CN106800755A - A kind of method that utilization black liquid prepares high-toughness polylactic acid - Google Patents
A kind of method that utilization black liquid prepares high-toughness polylactic acid Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The present invention relates to a kind of method that utilization black liquid prepares high-toughness polylactic acid, belong to field of polymer material preparing technology.The present invention is using the cellulose in natural organic acids acidolysis removal black liquid, lignin is obtained with hydrochloric acid acid out, using lignin and cobweb as toughening material, surface is carried out to lignin and cobweb using natural resin peach gum in the presence of microorganism to be modified, increase the resin particle on toughening material surface, improve the compatibility with PLA, wherein lignin is similar with PLA polarity, intermolecular hydrogen bonding is formed between carbon-based and lignin hydroxyl in PLA, benzene ring structure in lignin improves thermal oxide and the photooxidation stability of PLA again, and lignin and cobweb toughness is splendid in itself, increased the toughness of PLA again as filler.The good toughness of PLA prepared by the present invention, its elongation at break reaches more than 17.8%；Thermal oxide and photooxidation stability are high, and its heat distortion temperature is up to 79~82 DEG C.
Description
Technical field
The present invention relates to a kind of method that utilization black liquid prepares high-toughness polylactic acid, belong to macromolecular material and prepare skill
Art field.
Background technology
Have a hydroxyl and a carboxyl in single lactic acid molecules, multiple lactic acid molecules together ,-OH and other molecule
- COOH dehydrating condensations ,-OH the dehydrating condensations of-COOH and other molecule, like this, they hand in hand and form polymer, cry
Do PLA.PLA is also referred to as polylactide, belongs to polyester family.PLA is that main polymerizable raw material is obtained with lactic acid
Polymer, raw material sources are abundant and can regenerate.The production process of PLA is pollution-free, and product can with biodegradation,
The circulation in nature is realized, therefore is preferable Green Polymer Material.In industrial plastic application, PLA shows
Mechanical strength higher, preferable transparent and easier machine-shaping property.But its fancy price, heat change not high
Shape temperature, poor toughness, thermal oxide and photooxidation stability and uncontrollable degradation rate and degradation cycle are greatly limited
Its extensive use.
Black liquid is main accessory substance in pulping and papermaking process, dark thick shape liquid, with special foul smell, and
And containing 20%~30% lignin, it is biodegradable difficult because lignin structure is complicated, thus be global primary pollution source it
One.Lignin is the natural aromatic polymer of plant secondary metabolism synthesis, second is enriched in nature
Natural resources, is only second to cellulose, with recyclability.Because lignin phosphorus content is big, and containing various active functional group,
Such as hydroxyl, carbonyl, carboxyl, methyl and side-chain structure.Wherein hydroxyl exist in lignin it is more, with alcoholic extract hydroxyl group and phenolic hydroxyl group two
The form of kind is present, therefore can produce chemical bonding with many materials, and theory is provided to carry out toughening modifying to other materials
Basis.Lignin is added into macromolecular material, the benzene ring structure in lignin can improve thermal oxide and the light of matrix material
Oxidation stability.Lignin light weight, inexpensive, degradation property are excellent.Although lignin can assign height in being added into macromolecular material
The price of macromolecule lignin composite material is reduced while molecular composite material special degradation property, but due in lignin
There is very strong intramolecular or intermolecular hydrogen bonding effect and lignin cross-linked structure complicated in itself, therefore lignin is being filled out
Tend not to compatible with matrix well when filling macromolecule, this will directly cause the reduction of composite materials property.Therefore send out
It is bright go out a kind of with low cost, toughness is high, the polydactyl acid of thermal oxide and photooxidation good stability, industry tool is prepared to PLA
There is important meaning.
The content of the invention
The technical problems to be solved by the invention：There is price for common poly-lactic acid material at present high, toughness compared with
Difference, thermal oxide and photooxidation stability is not high, limits its wide variety of problem, there is provided one kind is carried from fruit zymotic fluid
Citric acid is taken, then acidolysis is blended and is removed cellulose and hemicellulose with acidified with citric acid winestone and with black liquid, then in hydrochloric acid
Auxiliary under acid out obtain lignin, then with peach gum is modified and polylactic acid blend granulates the method that obtains final product high-toughness polylactic acid.
