CN107603554A - Cellulose modified polyurethane adhesive of a kind of rice straw and preparation method thereof - Google Patents
Cellulose modified polyurethane adhesive of a kind of rice straw and preparation method thereof Download PDFInfo
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- CN107603554A CN107603554A CN201710805861.0A CN201710805861A CN107603554A CN 107603554 A CN107603554 A CN 107603554A CN 201710805861 A CN201710805861 A CN 201710805861A CN 107603554 A CN107603554 A CN 107603554A
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Abstract
The cellulose modified polyurethane adhesive of a kind of rice straw, it is characterised in that soaked first by alkali, sodium chlorite, acidleach and high-pressure homogeneous prepare rice straw cellulose；Secondly, acetylation rice straw cellulose is prepared；Then, PEPA is prepared so that acetylation rice straw is cellulose modified, finally, with PEPA, isocyanates and acrylate reactions, obtains a kind of cellulose modified polyurethane adhesive of rice straw.The adhesive of the present invention, heat endurance is good, and photooxidation resistant, water resistance are superior, and the glued membrane tack formed after solidification is good, and mechanical property is good.
Description
Technical field
The invention belongs to adhesive area, and in particular to a kind of cellulose modified polyurethane adhesive of rice straw and its
Preparation method.
Background technology
Polyurethane（Polyurethane, PU）Usually by binary or polynary organic isocyanate and polyol compound
（PPG or PEPA）React to each other and manufactured there is carbamate（-NH-COO-）Constitutional repeating unit
Polymer, be at present one of using wide high polymer material.Polyester, PPG are the weights for producing polyurethane material
Want chemical intermediate.Production polyester, the raw material of PPG are from the stronger petrochemical industry of toxicity and corrosivity at present
Product, such as phthalic anhydride, phthalic acid.However, receive great punching with increasingly exhaustion, the polyurethane industrial of petroleum resources
Hit.Further, since a large amount of uses of fossil resources, also result in the environmental problem of getting worse.
Cellulose is rich in biomass, the hydroxy radical content of cellulose is larger, and this has been provided for the synthesis of polyurethane material
The condition of profit.A large amount of existing hydroxyls can partly replace conventional polyol as synthesis of polyurethane material in cellulosic molecule
Raw material, by optimize technique, polyurethane material performance can be both improved to a certain extent, can substantially reduce the life of polyurethane again
Produce cost.It is the dosage and imparting product for reducing polyalcohol so using cellulose as one of polyurethane polyol component is prepared
One of desirable route of biodegradability, while also it is filled with new vitality for polyurethane industrial.
The content of the invention
It is an object of the invention to provide a kind of cost, low and excellent mechanical performance rice straw is cellulose modified gathers
Urethane adhesive and preparation method thereof.
In order to realize above-mentioned purpose, present invention employs following technical scheme：
The cellulose modified polyurethane adhesive of a kind of rice straw, it is characterised in that soaked first by alkali, sodium chlorite, acid
Leaching prepares rice straw cellulose with high-pressure homogeneous；Secondly, acetylation rice straw cellulose is prepared；Then, with acetylation water
Rice straw is cellulose modified to prepare PEPA, finally, with PEPA, isocyanates and acrylate reactions, obtains
A kind of cellulose modified polyurethane adhesive of rice straw.
