CN108084402A - A kind of hemicellulose base epoxy and preparation method thereof - Google Patents
A kind of hemicellulose base epoxy and preparation method thereof Download PDFInfo
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- CN108084402A CN108084402A CN201711354414.4A CN201711354414A CN108084402A CN 108084402 A CN108084402 A CN 108084402A CN 201711354414 A CN201711354414 A CN 201711354414A CN 108084402 A CN108084402 A CN 108084402A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
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Abstract
The invention discloses a kind of hemicellulose base epoxies and preparation method thereof, the hemicellulose base epoxy from viscose fiber wastewater to recycle the hemicellulose obtained as raw material, through with epoxides carry out it is etherification modified after hemicellulose based polyether polyol is made, continue to prepare hemicellulose base epoxy using the hemicellulose based polyether polyol as raw material.The present invention is using the hemicellulose of viscose rayon devil liquor recovery as raw material, hemicellulose base epoxy is prepared by hydroxyalkylation, epoxidation, it is low with viscosity, thermal stability is good, curing rate is fast, flexible, good with bisphenol A epoxide resin compatibility, 2.5~7.5% hemicellulose base epoxies are added in bisphenol A epoxide resin, the performances such as tensile strength, the impact strength of solidfied material are all significantly improved.This method not only saves production cost, improves the economic benefit of enterprise's production, and effectively organic liquid waste is avoided directly to discharge, so as to improve environmental quality.
Description
Technical field
The invention belongs to field of chemical technology, and in particular to a kind of hemicellulose base epoxy and preparation method thereof.
Background technology
Hemicellulose is a kind of polysaccharide compound from plant, different types of plant, and structure has more very much not
Together, the structural unit for forming hemicellulose mainly has：D- xyloses, D-Glucose, D-MANNOSE, D- galactolipins, L-arabinose,
L-fucose, D-Glucose aldehydic acid, 4-O- methyl-D-glucoses aldehydic acid, D- galacturonic acids and a small amount of L- rhamnoses and each
Neutral sugar that kind O- methylates etc..Otherness between the chemical constitution of hemicellulose mostly come from different sugar unit structures,
Short strand, substantial amounts of molecule branch, inhomogenous main chain etc., wherein branched structure is more, and chemical constitution is complicated.Hemicellulose
There are two features for element：First, the dissolving sex differernce of hemicellulose is very big, under normal circumstances containing the free hydroxyl group of one to two
Pure natural hemicellulose can be dissolved in water, it is substantially insoluble by modified obtained hemicellulose based compound
In water；Second is that hemicellulose is different because of species, monose composition and chemical constitution are also different.On hemicellulose
Main chain and side chain all comprising substantial amounts of active hydroxy group, hemicellulose, main modification side are modified by chemical modification
Method includes the chemical reactions such as esterification, etherificate, graft copolymerization, oxidation and crosslinking, it is enable preferably to be used in industrial aspect.
All comprising substantial amounts of active hydroxy group, physical and chemical performance is unique, derives from a wealth of sources for main chain and side chain on hemicellulose,
The research of hemicellulose is gradually increased in recent years, but due to the complexity of its structure, has one in actual commercial Application
How fixed limitation it is particularly important effectively utilize abundant hemicellulose resource.Hemicellulose main application has at present：
The fine chemicals such as hydrolysed ferment production ethyl alcohol, fodder yeast, furfural, xylose, xylitol, D-sorbite (hexitol), half fiber
The chemical modifications such as the plain esterification of dimension, etherificate, graft copolymerization, oxidation and crosslinking prepare hemicellulose and derive chemicals.
With the presence of substantial amounts of hydroxyl group on the main chain and branched structure of hemicellulose, the derivative with carboxylic acid and carboxylic acid
Object is chemically reacted, and obtained modified product not only has good thermoplastic property, but also hydrophobic performance also obtains further
Raising, because hemicellulose have biodegradability excellent performance, be modified as raw material can prepare can biology
The film of degradation.Current research is that directly the active group of hemicellulose is modified, and is carried out in heterogeneous system, is changed
The yield of reaction is relatively low, and industrialized application is restricted.By pre-activate hemicellulose, then carried out in homogeneous system
Chemical modification, the rate of chemical reaction are significantly improved, and the degree of substitution of product can control, the rate of recovery of product also significantly carries
It rises, possibility is provided for industrial applications.
