CN101348558A - Enzymatic hydrolysis lignin epoxide resin and preparation thereof - Google Patents
Enzymatic hydrolysis lignin epoxide resin and preparation thereof Download PDFInfo
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- CN101348558A CN101348558A CNA2008100717466A CN200810071746A CN101348558A CN 101348558 A CN101348558 A CN 101348558A CN A2008100717466 A CNA2008100717466 A CN A2008100717466A CN 200810071746 A CN200810071746 A CN 200810071746A CN 101348558 A CN101348558 A CN 101348558A
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- CN
- China
- Prior art keywords
- enzymatic hydrolysis
- dianhydride
- epoxide resin
- enzymolysis xylogen
- hydrolysis lignin
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 50
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 37
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000007071 enzymatic hydrolysis Effects 0.000 title claims description 31
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 title claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000728 polyester Polymers 0.000 claims abstract description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 6
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 6
- 241001330002 Bambuseae Species 0.000 claims abstract description 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 6
- 239000011425 bamboo Substances 0.000 claims abstract description 6
- 238000000855 fermentation Methods 0.000 claims abstract description 6
- 230000004151 fermentation Effects 0.000 claims abstract description 6
- 239000002023 wood Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 5
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 5
- 239000004593 Epoxy Chemical class 0.000 claims description 47
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 31
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- -1 phenolic aldehyde Chemical class 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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 group 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 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
- 239000012764 mineral filler Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 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
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 229920006295 polythiol Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 abstract 2
- 238000006266 etherification reaction Methods 0.000 abstract 2
- 239000000945 filler Substances 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920001732 Lignosulfonate Polymers 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 235000019357 lignosulphonate Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 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 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 239000000243 solution Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- LFMVFTMUPCOARK-UHFFFAOYSA-N ethane-1,2-diol;oxirane Chemical compound C1CO1.OCCO LFMVFTMUPCOARK-UHFFFAOYSA-N 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003960 organic solvent 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
- 230000008569 process Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
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- Epoxy Resins (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention provides an enzymolysis lignin epoxy resin and a preparation method thereof. The raw materials include: an enzymolysis lignin-dianhydride prepolymer, a glycidol ether, a catalyst, a curing agent and a filler. The preparation method comprises the following steps that: under the action of the catalyst, an etherification of a hydroxyl group contained in the enzymolysis lignin or a derivative of the enzymolysis lignin and dianhydride is carried to synthesize a prepolymer of enzymolysis lignin-dianhydride; then the prepolymer reacts with the glycidol ether and undergoes etherification and ring closing reaction to obtain an enzymolysis lignin--polyester type epoxy resin. The enzymolysis lignin adopted by the method is natural macromolecular material extracted from the residues which is produced in the preparation of alcohol through the fermentation of wood chips, bamboo and stalk, thereby not only effectively utilizing biological resources, but also replacing petrochemical raw materials. The enzymolysis lignin epoxy resin which can be used as a modifier for engineering materials, adhesives, paints and macromolecular materials has a broad application prospect.
Description
Technical field
The invention belongs to biomass resource comprehensive utilization and Resins, epoxy manufacturing technology field, more specifically relate to a kind of enzymatic hydrolysis lignin epoxide resin and preparation method thereof.
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 (national inventing patent ZL200410061295.X) 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.Use dihydroxyphenyl propane to be important source material when adopting high-boiling alcohol lignin to prepare Resins, epoxy in addition, and dihydroxyphenyl propane is a kind ofly can produce the environmental hormone of untoward reaction to HUMAN HEALTH, needs the novel wooden prime ring epoxy resins of exploitation without dihydroxyphenyl propane.
Summary of the invention
The object of the invention provides a kind of enzymatic hydrolysis lignin epoxide resin and preparation method thereof, this composition of raw materials is scientific and reasonable, the material purity height that adopts, epoxy resin product tensile strength height, the flexibility of preparation are strong, and modified effect is good, and cost is lower, environment-protecting asepsis, be with a wide range of applications, preparation is simple, workable.
Enzymatic hydrolysis lignin epoxide resin of the present invention is characterized in that: each component comprises according to parts by weight in the composition of raw materials of described enzymatic hydrolysis lignin epoxide resin:
Enzymolysis xylogen-dianhydride performed polymer 5-85 part
Glycidyl ether 10-95 part
Catalyzer 0.01-5 part
Solidifying agent 1-20 part
Weighting agent 0-80 part.
