CN105542115B - A kind of preparation method of the humic acid modified Waterborne PU Composite of coal base - Google Patents
A kind of preparation method of the humic acid modified Waterborne PU Composite of coal base Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/48—Polyethers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
Abstract
The invention belongs to macromolecule synthesising technology field, is related to aqueous polyurethane emulsion modification, more particularly to the preparation method of the humic acid modified Waterborne PU Composite of coal base.A kind of preparation method of the humic acid modified aqueous polyurethane of coal base, humic acid is made from coal using alkali-soluble acid analysis method is improved, is then dissolved in N, aqueous polyurethane is modified in N ' dimethylformamides.The preparation method of the humic acid modified Waterborne PU Composite of coal base disclosed in this invention, humic acid modified polyurethane is made using alkali-soluble acid analysis method is improved, the emulsion of obtained composite is homogeneous, stably, cured film has good mechanical property, can be in the various fields application such as printing, packaging, furniture, advertisement, building materials, ship dead works thing, cabin, steel construction metallic support, instrument and meter, Medical Devices, motor device, micro metal part, instrument board, floor, timber, paper application, leather, plastics, communication, space flight, aviation.
Description
Technical field
The invention belongs to macromolecule synthesising technology field, is related to aqueous polyurethane emulsion modification, more particularly to a kind of coal base
The preparation method of humic acid modified Waterborne PU Composite.
Background technology
Polyurethane (PU) be by polyisocyanates, macromolecular PEPA or PPG and small molecule polyol and
The polymer that polynary amine chain extender addition polymerization forms.Polyurethane has that hardness is big, wear-resistant, pliability is good, adhesion property
And the advantages that light unfading is excellent is protected, and easily designed and processing, thus it is widely used in coating, adhesive, foam plastic
The fields such as material, ink and rubber.It is heat-resisting, resistance to but polyurethane has that impact resistance is bad, easy to foaming, resistance to acids and bases is poor in case of wet
The poor performance such as water, antistatic, it is restricted its application in some fields.
Humic acid substance is one for being decomposed and being synthesized under microorganism and geochemistry process by animal, plant residue
Class natural organic high-molecular polymer.The reserves of tellurian humic acid substance are huge, as a kind of natural resources, deposit extensively
In soil, lake, river, ocean.Humic acid substance molecular structure is different from other natural polymers, without certain
The chemical constitution and conformation configuration completely determined, it is a kind of macromolecule hydroxyl inconsistent by molecular size range difference, structure composition
The complex mixture of base aromatic carboxylic acids same clan material composition, thus it has diversity, complexity, inhomogenous property, causes
The analysis of humic acid substance is extremely difficult.Humic acid substance contains phenolic hydroxyl group, alcoholic extract hydroxyl group, hydroxyquinone, enol base, sulfonic acid
A variety of functional groups such as base, amido, quinonyl, half quinonyl, methoxyl group and carboxyl, and a small amount of amino acid, vitamin, enzyme and more
Kind trace element, its main component is C, H, O, N and S.Due to having various active functional group in molecule, acid is made it have
Property, hydrophily, interfacial activity, cation exchange capacity (CEC), complexing and absorption dispersibility, thus humic acid substance is in ring
Fields such as guarantor, oil exploitation, agricultural gardening, medicine, analytical chemistry, battery industry etc. all have a wide range of applications.It is main at present
Achievement in research be：
(1) uv photopolymerization method prepares cotton stalk fiber element grafted propylene acid-humic acid high hydroscopic resin and its performance, function
Macromolecule journal, 2014,27 (2):224-230.Report with acrylic acid (AA), modified cotton stalk fiber plain (MCSC) and humic acid
(HA) it is raw material, 2,2- dimethoxy-phenylf ketones are that spectrum and ESEM have carried out sign initiator to product, and use is ultraviolet
Light polymerization method is prepared for degradability composite highly-absorbent resin (MCSC-g-PAA/HA).It has studied containing for AA concentration, MCSC and HA
The influences of the factor to the resin swelling performance such as the addition of amount, reaction time and light trigger.As a result show, in optimal conditions
Under, gained resin is in distilled water and saline solution (ωNaCl=0.9%) pick up respectively reaches 870g/g and 94g/g.It is but right
The performance of modified composite material such as viscosity, surface tension and the hardness of resin, tensile strength etc. all do not make a search.