The cellulose modified polyurethane adhesive of described rice straw, it is characterised in that it is by following specific steps system
It is standby to form：
（1）Rice straw is cleaned up using water, 50-60 DEG C of low temperature drying, pulverizer crushes, and crosses 40-60 mesh sieves, 50-
60 DEG C of low temperature dryings, obtain rice straw powder, standby；The sodium hydroxide that rice straw powder is added to 18-20 times of parts by weight is molten
It is stirred in liquid, 75-80 DEG C of temperature constant magnetic stirring 1.5-2h, centrifuge washing to neutrality, filter residue is added to 18-20 times of parts by weight
Sodium chlorite solution in, using acetic acid-sodium acetate buffer solution, regulation system pH is 4-5,75-80 DEG C of temperature constant magnetic stirring
1.5-2h, centrifuge washing to neutrality, machine crushing is dry, pulverize in 50-60 DEG C of vacuum drying chamber；Product after drying and crushing is added
Enter into the sulfuric acid solution of 18-20 times of parts by weight, 75-85 DEG C of temperature constant magnetic stirring 1.5-2h, centrifuge washing to neutrality, 50-60
Sieving is dry, pulverize in DEG C vacuum drying chamber, the particle of 150-200 mesh is obtained, obtains rice straw cellulose；
（2）Rice straw cellulose is added in the deionized water of 10-12 times of parts by weight, ultrasonic vibration 20-30min, added
The acetic anhydride of 1.2-1.5 times of parts by weight and the catalyst of 0.008-0.01 times of parts by weight, 40-50 DEG C of temperature constant magnetic stirring 50-
60min, reaction terminate rear centrifuge washing to neutrality, and homogenization is carried out in high pressure homogenizer under 50-60MPa, obtains acetylation
Rice straw cellulose；
（3）By phthalic anhydride, glycerine, acetylation rice straw cellulose, adipic acid and neopentyl glycol with 1：0.5-0.6：
0.12-0.15：0.18-0.2：0.4-0.45 mass ratio mixing, heating stirring to system is into homogeneous liquid phase, and rise temperature is extremely
130-140 DEG C, temperature constant magnetic stirring 5-6h, 180-190 DEG C is continuously heating to, condensing unit is changed to a point water condensing unit, it is permanent
Warm magnetic agitation 3-4h, cooling, stop reaction, obtain PEPA；
（4）Isophorone-diisocyanate is placed in reaction vessel, is mixed evenly, at room temperature, while stirring with 2-
The speed of 3s/ drops is slowly added to PEPA and the positive fourth tin of tin dilaurate two with 1：What 0.002-0.003 mass ratio was prepared
Mixed liquor, after being added dropwise, it is 50-55 DEG C to control temperature, temperature constant magnetic stirring reaction 2-3h, adds the ethoxy of γ-aminopropyl three
Base silane, rise temperature continue temperature constant magnetic stirring reaction 4-6h, add hydroxyethyl methacrylate, continue permanent to 70-75 DEG C
Warm magnetic agitation reaction 1-2h, acetone is slowly added dropwise under quick stirring, is continued temperature constant magnetic stirring reaction 60-80min, is cooled,
Obtain the cellulose modified polyurethane adhesive of rice straw.
The preparation method of the cellulose modified polyurethane adhesive of described rice straw, it is characterised in that step（1）In
The concentration of sodium hydroxide solution is 0.1-0.12mol/L, and the concentration of sodium chlorite solution is 0.05-0.06mol/L, sulfuric acid solution
Concentration be 0.1-0.12mol/L, by isometric 0.1mol/L acetic acid solution and 0.1mol/L sodium acetate solution mix
Configuration obtains.
The preparation method of the cellulose modified polyurethane adhesive of described rice straw, it is characterised in that step（2）In
The preparation method of catalyst is：By morpholine, Isosorbide-5-Nitrae-butane sultone and absolute ethyl alcohol with 1：0.8-0.9：4-5 mass ratio is put
Mixed in container, 50-55 DEG C of temperature constant magnetic stirring 4-5h, filter, using ether wash 2-3 time, drying, obtain 1- alkyl-
3- (butyl -4- sulfonic groups) alkylbenzyldimethylasaltsum saltsum；1- alkyl -3- (butyl -4- sulfonic groups) alkylbenzyldimethylasaltsum saltsum is placed in container, delayed while stirring
The oleum of the quality such as slow dropwise addition, 75-85 DEG C of temperature constant magnetic stirring 5-6h, is washed 2-3 times using ether, and revolving removes second
Ether, obtain catalyst.
The preparation method of the cellulose modified polyurethane adhesive of described rice straw, it is characterised in that step（4）In
Isophorone-diisocyanate, PEPA, gamma-aminopropyl-triethoxy-silane, hydroxyethyl methacrylate and acetone
Mass ratio is 1：0.5-0.6：0.15-0.2：0.15-0.2：2-3.