Hydroxyl in hemicellulose has good dissolubility by etherification modified obtained hemicellulose polyethers, glues simultaneously
Spend low, thermal stability is also improved, therefore scope of its application is more extensive.The etherification reaction of hemicellulose is main at present
It is：The carboxy methylation of hemicellulose methylates, is quaternized, the reactions such as Benzylation and sulfoalkylation.
One of important method being graft-polymerized as high glycan chemical modification is modified high poly- by accessing new functional group
The chemical property of sugar.Hydroxyl in hemicellulose can be graft-polymerized with grafted monomers under the action of initiator.Grafting
Copolymer has been provided simultaneously with the performance of hemicellulose and grafted monomers.Grafted monomers mainly have acrylonitrile, methacrylic acid, propylene
Sour octadecyl ester, octadecyl methacrylate etc..
Epoxy resin is to refer to the organic compound containing two or more epoxide groups, molecular structure in molecule
It is to contain active epoxide group in strand as its feature, due to containing active epoxide group in molecular structure, make it
Can be crosslinked with polytype curing agent reaction and form the insoluble high polymer with three-dimensional net structure.It is cured
Epoxy resin has good physics, chemical property, has excellent adhesive strength, and dielectric properties are good, and deformation retract rate is small,
Product size stability is good, and hardness is high, and flexibility is preferable, to alkali and most of solvent-stable, is widely used in national defence, national warp
It helps all departments, pours into a mould, impregnates, the purposes such as lamination material, bonding agent, coating.
Since bisphenol A type epoxy resin raw materials bisphenol A has unsustainable property and toxicity problem, environment-friendly type can be substituted
The research of bisphenol A type epoxy resin is particularly important.At present, it is to solve the problems, such as this most with organism-based raw material synthetic epoxy resin
Practical method has important real value and wide development space.It has recently been demonstrated that using lignin as raw material with
The research of epoxychloropropane (ECH) modified synthesis Lignin-based epoxy resin is more.Also with tung oil, rosin, no itaconic acid, food
Sub- acid is the research of Material synthesis biology base epoxy.
Li Chao has synthesized isobide base epoxy and epoxy hardener using isobide as raw material.And with synthesis
Two kinds of substances are cured by standard proportional, obtain possessing good tensile deformation fixed rate, shape recovery rate and excellent heat resistance energy
Isobide base shape memory material.
As raw material, the modified synthesis under catalyst action is resistance to ECH using the high Vinsol that is extracted in maize straw by Liu Yaou
The higher Lignin-based epoxy resin of hot property.
Feng Pan with acetic acid lignin (AAL) be raw material, by being obtained after different modes and epoxy blend through epoxidation
A variety of lignin modification epoxy resin, while inquired into epoxy resin property of the architectural characteristic to synthesis of the different fractions of AAL
Influence.
Propoxyl group is obtained by the reaction with PO after alkali soluble, sour heavy and purification procedures using Wheat Straw Lignin from Alkali Pulping as raw material in Xu Hui
Change lignin.It is successfully synthesized simultaneously with triethylene tetramine (TETA) and phenol aldehyde modified amine (T-31) for curing agent with casting method
Lignin epoxide resin composite foam material.
The mixed liquor that fourth Na obtains after being reacted two hours by diethanol amine and formaldehyde is added dropwise in lignin liquor
Method of modifying to lignin carry out chemical modification, add the methylol of original lignin and the quantity of phenolic hydroxyl group.In this base
The better heat stability of the epoxy resin synthesized on plinth.
Wang Haiyang obtains the oxonium base lignin of bagasse with the dissolved lignin in acid-precipitation method separation and Extraction pulping waste liquor.It is logical
Cross after phenol and bisphenol A modified lignin again with ECH synthesis modification Lignin-based epoxy resins.
Wu Wenshuo is with gained maize straw liquefied substance under the conditions of microwave catalysis and the Open-closed-loops repeatedly of ECH in alkaline conditions
Reaction synthetic epoxy resin and curing agent are combined with other auxiliary agents, and the epoxy resin adhesive of preliminary practicability is made.
