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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- CN1966545A CN1966545A CNA2006100695294A CN200610069529A CN1966545A CN 1966545 A CN1966545 A CN 1966545A CN A2006100695294 A CNA2006100695294 A CN A2006100695294A CN 200610069529 A CN200610069529 A CN 200610069529A CN 1966545 A CN1966545 A CN 1966545A
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- enzymatic hydrolysis
- epoxy
- epoxy chloropropane
- hydrolysis lignin
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- 229920005610 lignin Polymers 0.000 title claims abstract description 40
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 39
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 10
- 230000007071 enzymatic hydrolysis Effects 0.000 title claims description 26
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 title claims description 26
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- -1 bisphenol A compound Chemical class 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 42
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 239000004593 Epoxy Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000006837 decompression Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 4
- 229930013930 alkaloid Natural products 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000012764 mineral filler Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920006295 polythiol Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 abstract description 4
- 235000017491 Bambusa tulda Nutrition 0.000 abstract description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 abstract description 4
- 239000011425 bamboo Substances 0.000 abstract description 4
- 239000002023 wood Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000002255 enzymatic effect Effects 0.000 abstract 6
- 239000000945 filler Substances 0.000 abstract 2
- 239000002861 polymer material Substances 0.000 abstract 2
- 244000025254 Cannabis sativa Species 0.000 abstract 1
- 244000082204 Phyllostachys viridis Species 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 229920005615 natural polymer Polymers 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000010902 straw Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229920001732 Lignosulfonate Polymers 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 235000019357 lignosulphonate Nutrition 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Epoxy Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
本发明提供一种酶解木质素环氧树脂的原料配方及其制备方法，配方为酶解木质素或其衍生物，双酚A型化合物，环氧氯丙烷或它与有机溶剂混合液，催化剂，固化剂，填充剂；制备方法为将酶解木质素或其衍生物加入环氧氯丙烷溶液或它与有机溶剂的混合液中，搅拌溶解再加入催化剂同时加入固化剂或固化剂和填充剂的混合物加热使反应完全，最终反应物减压蒸出过量环氧氯丙烷或有机溶剂得不溶于水的棕色固体，经水洗烘干得酶解木质素环氧树脂。该法采用的酶解木质素是从木片、竹子、草木秸秆中提取的天然高分子材料，既有效利用生物资源又可替代石化原料，制得的酶解木质素环氧树脂可用于工程材料、胶粘剂、涂料或高分子材料的改性剂，有广泛的应用前景。The invention provides a raw material formula of enzymatic lignin epoxy resin and its preparation method. The formula is enzymatic lignin or its derivatives, bisphenol A compound, epichlorohydrin or its mixed solution with an organic solvent, and a catalyst , curing agent, filler; the preparation method is to add enzymatic lignin or its derivatives to epichlorohydrin solution or its mixed solution with organic solvent, stir and dissolve, then add catalyst and add curing agent or curing agent and filler at the same time The mixture is heated to complete the reaction, and the final reactant is evaporated under reduced pressure to remove excess epichlorohydrin or organic solvent to obtain a water-insoluble brown solid, which is washed with water and dried to obtain an enzymatic lignin epoxy resin. The enzymatic lignin used in this method is a natural polymer material extracted from wood chips, bamboo, and grass straw, which not only effectively utilizes biological resources but also can replace petrochemical raw materials. The enzymatic lignin epoxy resin prepared can be used for engineering materials, Adhesives, coatings or modifiers of polymer materials have broad application prospects.
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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