Using above-mentioned technical scheme, the beneficial effects of the invention are as follows：
The present invention is soaked by alkali, sodium chlorite, acidleach and high-pressure homogeneous prepares rice straw cellulose；Adopted under catalyst action
Esterification occurs with acetic anhydride and rice straw cellulose and prepares acetylation rice straw cellulose；Prepare acetylation rice straw
During stalk fiber element, reaction condition is gentle so that cellulose as the substantive characteristics of reinforcer rigid crystalline structure and
Rod-like shape is maintained, and has high-crystallinity, high-modulus, renewable, biodegradable, advantages of environment protection；Using two
First carboxylic acid, dihydric alcohol, trihydroxylic alcohol oligomerisation, acetylation rice straw is cellulose modified, obtains PEPA；With acetylation rice
Stalk cellulose modification prepares PEPA so that PEPA has excellent heat resistance and suitable viscosity；This
Invention prepares polyaminoester emulsion with the PEPA, isocyanates, siloxanes and the acrylate reactions that are prepared again, prepares
Cellulose has rigid crystalline structure and Rod-like shape, and the introducing of element silicon in obtained PEPA, then passes through third
Olefin(e) acid ester is appropriately crosslinked, and polyurethane adhesive has good heat endurance and adhesive force.The adhesive of the present invention, heat endurance
Good, photooxidation resistant, water resistance are superior, and the glued membrane tack formed after solidification is good, and mechanical property is good, and whole preparation method has work
The advantages of skill is simple, cost is cheap, environment-friendly, quickness and high efficiency.
Embodiment
The cellulose modified polyurethane adhesive of the rice straw of the present embodiment, it is prepared by following specific steps：
（1）Rice straw is cleaned up using water, 60 DEG C of low temperature dryings, pulverizer crushes, and crosses 60 mesh sieves, and 60 DEG C of low temperature dry
It is dry, rice straw powder is obtained, it is standby；Rice straw powder is added in the sodium hydroxide solution of 20 times of parts by weight and is stirred,
80 DEG C of temperature constant magnetic stirring 2h, centrifuge washing to neutrality, filter residue is added in the sodium chlorite solution of 20 times of parts by weight, using second
Acid-sodium acetate buffer solution, regulation system pH are 5,80 DEG C of temperature constant magnetic stirring 2h, centrifuge washing to neutrality, and 60 DEG C of vacuum are done
Machine crushing is dry, pulverize in dry case；Product after drying and crushing is added in the sulfuric acid solution of 20 times of parts by weight, 85 DEG C of constant temperature
Magnetic agitation 2h, centrifuge washing to neutrality, sieving is dry, pulverize in 60 DEG C of vacuum drying chambers, the particle of 200 mesh is obtained, obtains
Rice straw cellulose；
（2）Rice straw cellulose is added in the deionized water of 12 times of parts by weight, ultrasonic vibration 30min, adds 1.5 times of weights
The acetic anhydride of part and the catalyst of 0.01 times of parts by weight, 50 DEG C of temperature constant magnetic stirring 50-60min are measured, reaction is centrifuged after terminating and washed
Wash to neutrality, homogenization is carried out in high pressure homogenizer under 60MPa, obtains acetylation rice straw cellulose；
（3）By phthalic anhydride, glycerine, acetylation rice straw cellulose, adipic acid and neopentyl glycol with 1：0.6：0.15：
0.2：0.45 mass ratio mixing, heating stirring to system into homogeneous liquid phase, rise temperature to 140 DEG C, temperature constant magnetic stirring 6h,
180 DEG C are continuously heating to, condensing unit is changed to a point water condensing unit, temperature constant magnetic stirring 4h, cooling, stops reaction, obtains
PEPA；
（4）Isophorone-diisocyanate is placed in reaction vessel, is mixed evenly, at room temperature, while stirring with 3s/
The speed of drop is slowly added to PEPA and the positive fourth tin of tin dilaurate two with 1：The mixed liquor that 0.003 mass ratio is prepared, drop
After adding, it is 55 DEG C to control temperature, temperature constant magnetic stirring reaction 3h, adds gamma-aminopropyl-triethoxy-silane, raises temperature
To 75 DEG C, continue temperature constant magnetic stirring reaction 6h, add hydroxyethyl methacrylate, continue temperature constant magnetic stirring reaction 2h, soon
Acetone is slowly added dropwise under speed stirring, continues temperature constant magnetic stirring reaction 80min, cooling, it is cellulose modified to obtain rice straw
Polyurethane adhesive.