The preparation method of enzymatic hydrolysis lignin epoxide resin of the present invention, it is characterized in that: the preparation method of described enzymatic hydrolysis lignin epoxide resin is: the preparation method of described enzymatic hydrolysis lignin epoxide resin is: the enzymolysis xylogen that will make-dianhydride performed polymer reacts with glycidyl ether under catalyst action again, carry out etherificate, ring-closure reaction obtains enzymolysis xylogen-polyester type Resins, epoxy: described enzymolysis xylogen-dianhydride performed polymer and glycidyl ether are pressed described mixed, in the toluene that is dissolved in, the consumption of described toluene is the 5-50% of the gross weight of performed polymer and glycidyl ether, the catalyzer that adds 0.01 to 0.3 part earlier, be incubated 0.5-3h down at 75-95 ℃, and progressively add 0.01 to 4.7 part catalyzer, at 80-100 ℃ of reaction 1-4h down; After the reaction, remove excessive glycidyl ether and toluene through underpressure distillation, again through the pure water washing, branch vibration layer, the Resins, epoxy that last vacuum-drying obtains is a kind of brown look high viscosity liquid, adds weighting agent as required, adds solidifying agent in the Resins, epoxy that makes, solidify 1-4h down at 90-120 ℃, make lignin modification Resins, epoxy.
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, after producing performed polymer, they and two compound anhydrides react with glycidyl ether again, form the lignin epoxide resin network structure, 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%-60%, 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 generate the performed polymer of the xylogen-dianhydride of different structure with the reaction of two compound anhydrides, further reaction takes place in these performed polymers and dissimilar glycidyl ether, can prepare number of different types Resins, epoxy as required.
6. the enzymatic hydrolysis lignin epoxide resin of the present invention's preparation does not use bisphenol-A to be raw material, and than the environmental protection more of traditional bisphenol-A type Resins, epoxy, cost is lower.
7. 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
Each component comprises according to parts by weight in the composition of raw materials of enzymatic hydrolysis lignin epoxide resin:
Enzymolysis xylogen-dianhydride performed polymer 5-85 part
Glycidyl ether 10-95 part
Catalyzer 0.01-5 part
Solidifying agent 1-20 part
Weighting agent 0-80 part.
The parts by weight of each component comprise in the prescription of enzymolysis xylogen in the composition of raw materials of described enzymatic hydrolysis lignin epoxide resin-dianhydride performed polymer:
Enzymolysis xylogen or its derivative 5-70 part
Dianhydride 5-80 part
Ethylene glycol 15-75 part
Sulfuric acid catalyst 0.1-5 part,
Described enzymolysis xylogen is to adopt solvent method from wood chip, and bamboo, vegetation stalk fermentation prepare in the residue of ethanol, functional polysaccharide and extract the new type natural macromolecular material that obtains; Described enzymolysis xylogen derivative is through enzymolysis xylogen and aldehydes, epoxy compounds, isocyanic ester, phenols, halid chemical reaction or enzymolysis xylogen and other high polymer monomer graft copolymerization formation.
Described dianhydride is meant the organic compound that contains two anhydride groups in the molecule.
Described glycidyl ether is linear phenolic aldehyde polyglycidyl ether, Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether or bisphenol type diglycidylether.
Described catalyzer is one or more a mixture of water-soluble bases, as NaOH.
Described solidifying agent is one or more a mixture of amine, phenolic, polythiol type or multicomponent isocyanate solidifying agent.
Described weighting agent is one or more a mixture of needle-like, fibrous mineral filler, as metals such as silicon-dioxide, clay, lime carbonate, aluminium, magnesium and compound thereof etc.
The preparation method of described enzymolysis xylogen-dianhydride performed polymer is: according to described formula rate, in enzymolysis xylogen and dianhydride dissolving ethylene glycol, put into the reactor thorough mixing that agitator, thermometer, reflux condensing tube are housed then, add sulfuric acid catalyst, 110-145 ℃ of control reaction temperature temperature, taking out cooling behind the reaction 1-8h under constantly stirring leaves standstill, equal 7 with NaOH solution neutralization reaction product to pH value, and remove moisture with underpressure distillation, promptly get enzymolysis xylogen-dianhydride performed polymer.