(2) new humic acid polymeric adsorbent synthesis and its research to Fe (III) adsorption effect, humic acid, 2013,1：5-
8.Report using natural humus acid as raw material, acrylic acid and diethanol amine are that graft copolymerization monomer has been synthesized with absorption property
New humic acid-acrylic acid diethanol amine resin (PHAE), has inquired into adsorption temp, time, pH value, Fe3+Initial concentration, tree
Fat dosage is to micro Fe in water3+The influence of adsorption effect.As a result Fe in the aqueous solution is shown3+Concentration is 50mg/L, pH 5, temperature
Spend for 30 DEG C when, add PHHA resins by 2g/L, adsorbance is up to 5.26mg/g, Fe during adsorption equilibrium3+Clearance reach
89.65%.
(3) synthesis of glucose modified aqueous polyurethane and performance study, University of Anhui, master thesis in 2014.
Report uses the glucose (Glc) that nature is widely present as cross-linked modifier, and cross-linking modified, preparation is carried out to aqueous polyurethane
Go out a series of glucose modified polyurethane material, have studied the addition of glucose to the property such as water resistance, tensile strength, hardness
The influence of energy.As a result show, with the increase of glucose content, glued membrane water resistance is improved, and heat resistance is improved, glue
The hardness and mechanical property of film also significantly improve.
The content of the invention
For above-mentioned the deficiencies in the prior art, the invention discloses a kind of humic acid modified aqueous polyurethane of coal base
Preparation method.
A kind of preparation method of the humic acid modified Waterborne PU Composite of coal base, using improving alkali-soluble acid analysis method from coal
In be made humic acid, be then dissolved in N, aqueous polyurethane be modified in N '-dimethyl formamide, preparation process is such as
Under：
A, in the container equipped with agitator, reflux condensing tube, thermometer and feeding device, the isocyanide of isophorone two is added
Acid esters (IPDI) and with N, the humic acid solution of N '-dimethyl formyl amine solvent, 70~90 DEG C of 1~4h of reaction, preferably 80 DEG C anti-
Answer 2h；
B, PPG NJ-220 and dihydromethyl propionic acid (DMPA) are subsequently added into, catalyst dibutyl tin osmanthus is added dropwise
Sour tin (T-12), 65~95 DEG C of reactions 1~4h, preferably 80 DEG C reaction 2h；
C, system temperature is down to 40 DEG C, added in triethylamine and 0.5h, obtain performed polymer；
D, added into performed polymer and chain extension and scattered, obtained coal are carried out as the ethylenediamine solution of solvent with deionized water
The humic acid modified Waterborne PU Composite of base；
Wherein, improvement alkali-soluble acid analysis method of the present invention is included by humic acid, preparation process are made in coal：
Coal dust is added in reaction vessel first, with solid-to-liquid ratio 1g:5mL ratio adds 1.5mol/L HNO3, constant temperature
Heating water bath, 60 DEG C of keeping temperature, magnetic agitation 60min carry out oxidation pre-treatment, are filtrated to get the solid powder of pre-oxidation；So
Afterwards according to solid-to-liquid ratio 1g:10mL ratio adds 1.5% NaOH solution to solid powder, 60 DEG C of extracting 60min, is filtrated to get
Sodium humate solution；Salt acid for adjusting pH value is added into sodium humate solution again to 1~2,24h is stood, after removing supernatant liquor
Mixture is centrifuged, washed with watery hydrochloric acid, then is washed with a small amount of deionized water, is produced after being ground after 60 DEG C of dryings of vacuum.
The quality of each reactive material is respectively in preparation process disclosed in this invention：
The dosage of the humic acid is that IPDI, PPG NJ-210 and dihydromethyl propionic acid are total
The 0.005~0.30% of quality, preferably 0.06%；
N, the dosage of N '-dimethyl formamide for humic acid and IPDI gross mass 98.23~
109.02%, preferably 103.33%；
PPG NJ-220 dosage be humic acid and IPDI gross mass 168.02~
195.55%, preferably 180.83%；
The dosage of dihydromethyl propionic acid is the 16.13~19.74% of humic acid and IPDI gross mass,
It is preferred that 17.91%；
T-12 dosage is the 0.44~0.62% of humic acid and IPDI gross mass, preferably
0.54%；
The dosage of triethylamine is the 12.47~14.33% of humic acid and IPDI gross mass, preferably
13.65%；
The dosage of ethylenediamine is the 12.94~14.34% of humic acid and IPDI gross mass, preferably
13.58%；
The dosage of deionized water is the 799.00~947.96% of humic acid and IPDI gross mass, excellent
Select 874.45%.