The step of the present embodiment（1）The concentration of middle sodium hydroxide solution is 0.1mol/L, and the concentration of sodium chlorite solution is
0.05mol/L, the concentration of sulfuric acid solution is 0.1mol/L, by isometric 0.1mol/L acetic acid solution and 0.1mol/L second
Acid sodium solution mixed configuration obtains.
The step of the present embodiment（2）The preparation method of middle catalyst is：By morpholine, Isosorbide-5-Nitrae-butane sultone and anhydrous second
Alcohol is with 1：0.9：5 mass ratio, which is placed in container, to be mixed, 55 DEG C of temperature constant magnetic stirring 5h, filtering, is washed 3 times using ether, is done
It is dry, obtain 1- alkyl -3- (butyl -4- sulfonic groups) alkylbenzyldimethylasaltsum saltsum；1- alkyl -3- (butyl -4- sulfonic groups) alkylbenzyldimethylasaltsum saltsum is placed in appearance
In device, the oleum of quality such as it is slowly added dropwise while stirring, 85 DEG C of temperature constant magnetic stirring 6h, is washed 3 times using ether, revolving
Ether is removed, obtains catalyst.
The step of the present embodiment（4）Middle isophorone-diisocyanate, PEPA, gamma-aminopropyl-triethoxy silicon
The mass ratio of alkane, hydroxyethyl methacrylate and acetone is 1：0.6：0.2：0.2：3.
Claims (5)
- A kind of 1. cellulose modified polyurethane adhesive of rice straw, it is characterised in that soaked first by alkali, sodium chlorite, Acidleach and high-pressure homogeneous prepare rice straw cellulose；Secondly, acetylation rice straw cellulose is prepared；Then, with acetylation Rice straw is cellulose modified to prepare PEPA, finally, with PEPA, isocyanates and acrylate reactions, obtains The polyurethane adhesive cellulose modified to a kind of rice straw.
- 2. the cellulose modified polyurethane adhesive of rice straw according to claims 1, it is characterised in that it is by such as Lower specific steps are prepared：（1）Rice straw is cleaned up using water, 50-60 DEG C of low temperature drying, pulverizer crushes, and crosses 40-60 mesh sieves, 50- 60 DEG C of low temperature dryings, obtain rice straw powder, standby；The sodium hydroxide that rice straw powder is added to 18-20 times of parts by weight is molten It is stirred in liquid, 75-80 DEG C of temperature constant magnetic stirring 1.5-2h, centrifuge washing to neutrality, filter residue is added to 18-20 times of parts by weight Sodium chlorite solution in, using acetic acid-sodium acetate buffer solution, regulation system pH is 4-5,75-80 DEG C of temperature constant magnetic stirring 1.5-2h, centrifuge washing to neutrality, machine crushing is dry, pulverize in 50-60 DEG C of vacuum drying chamber；Product after drying and crushing is added Enter into the sulfuric acid solution of 18-20 times of parts by weight, 75-85 DEG C of temperature constant magnetic stirring 1.5-2h, centrifuge washing to neutrality, 50-60 Sieving is dry, pulverize in DEG C vacuum drying chamber, the particle of 150-200 mesh is obtained, obtains rice straw cellulose；（2）Rice straw cellulose is added in the deionized water of 10-12 times of parts by weight, ultrasonic vibration 20-30min, added The acetic anhydride of 1.2-1.5 times of parts by weight and the catalyst of 0.008-0.01 times of parts by weight, 40-50 DEG C of temperature constant magnetic stirring 50- 60min, reaction terminate rear centrifuge washing to neutrality, and homogenization is carried out in high pressure homogenizer under 50-60MPa, obtains acetylation Rice straw cellulose；（3）By phthalic anhydride, glycerine, acetylation rice straw cellulose, adipic acid and neopentyl glycol with 1：0.5-0.6： 0.12-0.15：0.18-0.2：0.4-0.45 mass ratio mixing, heating stirring to system