The content of the invention
Goal of the invention：For the deficiencies in the prior art, the object of the present invention is to provide a kind of hemicellulose basic rings
Oxygen resin by the use of the polyhydroxy hemicellulose that viscose fiber wastewater recycles as raw material, is modified by hydroxyalkylation and hemicellulose is made
Plain based polyether polyol, then hemicellulose group liquid epoxies is prepared with epoxychloropropane, sodium hydroxide reaction, there is viscosity
Low, flexibility is good, with bisphenol A type epoxy resin compatibility it is good the advantages that, being added on a small quantity in bisphenol A epoxide resin significantly to carry
The performances such as the stretching and shock resistance of high solidification object, it is widely used, the reasonable utilization of waste resource is effectively realized, reduces environment pressure
Power.It is a further object of the present invention to provide a kind of preparation methods of above-mentioned hemicellulose base epoxy.
Technical solution：In order to realize foregoing invention purpose, the technical solution adopted by the present invention is：
A kind of hemicellulose base epoxy, prepares and contains hemicellulose in raw material.
The hemicellulose is recycled from viscose fiber wastewater and obtained, through with epoxides carry out it is etherification modified after be made
Hemicellulose based polyether polyol continues to prepare hemicellulose group using the hemicellulose based polyether polyol as raw material
Epoxy resin.
A kind of method for preparing the hemicellulose base epoxy, step are as follows：
1) hemicellulose, solvent and catalyst are added in into autoclave, with the air in nitrogen displacement kettle, temperature control stirs
It mixes, is passed through ethylene oxide or propylene oxide or their mixture, control reaction pressure is no more than 0.6MPa, after leading to material,
Heat preservation is vented simultaneously cooling discharge, obtains thick hemicellulose polyether polyol until reactor pressure no longer declines；Refined standby
With.
2) hemicellulose polyether polyol, epoxychloropropane are taken, is added to equipped with blender, thermometer and ball-type condenser
Four-hole boiling flask in, temperature control is added dropwise liquid sodium hydroxide or is added portionwise solid sodium hydroxide, feeds and finishes insulation reaction, cools down out
Material, through NaH2PO4It neutralizes, filter, vacuum distillation recycling excess epoxy chloropropane, refinement treatment obtains product hemicellulose group epoxy
Resin.
In step 1), solvent is toluene, dioxane or dimethylformamide；The dosage of solvent is hemicellulose quality
3~10 times.
In step 1), catalyst is potassium hydroxide, potassium methoxide, sodium hydroxide or sodium methoxide, and catalyst amount is hemicellulose
The 2~8% of quality amount.
In step 1), raw material proportioning m (EO or PO):M (Hcel-OH) is 9~13:1,90~140 DEG C of reaction temperature is added dropwise
2~6h of reaction time.
In step 2), raw material proportioning n (ECH):N (hydroxyl):N (NaOH) is 5~10:1:1.
In step 2), 30~60 DEG C of reaction temperature.
In step 2), 2~8h of sodium hydroxide addition time, insulation reaction 1h.
Application of the hemicellulose base epoxy in bisphenol A epoxide resin is prepared.
The present invention hemicellulose base epoxy, using the hemicellulose recycled in viscose fiber wastewater as raw material, through with
Epoxides carries out etherification modified rear obtained hemicellulose based polyether polyol, can form flexible linear chain, assign hemicellulose
Its good amphipathic property increases its dissolubility, and brittleness reduces, viscoplasticity increase.Its reaction principle is Hcel-OH (half
Cellulose) as nucleopilic reagent, it is anti-that nucleophilic displacement of fluorine occurs with ethylene oxide (EO), propylene oxide (PO) or their mixture
Should, generation hemicellulose based polyether polyol (HCPE).In order to improve reactivity, KOH can be provided as catalyst for reaction
One alkaline environment makes the-OH in hemicellulose molecule be converted into negative oxygen ion, the nucleophilie nucleus ability of enhancing-OH.Main reaction equation
Formula is as follows：
R-OH+KOH→R-O-K++H2O
Hemicellulose base epoxy, reaction side are obtained through one-step method Open-closed-loop to the HCPE and ECH, NaOH of above-mentioned synthesis
Formula is as follows：
In hemicellulose polyether polyol preparation process, solvent is toluene, dioxane or dimethylformamide；Catalysis
Agent is potassium hydroxide, potassium methoxide, sodium hydroxide or sodium methoxide；Raw material proportioning m (EO or PO):M (Hcel-OH) is 9~13:1, it is molten
The dosage of agent is 3~10 times (mass ratioes) of hemicellulose, and catalyst amount is the 2~8% of hemicellulose quality, reaction temperature
90~140 DEG C, reaction pressure be less than 0.6MPa, EO or PO 2~6h of dropwise reaction time, then keep the temperature to reaction pressure no longer under
It is reduced to only, cooling discharge, HCPE is made in vacuum distillation removing solvent.