, further can be by the obtained humic acid modified aqueous polyurethane composite wood of coal base in the preferred embodiment of the present invention
60 DEG C of dry 24h, which are warming up to, on expecting emulsion down to polytetrafluoroethylene (PTFE) into membranous disc, after 30 DEG C of vacuum drying 24h obtains coal base humic acid
Modified aqueous polyurethane cured film.
The present invention is to the viscosity of obtained water-based humic acid/polyurethane-emulsion, particle diameter, surface tension and cured film
Mechanical property etc. determines.
Sodium hydroxide, concentrated nitric acid, hydrochloric acid, dibutyl tin dilaurate (T-12), N, N dimethyl formyl used in the present invention
Amine, ethylenediamine (EDA) and triethylamine (TEA), Chemical Reagent Co., Ltd., Sinopharm Group；PPG NJ-220, Jurong City
Ningwu Chemical Co., Ltd.；Dihydromethyl propionic acid (DMPA), Shanghai Rong Rong Chemical Co., Ltd.s；Different Buddhist diisocyanates
(IPDI), Switzerland PERSTOP companies.
Beneficial effect
The preparation method of the humic acid modified Waterborne PU Composite of coal base disclosed in this invention, using improving alkali soluble
Acid-precipitation method is made humic acid modified polyurethane, and the emulsion of obtained composite is homogeneous, stably, and cured film has good mechanics
Performance, can be in printing, packaging, furniture, advertisement, building materials, ship dead works thing, shell, cabin, steel construction metal branch
Frame, bridge, high frame iron tower, derrick, instrument and meter, Medical Devices, motor device, micro metal part, instrument board, floor, wood
The various fields applications such as material, paper application, leather, plastics, household electrical appliances, electronics, communication, space flight, aviation.
Embodiment
With reference to example, the present invention is described in detail, so that those skilled in the art more fully understand the present invention,
But the invention is not limited in following instance.
The preparation process that improvement alkali-soluble acid analysis legal system obtains humic acid includes：
10g coal dusts are added in beaker, according to solid-to-liquid ratio 1:5 add 50mL 1.5mol/L HNO3, water bath with thermostatic control adds
Heat, 60 DEG C are maintained the temperature at, magnetic agitation 60min carries out oxidation pre-treatment, is filtrated to get the solid powder of pre-oxidation；
100mL 1.5% NaOH extracts are added into powder, 60 DEG C of extracting 60min, it is molten to be filtrated to get sodium humate
Liquid；
Salt acid for adjusting pH value is added into sodium humate solution to 1~2, stands 24h, is removed after supernatant liquor to mixture
Centrifuged, washed with watery hydrochloric acid, then washed with a small amount of deionized water, ground after 60 DEG C of dryings of vacuum, obtain humic acid
Powder.
Embodiment 1
In the 500mL four-hole bottles equipped with agitator, reflux condensing tube, thermometer and feeding device, it is different to add 3.868g
Isophorone diisocyanate (IPDI) and with 3.8g N, the humic acid containing 0.0006g of N '-dimethyl formamide solution ultrasonic disperse
Solution, 90 DEG C of reaction 1h, is subsequently added into 6.5g PPG NJ-220 and 0.7335g dihydromethyl propionic acids (DMPA), is added dropwise
0.020g catalyst T-12,65 DEG C of reaction 3h；40 DEG C are cooled to add in triethylamine 0.545g and 0.5h, be then added dropwise with go from
Sub- water carries out chain extension, scattered, wherein ethylenediamine 0.505g, deionized water 30.91g as the ethylenediamine solution of solvent, at a high speed
30min is stirred, water-based humic acid/polyaminoester emulsion (HA-WPU-1) is made.
Embodiment 2
In the 500mL four-hole bottles equipped with agitator, reflux condensing tube, thermometer and feeding device, it is different to add 5.775g
Isophorone diisocyanate (IPDI) and with 6.3g N, the humic acid containing 0.0037g of N '-dimethyl formamide solution ultrasonic disperse
Solution, 70 DEG C of reaction 3h, is subsequently added into 11.3g PPG NJ-220 and 1.141g dihydromethyl propionic acids (DMPA), is added dropwise
0.032g catalyst T-12,95 DEG C of reaction 1h；40 DEG C are cooled to add in triethylamine 0.828g and 0.5h, be then added dropwise with go from
Sub- water carries out chain extension, scattered, wherein ethylenediamine 0.748g, deionized water 54.78g as the ethylenediamine solution of solvent, at a high speed
30min is stirred, water-based humic acid/polyaminoester emulsion (HA-WPU-2) is made.
