, epoxy goods as the main raw material of Resins, epoxy, increase the flexibility of Resins, epoxy, than traditional sulfonated lignin better modified effect are arranged.Enzymolysis xylogen and derivative thereof are network-like superpolymer, form the lignin epoxide resin network structure after they and epoxy chloropropane one react, and have therefore improved the tensile strength of Resins, epoxy goods, increase the flexibility of Resins, epoxy.Enzymolysis xylogen and derivative thereof keep more multi-active base group than traditional sulfonated lignin, thereby better modified effect is arranged.
4. enzymolysis xylogen and derivative thereof the addition in the Resins, epoxy goods can be according to the needs and the decision of enzymolysis xylogen derivative type characteristics of Resins, epoxy performance, generally can be between 5%-80%, its result had both improved the performance of Resins, epoxy goods, can reduce the production cost of Resins, epoxy again, improve competitiveness of product.
5. enzymolysis xylogen and derivative thereof can (comprise the Bisphenol F type with dihydroxyphenyl propane or with other Resins, epoxy raw material parents, the bisphenol S type, the Hydrogenated Bisphenol A type, linear phenol aldehyde type, multi-functional basic Racemic glycidol resin and halogenated epoxy resin with specific function) be mixed, again with and epichlorohydrin reaction, obtain the mixture of broad variety Resins, epoxy.
6. the enzymatic hydrolysis lignin epoxide resin that makes of the present invention can be used for engineering materials, tackiness agent, and the properties-correcting agent of coating or macromolecular material has wide practical use.
Embodiment
With weight fraction than being enzymolysis xylogen of 5-80 part or its derivative, the epoxy chloropropane of 0-85 part bisphenol A-type compound and 10-95 part or the mixing solutions Hybrid Heating or the heating and pressurizing of epoxy chloropropane and organic solvent, Heating temperature is 60-120 ℃, the pressure of pressurization is 0-2.0Pa, and constantly stirred 15-90 minute, allowing enzymolysis xylogen or its derivative fully dissolve with epoxy chloropropane mixes, in 15-90 minute, add 0.01-3 part alkaloids catalyzer then, stirring and refluxing 0.5-5 hour, in pressure range is 5-20mmHg, time 0.5-3.0 hour, temperature 60-120 ℃ decompression steams to reduce pressure under the condition and steams excessive epoxy chloropropane, obtain epoxy chloropropane and water insoluble and have certain elastic brown solid, in temperature is 80-120 ℃, the time be under 0.5-3.0 hour the drying condition through washing dry fragility brown solid enzymatic hydrolysis lignin epoxide resin.
Wherein the organic solvent in the raw material is one or more a mixture of alcohols, tetrahydrofuran (THF), dioxane or dimethyl formamide; Catalyzer is an alkaloids; Solidifying agent is one or more a mixture of amine, anhydrides, phenolic or polythiol type, multicomponent isocyanate solidifying agent; Weighting agent can be clay, lime carbonate, the mixture of one or more of needle-like such as metal such as aluminium, magnesium and compound thereof, fibrous mineral filler; The bisphenol A-type compound comprises dihydroxyphenyl propane or other Resins, epoxy raw materials, and other Resins, epoxy raw materials are one or more mixture of Bisphenol F type, bisphenol S type, Hydrogenated Bisphenol A type, linear phenol aldehyde type, multi-functional basic Racemic glycidol resin and the halogenated epoxy resin with specific function.
Wherein epoxy chloropropane and organic solvent mixed solution are that epoxy chloropropane and organic solvent are by any ratio blended solution.
In preparation process, the alkali catalyst of 0.01-5 part, the solidifying agent of 0.05-5 part and other addition materials add according to the needs of Resins, epoxy product properties.
Embodiment 1
Measure the 21ml epoxy chloropropane, add in the clean 250ml there-necked flask, take by weighing the 5g enzymolysis xylogen, pour in the flask container, be warming up to 50 ℃, stir 30min, allowing xylogen fully dissolve with epoxy chloropropane mixes, in 20 minutes, add 0.8ml30%NaOH solution, be warmed up to 55-60 ℃, stirring and refluxing 1 hour, be warmed up to 70 ℃, added the NaOH solution of 2ml30% in 20 minutes, restir refluxed 1 hour, at pressure range 5-10mmHg, time 1.5-2.0 hour, decompression steams excessive epoxy chloropropane under the condition that temperature is 90 ℃, obtains 10ml epoxy chloropropane and water insoluble and have certain elastic brown solid, through washing dry 10.85g fragility brown solid enzymatic hydrolysis lignin epoxide resin.