In hemicellulose base epoxy preparation process, hemicellulose polyether polyol carries out a step with ECH, sodium hydroxide
Method is reacted, raw material proportioning n (ECH):N (hydroxyl):N (NaOH) is 5~10:1:1,30~60 DEG C of reaction temperature, sodium hydroxide adds
2~8h of time, insulation reaction 1h are expected, after reaction, through NaH2PO4It neutralizes, filter, vacuum distillation is dehydrated, excess epoxy chlorine third
The refinement treatments such as alkane obtain rufous low-viscosity (mobile) liquid hemicellulose base epoxy, 0.10~0.15eg/100g of epoxide number.
In hemicellulose polyether polyol preparation process of the present invention, epoxide EO, PO or their mixtures are excellent
Select EO；Catalyst is preferably potassium hydroxide, and dosage is preferably to account for the percentage 4~5% of hemicellulose quality.
In hemicellulose polyether polyol preparation process of the present invention, reaction temperature is low, and reaction speed is slow；Reaction temperature
Height, reaction speed is fast, and suitable reaction temperature is 100~130 DEG C；EO or PO is added dropwise, and feed time is too fast, and reaction heat has little time
It removes, brings safety problem；Charging rate is excessively slow, and production efficiency is low, suitable 3~4h of feed time, in epoxide
Charging is finished, and reactant system is kept until pressure no longer declines.
In hemicellulose base epoxy preparation process of the present invention, preferred ECH, the dosage of sodium hydroxide are n
(ECH):N (hydroxyl):N (NaOH) is 6~9:1:1.Sodium hydroxide is solid, point multiple batches of charging, suitable for sodium hydroxide addition
3~4h of time, sodium hydroxide finish, insulation reaction time 1h.Reaction temperature is low, and reaction speed is slow；Reaction temperature is high, hands over
The side reactions such as connection, preferred suitable reaction temperature is 35~45 DEG C.
Advantageous effect：Compared with prior art, the present invention makes full use of the half fiber recycled in the waste liquid that viscose fiber produces
Dimension element carries out the preparation of hemicellulose base epoxy, not only saves production cost, improve the economy of enterprise's production as raw material
Benefit, and effectively organic liquid waste is avoided directly to discharge, so as to improve environmental quality, there is certain economic benefit and society
Benefit.Specifically, using the hemicellulose of viscose rayon devil liquor recovery as raw material, hemicellulose is prepared by hydroxyalkylation, epoxidation
Plain base epoxy, low with viscosity, thermal stability is good, and curing rate is fast, flexible, good with bisphenol A epoxide resin compatibility
The features such as, 2.5~7.5% hemicellulose base epoxies are added in bisphenol A epoxide resin, the tensile strength of solidfied material resists
The performances such as impact strength are all significantly improved.
Specific embodiment
The invention is further illustrated by the following examples, but is not limited to lifted embodiment.
The raw material ethylene oxide that the present invention uses is technical grade, and Yangzi Petrochemical Co., Ltd produces；Epoxy third
Alkane is technical grade, and Shandong petrochemical industry limited company produces；Epoxychloropropane is technical grade；Jiangsu Yang Nongjin lakes chemical industry has
Limit company produces；Sodium hydroxide, toluene are chemical pure, Nanjing Chemistry Reagent Co., Ltd..