Enzymolysis xylogen-dianhydride the performed polymer that has made is reacted with glycidyl ether under catalyst action again, carry out etherificate, ring-closure reaction obtains enzymolysis xylogen-polyester type Resins, epoxy: the preparation method of described enzymatic hydrolysis lignin epoxide resin is: the enzymolysis xylogen that will make-dianhydride performed polymer reacts with glycidyl ether under catalyst action again, carry out etherificate, ring-closure reaction obtains enzymolysis xylogen-polyester type Resins, epoxy: described enzymolysis xylogen-dianhydride performed polymer and glycidyl ether are pressed described mixed, in the toluene that is dissolved in, the consumption of described toluene is the 5-50% of the gross weight of performed polymer and glycidyl ether, the catalyzer that adds 0.01 to 0.3 part earlier, be incubated 0.5-3h down at 75-95 ℃, and progressively add 0.01 to 4.7 part catalyzer, at 80-100 ℃ of reaction 1-4h down; After the reaction, remove excessive glycidyl ether and toluene through underpressure distillation, again through the pure water washing, branch vibration layer, the Resins, epoxy that last vacuum-drying obtains is a kind of brown look high viscosity liquid, adds weighting agent as required, adds solidifying agent in the Resins, epoxy that makes, solidify 1-4h down at 90-120 ℃, make lignin modification Resins, epoxy.
In preparation process, the alkali catalyst of 0.01-5 part, the solidifying agent of 1-20 part and other addition materials add according to the needs of Resins, epoxy product properties.
Raw material: the residue that enzymolysis xylogen and derivative thereof utilize Shandong, Henan stalk fermentation to prepare alcohol by the inventor extracts preparation and (consults " separating and extracting method of enzymolysis xylogen ", national inventing patent application number 200410061438.7; " method for organically separating and extracting of enzymolysis xylogen ", national inventing patent application number 2006101438894).Other raw materials such as catalyzer, MALEIC ANHYDRIDE, Pyroglutaric acid, Tetra Hydro Phthalic Anhydride, ethylene glycol, ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol, trivinyl tetramine etc. are the chemically pure reagent that reagent company provides.
Below be several specific embodiment of the present invention, further specify the present invention, but the present invention be not limited only to this.
Embodiment 1.
50 gram enzymolysis xylogens and 100 gram MALEIC ANHYDRIDE are dissolved in the 50 gram ethylene glycol, add 15 gram weight concentration again and be 50% aqueous sulfuric acid as catalyzer, put into the three neck round-bottomed flask thorough mixing that magnetic stirring apparatus, thermometer, reflux condensing tube are housed then, the heating control reaction temperature is 130 ℃, open nitrogen protection, under constantly stirring, take out cool to room temperature behind the reaction 5h, with 6.2 gram NaOH solution neutralization reaction products, and remove moisture with underpressure distillation, obtain 186.4 gram performed polymers; Performed polymer is divided into five parts, in every part of performed polymer, adds ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol, 10 gram toluene and 3.5 gram sodium hydroxide catalysts respectively, taking out cool to room temperature behind the reaction 2.0h under 80 ℃ of conditions in table 1 ratio; Product washs with pure water, removes water soluble component, and places 60 ℃ of vacuum drying oven dryings, obtains a kind of brown look high viscosity liquid, promptly obtains the polyester type lignin epoxide resin.Measure oxirane value with the pyridine hydrochloride method.The solidifying agent trivinyl tetramine that adds 7.5 grams in the Resins, epoxy that makes respectively after solidifying 2h under 150 ℃, is measured adhesive shear strength.Along with the increase of performed polymer content, the gluing shearing resistance of epoxy resin cured product increases afterwards earlier and reduces.The performed polymer content ratio hour though oxirane value is higher, owing to also having more unreacted ethylene glycol bisthioglycolate epoxy glycerite ether monomer, has reduced the cross-linking density of system.Increase along with performed polymer content, epoxy group(ing) in the ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol and carboxylic acid group's reaction are abundant more, free glycols diglycidyl ether monomer reduces gradually, increase xylogen amount along with performed polymer content also increases thereupon simultaneously, this can increase the cross-linking density of Resins, epoxy, thereby improves the gluing shearing resistance.When performed polymer content was 50%, the gluing shearing resistance of Resins, epoxy reached maximum value.