is into homogeneous liquid phase, and rise temperature is extremely 130-140 DEG C, temperature constant magnetic stirring 5-6h, 180-190 DEG C is continuously heating to, condensing unit is changed to a point water condensing unit, it is permanent Warm magnetic agitation 3-4h, cooling, stop reaction, obtain PEPA；（4）Isophorone-diisocyanate is placed in reaction vessel, is mixed evenly, at room temperature, while stirring with 2- The speed of 3s/ drops is slowly added to PEPA and the positive fourth tin of tin dilaurate two with 1：What 0.002-0.003 mass ratio was prepared Mixed liquor, after being added dropwise, it is 50-55 DEG C to control temperature, temperature constant magnetic stirring reaction 2-3h, adds the ethoxy of γ-aminopropyl three Base silane, rise temperature continue temperature constant magnetic stirring reaction 4-6h, add hydroxyethyl methacrylate, continue permanent to 70-75 DEG C Warm magnetic agitation reaction 1-2h, acetone is slowly added dropwise under quick stirring, is continued temperature constant magnetic stirring reaction 60-80min, is cooled, Obtain the cellulose modified polyurethane adhesive of rice straw.
- 3. the preparation method of the cellulose modified polyurethane adhesive of rice straw according to claims 2, its feature It is, step（1）The concentration of middle sodium hydroxide solution is 0.1-0.12mol/L, and the concentration of sodium chlorite solution is 0.05- 0.06mol/L, the concentration of sulfuric acid solution is 0.1-0.12mol/L, and acetic acid-sodium acetate buffer solution is by isometric 0.1mol/L Acetic acid solution and 0.1mol/L sodium acetate solution mixed configuration obtain.
- 4. the preparation method of the cellulose modified polyurethane adhesive of rice straw according to claims 2, its feature It is, step（2）The preparation method of middle catalyst is：By morpholine, Isosorbide-5-Nitrae-butane sultone and absolute ethyl alcohol with 1：0.8- 0.9：4-5 mass ratio, which is placed in container, to be mixed, 50-55 DEG C of temperature constant magnetic stirring 4-5h, filtering, is washed 2-3 times using ether, Dry, obtain 1- alkyl -3- (butyl -4- sulfonic groups) alkylbenzyldimethylasaltsum saltsum；1- alkyl -3- (butyl -4- sulfonic groups) alkylbenzyldimethylasaltsum saltsum is placed in In container, the oleum of quality such as it is slowly added dropwise while stirring, 75-85 DEG C of temperature constant magnetic stirring 5-6h, is washed using ether 2-3 times, revolving removes ether, obtains catalyst.
- 5. the preparation method of the cellulose modified polyurethane adhesive of rice straw according to claims 2, its feature It is, step（4）Middle isophorone-diisocyanate, PEPA, gamma-aminopropyl-triethoxy-silane, methacrylic acid The mass ratio of hydroxyl ethyl ester and acetone is 1：0.5-0.6：0.15-0.2：0.15-0.2：2-3.
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| CN108722423A (en) * | 2018-05-16 | 2018-11-02 | 芜湖市创源新材料有限公司 | A kind of preparation method of biomass tar cracking catalyst |
| CN109485735A (en) * | 2018-10-25 | 2019-03-19 | 深圳大学 | Cellulose esters and its preparation method and application |
| WO2020082294A1 (en) * | 2018-10-25 | 2020-04-30 | 深圳大学 | Cellulose ester and preparation method therefor and application thereof |
| CN111116865A (en) * | 2020-01-06 | 2020-05-08 | 万华化学集团股份有限公司 | High-water-resistance and hydrophilic polyisocyanate curing agent and preparation method and application thereof |
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| CN111116865A (en) * | 2020-01-06 | 2020-05-08 | 万华化学集团股份有限公司 | High-water-resistance and hydrophilic polyisocyanate curing agent and preparation method and application thereof |
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