According to national standard GB/T 4612-2008《The measure of plastics epoxide epoxide equivalent》Described in method to epoxy
The equivalent of compound epoxy is measured.
Embodiment 1
The preparation of hemicellulose (from Chengdu Liya Fibre Co., Ltd.'s viscose fiber wastewater extraction)：Ethyl alcohol and viscose glue
Waste liquid is respectively with 2:1 (volume ratio) mixes, and is filtered suspension with Buchner funnel after standing half an hour, and is washed with distillation
It washs 3 times；Obtained filter cake is with industrial alcohol with 2:1 (volume ratio) is stirred evenly with glass bar, stands 12h；Soak is filtered
Afterwards, filter cake is taken out, is placed in 30 DEG C of vacuum drying chambers and dries to constant weight, pack spare.Measure hemicellulose moisture 18.8%,
Ash content 23.4%, the monosaccharide component of hemicellulose：Xylitol 1.5%, glucose 10.6%, xylose 72.9%, galactolipin
4.5%th, arabinose 10.6%, the hydroxyl value 490.5mgKOH/g of hemicellulose.
Embodiment 2
Hemicellulose 20g, potassium hydroxide 0.8g, the toluene 120g that precise embodiment 1 recycles are added to equipped with stirring
Device, thermometer, cycle condenser autoclave in, after nitrogen displacement time, be warming up to 100 DEG C, slowly opened under constant speed stirring
Begin continuous dropwise addition ethylene oxide 180g, and 4h is added, and between 120~130 DEG C, reaction pressure is less than controlling reaction temperature
0.6MPa, insulation reaction cool to less than 40 DEG C, discharging until pressure no longer declines；Removed under reduced pressure toluene solvant, is filtered
Rufous hemicellulose polyether polyol liquid, yield 89.5%, hydroxyl value 273.4mgKOH/g.
Accurate hemicellulose polyether polyol 53.2g, the epoxychloropropane 192g for weighing preparation, is added to equipped with stirring
Device, thermometer, cycle condenser four-hole boiling flask in, after nitrogen displacement 3 times, multiple batches of equal portions add in solid hydroxide in 3h
Sodium 10.3g, adds in 0.86g in every 15 minutes, 30~40 DEG C of controlling reaction temperature, sodium hydroxide finishes, and insulation reaction 1h is filtered out
By-product NaCl is removed, filtrate uses NaH2PO4PH is neutralized to as neutrality, vacuum distillation removing excess epoxy chloropropane filters to obtain product half
Cellulose base epoxy resin, epoxide number 0.151eg/100g.
At room temperature, hemicellulose base epoxy obtained, bisphenol A type epoxy resin (E-51) are mixed with 593 curing agent
Close uniform, pour into mold, be put into vacuum outgas 15min in vacuum drying chamber, after curing 2h in 80 DEG C of baking ovens of normal pressure.Sample
Product prepare three parallel battens, blank sample (E-51 epoxy resin 100g and 593 curing agent prepared by identical curing process altogether
28g mixes solidify afterwards) comparison of batten position, test data is averaged, and the results are shown in Table 1, it is seen then that in bisphenol A epoxide resin
2.5~7.5% hemicellulose base epoxies of middle addition, the performances such as tensile strength, the impact strength of solidfied material are all shown
It writes and is promoted.
1 test result of table
| Product 1 | Product 2 | Blank sample | |
| Hemicellulose base epoxy | 5g | 7.5g | 0g |
| E-51 | 95g | 92.5g | 100g |
| 593 curing agent | 28g | 28g | 28g |
| Tensile strength | 66.5MPa | 68.4MPa | 57.9MPa |
| Impact strength | 7.2kJ/m2 | 7.5kJ/m2。 | 4.95kJ/m2 |
Embodiment 3
Hemicellulose 20g, potassium hydroxide 1g, the toluene 160g that precise embodiment 1 recycles are added to equipped with stirring
Device, thermometer, cycle condenser autoclave in, after nitrogen displacement time, be warming up to 100 DEG C, slowly opened under constant speed stirring
Begin continuous dropwise addition ethylene oxide 200g, and 5h is added, and 110~120 DEG C of controlling reaction temperature, reaction pressure is less than 0.6MPa,
Insulation reaction cools to less than 40 DEG C, discharging until pressure no longer declines；Removed under reduced pressure toluene solvant filters to obtain rufous
Hemicellulose polyether polyol liquid, yield 89.1%, hydroxyl value 239.7mgKOH/g.