Table 1-1 lignin-base Resins, epoxy synthetic ratio and oxirane value
| Numbering | Give aggressiveness/ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol | Oxirane value (mol/100g) | Adhesive shear strength/MP |
| A B C D E | 10％ 20％ 30％ 40％ 50％ | 0.67 0.56 0.42 0.30 0.24 | 2.70 3.21 5.11 8.30 10.6 |
Embodiment 2.
25 gram enzymolysis xylogens and 40 gram Pyroglutaric acids are dissolved in the 30 gram ethylene glycol, add 6 gram weight concentration again and be 50% aqueous sulfuric acid as catalyzer, put into the three neck round-bottomed flask thorough mixing that magnetic stirring apparatus, thermometer, reflux condensing tube are housed then, the heating control reaction temperature is 140 ℃, open nitrogen protection, under constantly stirring, take out cool to room temperature behind the reaction 4h, obtain 90.4 gram performed polymers; Join 180 gram ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol, 25 gram toluene and 5.5 gram sodium hydroxide catalysts again, taking out cool to room temperature behind the reaction 2.0h under 80 ℃ of conditions; Product washs with pure water, removes water soluble component, and places 60 ℃ of vacuum drying oven dryings, obtains a kind of brown look high viscosity liquid, promptly obtains the polyester type lignin epoxide resin.The solidifying agent trivinyl tetramine that adds 35 grams in the Resins, epoxy that makes respectively after solidifying 2h under 150 ℃, makes enzymatic hydrolysis (EH) lignin modified Resins, epoxy, and measuring its adhesive shear strength is 8.71MP.
Embodiment 3.
25 gram enzymolysis xylogens and 37 gram Tetra Hydro Phthalic Anhydrides are dissolved in the 25 gram ethylene glycol, add 6 gram weight concentration again and be 50% aqueous sulfuric acid as catalyzer, put into the three neck round-bottomed flask thorough mixing that magnetic stirring apparatus, thermometer, reflux condensing tube are housed then, the heating control reaction temperature is 140 ℃, open nitrogen protection, under constantly stirring, take out cool to room temperature behind the reaction 4h, obtain 84.2 gram performed polymers; Join 185 gram ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol, 20 gram toluene and 5.5 gram sodium hydroxide catalysts again, taking out cool to room temperature behind the reaction 2.0h under 80 ℃ of conditions; Product washs with pure water, removes water soluble component, and places 60 ℃ of vacuum drying oven dryings, obtains a kind of brown look high viscosity liquid, promptly obtains the polyester type lignin epoxide resin.The solidifying agent trivinyl tetramine that adds 33 grams in the Resins, epoxy that makes respectively after solidifying 2h under 150 ℃, makes enzymatic hydrolysis (EH) lignin modified Resins, epoxy, and measuring its adhesive shear strength is 8.21MP.
The comparative example
25 gram calcium lignin sulphonates (paper mill, Guangzhou product) and 50 gram MALEIC ANHYDRIDE are dissolved in the 25 gram ethylene glycol, the sulfuric acid catalyst that adds 7 grams 50% again, put into the three neck round-bottomed flask thorough mixing that magnetic stirring apparatus, thermometer, reflux condensing tube are housed then, the heating control reaction temperature is 130 ℃, open nitrogen protection, under constantly stirring, take out cool to room temperature behind the reaction 5h, obtain 93.4 gram performed polymers; Add 180 gram ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol, 20 gram toluene and 6.5 gram sodium hydroxide catalysts again, taking out cool to room temperature behind the reaction 2.0h under 80 ℃ of conditions; Product washs with pure water, remove water soluble component, most of lignin sulfonate does not participate in the reaction of performed polymer by flush away, residue places 60 ℃ of vacuum drying oven dryings, obtain a kind of light brown heavy-gravity liquid, though obtain polyester type Resins, epoxy, xylogen is not attached among the Resins, epoxy, can't obtain lignin modification Resins, epoxy yet.
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 (10)
1. enzymatic hydrolysis lignin epoxide resin, it is characterized in that: each component comprises according to parts by weight in the composition of raw materials of described enzymatic hydrolysis lignin epoxide resin:
Enzymolysis xylogen-dianhydride performed polymer 5-85 part
Glycidyl ether 10-95 part
Catalyzer 0.01-5 part
Solidifying agent 1-20 part
Weighting agent 0-80 part.