Embodiment 3
In the 500mL four-hole bottles equipped with agitator, reflux condensing tube, thermometer and feeding device, it is different to add 4.637g
Isophorone diisocyanate (IPDI) and with 4.8g N, the humic acid containing 0.0083g of N '-dimethyl formamide solution ultrasonic disperse
Solution, 80 DEG C of reaction 2h, is subsequently added into 8.4g PPG NJ-220 and 0.832g dihydromethyl propionic acids (DMPA), is added dropwise
0.025g catalyst T-12,80 DEG C of reaction 2h；40 DEG C are cooled to add in triethylamine 0.634g and 0.5h, be then added dropwise with go from
Sub- water carries out chain extension, scattered, wherein ethylenediamine 0.631g, deionized water 40.62g as the ethylenediamine solution of solvent, at a high speed
30min is stirred, water-based humic acid/polyaminoester emulsion (HA-WPU-3) is made.
Embodiment 4
In the 500mL four-hole bottles equipped with agitator, reflux condensing tube, thermometer and feeding device, it is different to add 9.284g
Isophorone diisocyanate (IPDI) and with 9.9g N, the humic acid containing 0.0271g of N '-dimethyl formamide solution ultrasonic disperse
Solution, 80 DEG C of reaction 3h, is subsequently added into 16.3g PPG NJ-220 and 1.564g dihydromethyl propionic acids (DMPA), is added dropwise
0.058g catalyst T-12,70 DEG C of reaction 2h；40 DEG C are cooled to add in triethylamine 1.161g and 0.5h, be then added dropwise with go from
Sub- water carries out chain extension, scattered, wherein ethylenediamine 1.294g, deionized water 83.35g as the ethylenediamine solution of solvent, at a high speed
30min is stirred, water-based humic acid/polyaminoester emulsion (HA-WPU-4) is made.
Embodiment 5
In the 500mL four-hole bottles equipped with agitator, reflux condensing tube, thermometer and feeding device, it is different to add 7.721g
Isophorone diisocyanate (IPDI) and with 7.9g N, the humic acid containing 0.0699g of N '-dimethyl formamide solution ultrasonic disperse
Solution, 70 DEG C of reaction 4h, is subsequently added into 14.3g PPG NJ-220 and 1.257g dihydromethyl propionic acids (DMPA), is added dropwise
0.034g catalyst T-12,85 DEG C of reaction 4h；40 DEG C are cooled to add in triethylamine 1.016g and 0.5h, be then added dropwise with go from
Sub- water carries out chain extension, scattered, wherein ethylenediamine 1.117g, deionized water 66.73g as the ethylenediamine solution of solvent, at a high speed
30min is stirred, water-based humic acid/polyaminoester emulsion (HA-WPU-5) is made.
Determine the viscosity that water-based graphene oxide/poly- (urethane-acrylate) emulsion is made, particle diameter, surface tension and consolidate
Change the mechanical property of film, it is as a result as shown in table 1 below.
Table 1
| Sample | HA-WPU-1 | HA-WPU-2 | HA-WPU-3 | HA-WPU-4 | HA-WPU-5 |
| Viscosity (Pas) | 0.010 | 0.009 | 0.007 | 0.010 | 0.012 |
| Shore hardness | 88 | 91 | 96 | 94 | 90 |
| Tensile strength (MPa) | 10.17 | 11.33 | 15.24 | 12.12 | 9.24 |
As a result show, water-based humic acid/polyaminoester emulsion prepared by the present invention is homogeneous, stably, and cured film has preferable
Mechanical property, can printing, packaging, furniture, advertisement, building materials, ship dead works thing, shell, cabin, steel construction gold
Belong to support, bridge, high frame iron tower, derrick, instrument and meter, Medical Devices, motor device, micro metal part, instrument board,
The various fields applications such as plate, timber, paper application, leather, plastics, household electrical appliances, electronics, communication, space flight, aviation.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
The equivalent structure or equivalent flow conversion that bright specification is made, or other related technical areas are directly or indirectly used in,
Similarly it is included within the scope of the present invention.