Accurate hemicellulose polyether polyol 50.8g, the epoxychloropropane 140.6g for weighing preparation, is added to equipped with stirring
Device, thermometer, cycle condenser four-hole boiling flask in, after nitrogen displacement 3 times, multiple batches of equal portions add in solid hydrogen-oxygen in 2.5h
Change sodium 7.9g, add in 0.79g within every 15 minutes, 30~40 DEG C of controlling reaction temperature, sodium hydroxide finishes, insulation reaction 1h, filtering
Go out by-product NaCl, and filtrate uses NaH2PO4PH is neutralized to as neutrality, vacuum distillation removing excess epoxy chloropropane filters to obtain product
Hemicellulose base epoxy, epoxide number 0.127eg/100g.
Embodiment 4
Hemicellulose 20g, potassium hydroxide 1g, the dioxane 160g that precise embodiment 1 recycles are added to be equipped with and stir
In the autoclave for mixing device, thermometer, cycle condenser, after nitrogen displacement time, 100 DEG C are warming up to, constant speed is slow under stirring
Start continuous dropwise addition ethylene oxide 220g, 4h is added, and 120~130 DEG C of controlling reaction temperature, reaction pressure is less than
0.6MPa, insulation reaction cool to less than 40 DEG C, discharging until pressure no longer declines；Removed under reduced pressure dioxane solvent, mistake
Filter to obtain rufous hemicellulose polyether polyol liquid, yield 90.1%, hydroxyl value 205.1mgKOH/g.
Accurate hemicellulose polyether polyol 50.8g, the epoxychloropropane 120.3g for weighing preparation, is added to equipped with stirring
Device, thermometer, cycle condenser four-hole boiling flask in, after nitrogen displacement 3 times, multiple batches of equal portions add in solid hydroxide in 2h
Sodium 7.4g, adds in 1.0g in every 15 minutes, 35~45 DEG C of controlling reaction temperature, sodium hydroxide finishes, and insulation reaction 1h, filtering is gone out
By-product NaCl, filtrate use NaH2PO4PH is neutralized to as neutrality, vacuum distillation removing excess epoxy chloropropane filters to obtain product half fiber
The plain base epoxy of dimension, epoxide number 0.115eg/100g.
Embodiment 5
Hemicellulose 20g, potassium hydroxide 1g, the dioxane 160g that precise embodiment 1 recycles are added to be equipped with and stir
In the autoclave for mixing device, thermometer, cycle condenser, after nitrogen displacement time, 100 DEG C are warming up to, constant speed is slow under stirring
Start continuous dropwise addition ethylene oxide 240g, 6h is added, and 100~120 DEG C of controlling reaction temperature, reaction pressure is less than
0.6MPa, insulation reaction cool to less than 40 DEG C, discharging until pressure no longer declines；Removed under reduced pressure dioxane solvent, mistake
Filter to obtain rufous hemicellulose polyether polyol liquid, yield 90.0%, hydroxyl value 132.42mgKOH/g.
Accurate hemicellulose polyether polyol 52.4g, the epoxychloropropane 80.1g for weighing preparation, is added to equipped with stirring
Device, thermometer, cycle condenser four-hole boiling flask in, after nitrogen displacement 3 times, multiple batches of equal portions add in solid hydroxide in 2h
Sodium 5.0g, adds in 0.625g in every 15 minutes, 35~45 DEG C of controlling reaction temperature, sodium hydroxide finishes, and insulation reaction 1h is filtered out
By-product NaCl is removed, filtrate uses NaH2PO4PH is neutralized to as neutrality, vacuum distillation removing excess epoxy chloropropane filters to obtain product half
Cellulose base epoxy resin, epoxide number 0.113eg/100g.