Embodiment 2
Measure 25ml epoxy chloropropane and 15ml ethanol, add in the clean 250ml there-necked flask, take by weighing the 5g enzymolysis xylogen, pour in the flask container, add the 0.3g nano silicon again, be warming up to 50 ℃, stir 30min, allowing xylogen fully dissolve with epoxy chloropropane mixes, in 20 minutes, add 2.0ml30%NaOH solution, be warmed up to 55-60 ℃, stirring and refluxing 1 hour adds 0.4g quadrol solidifying agent and is warmed up to 70 ℃, restir refluxed 1 hour, at pressure range 5-10mmHg, time 1.5-2.0 hour, decompression steams excessive epoxy chloropropane under the condition that temperature is 90 ℃, obtains having certain elastic brown solid, through washing dry the enzymatic hydrolysis lignin epoxide resin of 10.60g nano silicon toughening modifying.
Embodiment 3
Measure the 25ml epoxy chloropropane, add in the clean 250ml there-necked flask, take by weighing 3g enzymolysis xylogen and 2.5g dihydroxyphenyl propane, pour in the flask container, be warming up to 50 ℃, stir 30min, allowing xylogen fully dissolve with epoxy chloropropane mixes, in 20 minutes, add 0.8ml30%NaOH solution, be warmed up to 55-60 ℃, stirring and refluxing 1 hour is warmed up to 70 ℃, adds the NaOH solution of 2ml30% in 20 minutes, restir refluxed 1 hour, in pressure range is 5-10mmHg, time 1.5-2.0 hour, the condition that temperature is 90 ℃ steams excessive epoxy chloropropane in decompression, obtains 10ml epoxy chloropropane and water insoluble and have certain elastic solid, dries to such an extent that the 11.30g color is a light brown solid enzymatic hydrolysis lignin epoxide resin through washing.
Embodiment 4
Measure 40ml epoxy chloropropane and 25ml ethanol, add in the clean 250ml there-necked flask, take by weighing 4.5g enzymolysis xylogen and 3.5g Hydrogenated Bisphenol A, pour in the flask container, add the 2.3g aluminium-hydroxide powder again, be warming up to 50 ℃, stir 30min, allowing xylogen fully dissolve with epoxy chloropropane mixes, in 20 minutes, add 2.0ml30%NaOH solution, be warmed up to 55-60 ℃, stirring and refluxing 1 hour adds 0.2g Bian Ji dimethylamine solidifying agent and is warmed up to 70 ℃, restir refluxed 1 hour, at pressure range 5-10mmHg, time 1.5-2.0 hour, decompression steams excessive epoxy chloropropane under the condition that temperature is 90 ℃, obtains having certain elastic brown solid, through washing dry the fire-retardant enzymatic hydrolysis lignin epoxide resin with improved weathering of 16.60g.
Different addition epoxy chloropropane are to the influence of lignin-base Resins, epoxy synthetic ratio, output and oxirane value
Proportioning by table 1-1, measuring epoxy chloropropane earlier adds in the beaker of 100ml, taking by weighing enzymolysis xylogen 2.5g again pours in the beaker, stirring allows its dissolving, if insoluble can the heating a little, generally to 40 ℃ of left and right sides Quan Rong, under agitation slowly splash into the 0.4ml30% sodium hydroxide solution, add back continuation stirring and left standstill 1 hour half an hour, continue under agitation to splash into 0.8ml30%NaOH solution, after stirring half an hour, left standstill 24 hours, product is the solid that certain elastic brownish black is arranged, through washing, the filter paper funnel filters, oven dry (90 ℃ of temperature, 2.5 hours time) obtain pale brown look brittle solid after, weighing is measured oxirane value with the pyridine hydrochloride method.
Table 1-1 lignin-base Resins, epoxy synthetic ratio, output and oxirane value
| Numbering | Enzymolysis xylogen (g) | Epoxy chloropropane (ml) | 30％NaOH (ml) | Reaction times (my god) | Lignin-base Resins, epoxy (g) | Oxirane value (mol/100g) |
| B C D E | 2.5 2.5 2.5 2.5 | 2.5 5.0 7.5 10.0 | 1.4 1.4 1.4 1.4 | 1-2 1-2 1-2 1-2 | 4.3 4.4 4.6 4.7 | 0.0835 0.0947 0.1103 0.1187 |
The comparison of resulting lignin-base Resins, epoxy of embodiment and bisphenol A type epoxy resin thermostability:
Synthetic bisphenol A type epoxy resin under embodiment and the similarity condition is carried out thermal stability analysis, and the result shows enzymatic hydrolysis lignin epoxide resin than bisphenol A type epoxy resin at high temperature (greater than 250 ℃), and thermal weight loss still less shows that it has thermostability preferably.
The present invention adopts from wood chip, bamboo, extracting the enzymolysis xylogen obtain in the residue of vegetation stalk microbe alcohol prepared by fermenting, to prepare Resins, epoxy be a significant improvement, and not only can effectively utilize biomass resource but also can substitute petrochemical materials has important practical value.