Claims (12)
1. a kind of preparation method of the humic acid modified Waterborne PU Composite of coal base, using improving alkali-soluble acid analysis method from coal
Humic acid is made, is then dissolved in N, aqueous polyurethane is modified in N '-dimethyl formamide, it is characterised in that system
Standby step is as follows：
A, in the container equipped with agitator, reflux condensing tube, thermometer and feeding device, IPDI is added
With with N, the humic acid solution of N '-dimethyl formyl amine solvent, 70~90 DEG C of 1~4h of reaction；
B, PPG NJ-220 and dihydromethyl propionic acid are subsequently added into, catalyst dibutyl tin dilaurate is added dropwise（T-
12）, 65~95 DEG C of 1~4h of reaction；
C, system temperature is down to 40 DEG C, added in triethylamine and 0.5h, obtain performed polymer；
D, added into performed polymer and chain extension and scattered, obtained coal base corruption are carried out as the ethylenediamine solution of solvent with deionized water
Grow sour modified aqueous polyurethane composite；
Wherein, described improvement alkali-soluble acid analysis method is included by humic acid, preparation process are made in coal：
Coal dust is added in reaction vessel first, with solid-to-liquid ratio 1g:5mL ratio adds 1.5mol/L HNO3, water bath with thermostatic control adds
Heat, 60 DEG C of keeping temperature, magnetic agitation 60min carry out oxidation pre-treatment, are filtrated to get the solid powder of pre-oxidation；Then according to
Solid-to-liquid ratio 1g:10mL ratio adds 1.5% NaOH solution to solid powder, 60 DEG C of extracting 60min, is filtrated to get humic acid
Sodium solution；Salt acid for adjusting pH value is added into sodium humate solution again to 1~2,24h is stood, will be mixed after removing supernatant liquor
Thing centrifuges, and is washed with watery hydrochloric acid, then is washed with a small amount of deionized water, is produced after being ground after 60 DEG C of dryings of vacuum.
2. the preparation method of the humic acid modified Waterborne PU Composite of coal base according to claim 1, its feature exist
In the quality of each reactive material is respectively in preparation process：
The dosage of the humic acid is IPDI, PPG NJ-220 and dihydromethyl propionic acid gross mass
0.005~0.30%；
N, the dosage of N '-dimethyl formamide for humic acid and IPDI gross mass 98.23~
109.02%；
PPG NJ-220 dosage be humic acid and IPDI gross mass 168.02~
195.55%；
The dosage of dihydromethyl propionic acid is the 16.13~19.74% of humic acid and IPDI gross mass；
T-12 dosage is the 0.44~0.62% of humic acid and IPDI gross mass；
The dosage of triethylamine is the 12.47~14.33% of humic acid and IPDI gross mass；
The dosage of ethylenediamine is the 12.94~14.34% of humic acid and IPDI gross mass；
The dosage of deionized water is the 799.00~947.96% of humic acid and IPDI gross mass.
3. the preparation method of the humic acid modified Waterborne PU Composite of coal base according to claim 1, its feature exist
In：In the step A, 80 DEG C of reaction 2h.
4. the preparation method of the humic acid modified Waterborne PU Composite of coal base according to claim 1, its feature exist
In：In the step B, 80 DEG C of reaction 2h.
5. the preparation method of the humic acid modified Waterborne PU Composite of coal base according to claim 2, its feature exist
In：The dosage of the humic acid is IPDI, PPG NJ-220 and dihydromethyl propionic acid gross mass
0.06%.
6. the preparation method of the humic acid modified Waterborne PU Composite of coal base according to claim 2, its feature exist
In：N, the dosage of N '-dimethyl formamide are the 103.33% of humic acid and IPDI gross mass.
7. the preparation method of the humic acid modified Waterborne PU Composite of coal base according to claim 2, its feature exist
In：PPG NJ-220 dosage is the 180.83% of humic acid and IPDI gross mass.
8. the preparation method of the humic acid modified Waterborne PU Composite of coal base according to claim 2, its feature exist
In：The dosage of dihydromethyl propionic acid is the 17.91% of humic acid and IPDI gross mass.
9. the preparation method of the humic acid modified Waterborne PU Composite of coal base according to claim 2, its feature exist
In：T-12 dosage is the 0.54% of humic acid and IPDI gross mass.
10. the preparation method of the humic acid modified Waterborne PU Composite of coal base according to claim 2, its feature exist
In：The dosage of triethylamine is the 13.65% of humic acid and IPDI gross mass.
11. the preparation method of the humic acid modified Waterborne PU Composite of coal base according to claim 2, its feature exist
In：The dosage of ethylenediamine is the 13.58% of humic acid and IPDI gross mass.
12. the preparation method of the humic acid modified Waterborne PU Composite of coal base according to claim 2, its feature exist
In：The dosage of deionized water is the 874.45% of humic acid and IPDI gross mass.
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