2. enzymatic hydrolysis lignin epoxide resin according to claim 1 is characterized in that: the parts by weight of each component comprise in the prescription of enzymolysis xylogen in the composition of raw materials of described enzymatic hydrolysis lignin epoxide resin-dianhydride performed polymer:
Enzymolysis xylogen or its derivative 5-70 part
Dianhydride 5-80 part
Ethylene glycol 15-75 part
Sulfuric acid catalyst 0.1-5 part,
The preparation method of described enzymolysis xylogen-dianhydride performed polymer is: according to described formula rate, in enzymolysis xylogen and dianhydride dissolving ethylene glycol, put into the reactor thorough mixing that agitator, thermometer, reflux condensing tube are housed then, add sulfuric acid catalyst, 110-145 ℃ of control reaction temperature temperature, taking out cooling behind the reaction 1-8h under constantly stirring leaves standstill, equal 7 with NaOH solution neutralization reaction product to pH value, and remove moisture with underpressure distillation, promptly get enzymolysis xylogen-dianhydride performed polymer.
3. enzymatic hydrolysis lignin epoxide resin according to claim 2, it is characterized in that: described enzymolysis xylogen is to adopt solvent method from wood chip, bamboo, vegetation stalk fermentation prepare and extract the new type natural macromolecular material that obtains in the residue of ethanol, functional polysaccharide; Described enzymolysis xylogen derivative is through enzymolysis xylogen and aldehydes, epoxy compounds, isocyanic ester, phenols, halid chemical reaction or enzymolysis xylogen and other high polymer monomer graft copolymerization formation.
4. enzymatic hydrolysis lignin epoxide resin according to claim 2 is characterized in that: described dianhydride is meant the organic compound that contains two anhydride groups in the molecule.
5. enzymatic hydrolysis lignin epoxide resin according to claim 2 is characterized in that: it is the aqueous sulfuric acid of 30%-70% that described sulfuric acid catalyst adopts weight concentration.
6. enzymatic hydrolysis lignin epoxide resin according to claim 1 is characterized in that: described glycidyl ether is linear phenolic aldehyde polyglycidyl ether, Fatty Alcohol(C12-C14 and C12-C18) glycidyl ether or bisphenol type diglycidylether.
7. enzymatic hydrolysis lignin epoxide resin according to claim 1 is characterized in that: described catalyzer is one or more a mixture of water-soluble bases.
8. enzymatic hydrolysis lignin epoxide resin according to claim 1 is characterized in that: described solidifying agent is one or more a mixture of amine, phenolic, polythiol type or multicomponent isocyanate solidifying agent.
9. enzymatic hydrolysis lignin epoxide resin according to claim 1 is characterized in that: described weighting agent is one or more a mixture of needle-like, fibrous mineral filler silicon-dioxide, clay, lime carbonate, aluminium, magnesium metal and compound thereof.
10. one kind as claim 1,2,3,4,5,6,7, the preparation method of 8 or 9 described enzymatic hydrolysis lignin epoxide resins, it is characterized in that: the preparation method of described enzymatic hydrolysis lignin epoxide resin is: the enzymolysis xylogen that will make-dianhydride performed polymer reacts with glycidyl ether under catalyst action again, carry out etherificate, ring-closure reaction obtains enzymolysis xylogen-polyester type Resins, epoxy: described enzymolysis xylogen-dianhydride performed polymer and glycidyl ether are pressed described mixed, in the toluene that is dissolved in, the consumption of described toluene is the 5-50% of the gross weight of performed polymer and glycidyl ether, the catalyzer that adds 0.01 to 0.3 part earlier, be incubated 0.5-3h down at 75-95 ℃, and progressively add 0.01 to 4.7 part catalyzer, at 80-100 ℃ of reaction 1-4h down; After the reaction, remove excessive glycidyl ether and toluene through underpressure distillation, again through the pure water washing, branch vibration layer, the Resins, epoxy that last vacuum-drying obtains is a kind of brown look high viscosity liquid, adds weighting agent as required, adds solidifying agent in the Resins, epoxy that makes, solidify 1-4h down at 90-120 ℃, make lignin modification Resins, epoxy.
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