Embodiment 6
Hemicellulose 20g, potassium hydroxide 1g, the toluene 160g that precise embodiment 1 recycles are added to equipped with stirring
Device, thermometer, cycle condenser autoclave in, after nitrogen displacement time, be warming up to 100 DEG C, slowly opened under constant speed stirring
Begin continuous dropwise addition propylene oxide 260g, and 6h is added, and 120~140 DEG C of controlling reaction temperature, reaction pressure is less than 0.6MPa,
Insulation reaction cools to less than 40 DEG C, discharging until pressure no longer declines；Removed under reduced pressure toluene solvant filters to obtain rufous
Hemicellulose polyether polyol liquid, yield 89.1%, hydroxyl value 129.2mgKOH/g.
Accurate hemicellulose polyether polyol 52.3g, the epoxychloropropane 78g for weighing preparation, be added to equipped with blender,
Thermometer, cycle condenser four-hole boiling flask in, after nitrogen displacement 3 times, multiple batches of equal portions add in solid sodium hydroxide in 2h
4.8g adds in 0.6g in every 15 minutes, and 35~45 DEG C of controlling reaction temperature, sodium hydroxide finishes, and insulation reaction 1h filters away pair
NaCl is produced, filtrate uses NaH2PO4PH is neutralized to as neutrality, vacuum distillation removing excess epoxy chloropropane filters to obtain product hemicellulose
Plain base epoxy, epoxide number 0.108eg/100g.
Claims (10)
1. a kind of hemicellulose base epoxy, which is characterized in that prepare and contain hemicellulose in raw material.
2. hemicellulose base epoxy according to claim 1, which is characterized in that the hemicellulose is fine from viscose glue
Tie up to recycle in waste water and obtain, through with epoxides carry out it is etherification modified after hemicellulose based polyether polyol is made, with described
Hemicellulose based polyether polyol continues to prepare hemicellulose base epoxy for raw material.
A kind of 3. method for preparing hemicellulose base epoxy described in claim 1, which is characterized in that step is as follows：
1) hemicellulose, solvent and catalyst are added in into autoclave, with the air in nitrogen displacement kettle, temperature control stirring,
Ethylene oxide or propylene oxide or their mixture are passed through, control reaction pressure is no more than 0.6MPa, after leading to material, heat preservation
Until reactor pressure no longer declines, simultaneously cooling discharge is vented, obtains thick hemicellulose polyether polyol；It is spare after refined.
2) hemicellulose polyether polyol, epoxychloropropane are taken, is added to four equipped with blender, thermometer and ball-type condenser
In mouth flask, temperature control is added dropwise liquid sodium hydroxide or solid sodium hydroxide is added portionwise, and insulation reaction after charging cools down out
Material, through NaH2PO4It neutralizes, filter, vacuum distillation recycling excess epoxy chloropropane, refinement treatment obtains product hemicellulose group epoxy
Resin.
4. the method according to claim 3 for preparing hemicellulose base epoxy, which is characterized in that molten in step 1)
Agent is toluene, dioxane or dimethylformamide；The dosage of solvent is 3~10 times of hemicellulose quality.
5. the method according to claim 3 for preparing hemicellulose base epoxy, which is characterized in that in step 1), urge
Agent is potassium hydroxide, potassium methoxide, sodium hydroxide or sodium methoxide, and catalyst amount is the 2~8% of hemicellulose quality.
6. the method according to claim 3 for preparing hemicellulose base epoxy, which is characterized in that former in step 1)
Material proportioning m (EO or PO):M (Hcel-OH) is 9~13:1,90~140 DEG C of reaction temperature, 2~6h of dropwise reaction time.
7. the method according to claim 3 for preparing hemicellulose base epoxy, which is characterized in that former in step 2)
Material proportioning n (ECH):N (hydroxyl):N (NaOH) is 5~10:1:1.
8. the method according to claim 3 for preparing hemicellulose base epoxy, which is characterized in that in step 2), instead
Answer 30~60 DEG C of temperature.
9. the method according to claim 3 for preparing hemicellulose base epoxy, which is characterized in that in step 2), hydrogen
Sodium oxide molybdena 2~8h of feed time, insulation reaction 1h.
10. application of the hemicellulose base epoxy described in claim 1 in bisphenol A epoxide resin is prepared.
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