Claims (11)
1. composition of raw materials of an enzymatic hydrolysis lignin epoxide resin and preparation method thereof, it is characterized in that: described composition of raw materials is:
Enzymolysis xylogen or its derivative 5-80 part
Bisphenol A-type compound 0-85 part
Epoxy chloropropane or epoxy chloropropane and organic solvent mixed solution 10-95 part
Catalyzer 0.01-5 part
Solidifying agent 0.05-10 part
Weighting agent 0-80 part
2. composition of raw materials of enzymatic hydrolysis lignin epoxide resin according to claim 1 and preparation method thereof is characterized in that: described organic solvent is one or more a mixture of alcohols, tetrahydrofuran (THF), dioxane or dimethyl formamide.
3. composition of raw materials of enzymatic hydrolysis lignin epoxide resin according to claim 1 and preparation method thereof, it is characterized in that: described catalyzer is an alkaloids.
4. composition of raw materials of enzymatic hydrolysis lignin epoxide resin according to claim 1 and preparation method thereof is characterized in that: described solidifying agent is one or more a mixture of amine, anhydrides, phenolic or polythiol type, multicomponent isocyanate solidifying agent.
5. composition of raw materials of enzymatic hydrolysis lignin epoxide resin according to claim 1 and preparation method thereof, it is characterized in that: described weighting agent can be clay, lime carbonate, the mixture of one or more of needle-like such as metal such as aluminium, magnesium and compound thereof, fibrous mineral filler.
6. composition of raw materials of enzymatic hydrolysis lignin epoxide resin according to claim 1 and preparation method thereof, it is characterized in that: described bisphenol A-type compound comprises dihydroxyphenyl propane or other Resins, epoxy raw materials.
7. the preparation method of enzymatic hydrolysis lignin epoxide resin according to claim 6 is characterized in that: described other Resins, epoxy raw materials are one or more mixture of Bisphenol F type, bisphenol S type, Hydrogenated Bisphenol A type, linear phenol aldehyde type, multi-functional basic Racemic glycidol resin and the halogenated epoxy resin with specific function.
8. the preparation method of enzymatic hydrolysis lignin epoxide resin according to claim 1, it is characterized in that: described epoxy chloropropane and organic solvent mixed solution, wherein epoxy chloropropane mixes by any ratio with organic solvent.
9. composition of raw materials of an enzymatic hydrolysis lignin epoxide resin and preparation method thereof, it is characterized in that: described preparation process is: enzymolysis xylogen or its derivative are joined in the mixing solutions of epoxy chloropropane solution or epoxy chloropropane and organic solvent, fully stir to make it to dissolve fully or under heated condition, fully stir and make it to dissolve fully, wherein Heating temperature 50-120 ℃, add catalyzer again and add the mixture of solidifying agent or solidifying agent and weighting agent simultaneously, make it to react completely through heating, Heating temperature is 50-120 ℃, in pressure range is 5-20mmHg, time 0.5-3.0 hour, temperature 60-120 ℃ decompression steams under the condition decompression of end reaction thing is steamed excessive epoxy chloropropane or organic solvent, obtain water insoluble and the rubber-like brown solid, in temperature is 80-120 ℃, and the time is to obtain enzymatic hydrolysis lignin epoxide resin through the washing oven dry under 0.5-3.0 hour the drying condition.
10. the preparation method of enzymatic hydrolysis lignin epoxide resin according to claim 9, it is characterized in that: with weight fraction than being enzymolysis xylogen of 5-80 part or its derivative, the epoxy chloropropane of 0-85 part bisphenol A-type compound and 10-95 part or the mixing solutions Hybrid Heating or the heating and pressurizing of epoxy chloropropane and organic solvent, Heating temperature is 60-120 ℃, the pressure of pressurization is 0-2.0Pa, and constantly stirred 15-90 minute, allowing enzymolysis xylogen or its derivative fully dissolve with epoxy chloropropane mixes, in 15-90 minute, add 0.01-3 part alkaloids catalyzer then, stirring and refluxing 0.5-5 hour, in pressure range is 5-20mmHg, time 0.5-3.0 hour, temperature 60-120 ℃ decompression steams to reduce pressure under the condition and steams excessive epoxy chloropropane, obtain epoxy chloropropane and water insoluble and have certain elastic brown solid, in temperature is 80-120 ℃, the time be under 0.5-3.0 hour the drying condition through washing dry fragility brown solid enzymatic hydrolysis lignin epoxide resin.
11. the preparation method according to claim 9 or 10 described enzymatic hydrolysis lignin epoxide resins is characterized in that: the alkali catalyst of described 0.01-5 part, the solidifying agent of 0.05-5 part and other addition materials add according to the needs of Resins, epoxy product properties.
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| CN106750179A (en) * | 2017-03-21 | 2017-05-31 | 南京林业大学 | A kind of preparation method of enzymolysis xylogen base epoxy |
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| CN114426715A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Large-particle-size lignin/styrene butadiene rubber composite particle and synthetic method thereof |
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