The present invention is using the cellulose in natural organic acids acidolysis removal black liquid, then obtains lignin with hydrochloric acid acid out, with wooden
Element and cobweb carry out table in the presence of microorganism using natural resin peach gum as toughening material to lignin and cobweb
Face is modified, and increases the resin particle on toughening material surface, improves its compatibility with PLA, wherein lignin and PLA pole
Property is similar, and intermolecular hydrogen bonding is formed between carbon-based and lignin the hydroxyl in PLA, and the benzene ring structure in lignin again may be used
Improve PLA thermal oxide and photooxidation stability, and lignin and cobweb toughness is splendid in itself, increase again as filler
The toughness of PLA is added.Obtained poly-lactic acid material toughness of the invention is strong, and thermal oxide and photooxidation stability are high, with lignin
Filling polylactic acid reduces the price of material again, has broad application prospects.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
（1）In mass ratio it is 10:1, Luo Wang fruits and belt leather grape are sequentially placed into tissue pulverizer and crush 30~40min, will
The crushed material for obtaining is moved into ceramic pot, then to the pectase and crushed material quality 2% that crushed material quality 1% is added in ceramic pot
Cellulase, tank mouth is sealed after stirring, and natural enzymolysis ferment 5~7 days at 30~40 DEG C；
（2）After after fermentation ends, tunning is obtained into filtrate with three layers of filtered through gauze, by the tartaric acid that mass fraction is 40%
Solution and filtrate are 1 in mass ratio:Mixed liquor is obtained after 3 stirring mixing；
（3）Collect black liquid and with above-mentioned mixed liquor by volume be 1:2, it is sequentially loaded into rustless steel container, to stainless steel
Container heating is until boiling, then naturally cools to 53~57 DEG C, and it is 0.5mol/L salt to continue to concentration is added in rustless steel container
To 2.5~3.0, insulation is centrifugally separating to obtain lignin deposit to acid for adjusting pH after standing 2~4h；
（4）It is 2 to take above-mentioned lignin deposit, peach gum and cobweb in mass ratio:1:It is transferred in fermentation tank after 1 mixing, then is received
Methane liquid is obtained in collection methane-generating pit and upper liquid is centrifugally separating to obtain, then added the upper liquid of above-mentioned lignin deposit quality 10%
Enter in fermentation tank, sealing tank mouth is fermented 1~3 day at 35~45 DEG C, is separated by filtration after fermentation ends and is obtained filter residue, and filter residue is put
Enter in baking oven, dry 1~2h obtains modifying agent at 40~50 DEG C；
（5）Count by weight, weigh 60~75 parts of PLAs, 20~25 parts of above-mentioned modifying agent, 2~3 parts of castor oil and 1~3
Part Silane coupling agent KH550 is sequentially loaded into banbury, and 10~15min of banburying, obtains polydactyl acid at 185~190 DEG C
Masterbatch；
（6）By extruding pelletization in above-mentioned polydactyl acid masterbatch immigration twin-screw melt extruder, high-ductility is can obtain after drying
Property PLA, the condition of work of the twin-screw melt extruder extruding pelletization is：One 130~150 DEG C of area, two areas 140~150
DEG C, three 150~170 DEG C of areas, four 160~180 DEG C of areas, five 170~190 DEG C of areas, six 170~190 DEG C of areas, seven areas 165~185
DEG C, 160~175 DEG C of head, screw speed is 300~500r/min, and extrusion pressure is 12~15MPa.
High-toughness polylactic acid heat distortion temperature prepared by the present invention is 79~82 DEG C, and tensile strength reaches more than 75.2MPa,
Elongation at break reaches more than 17.8%, and notch impact strength is 6.5~7.2kJ/m2, unnotched impact strength be 57.8~
62.8kJ/m2。
Compared with other method, Advantageous Effects are the present invention：
（1）The present invention is toughening material using cobweb and lignin, improves the toughness of PLA, and its elongation at break reaches
More than 17.8%；
（2）PLA thermal oxide and photooxidation stability prepared by the present invention is high, and its heat distortion temperature, can be wide up to 79~82 DEG C
It is general to be applied to polymeric material field；
（3）PLA prepared by the present invention is main with black liquid as raw material, and resource is recycled again, meets sustainable development
It is required that, and it is with low cost, have broad application prospects.
Specific embodiment
First in mass ratio it is 10:1, Luo Wang fruits and belt leather grape are sequentially placed into tissue pulverizer and crush 30~
40min, the crushed material that will be obtained is moved into ceramic pot, then to the pectase and crushed material of addition crushed material quality 1% in ceramic pot
The cellulase of quality 2%, tank mouth is sealed after stirring, and natural enzymolysis ferment 5~7 days at 30~40 DEG C；Treat fermentation ends
Afterwards, tunning is obtained into filtrate with three layers of filtered through gauze, by tartaric acid solution that mass fraction is 40% and filtrate in mass ratio
It is 1:Mixed liquor is obtained after 3 stirring mixing；Collect black liquid and with above-mentioned mixed liquor by volume be 1:2, it is sequentially loaded into not
In rust steel container, rustless steel container is heated until boiling, then naturally cools to 53~57 DEG C, continue in rustless steel container plus
It is 0.5mol/L salt acid for adjusting pH to 2.5~3.0 to enter concentration, and insulation is centrifugally separating to obtain lignin deposit after standing 2~4h；Take
Above-mentioned lignin deposit, peach gum and cobweb are 2 in mass ratio:1:It is transferred in fermentation tank after 1 mixing, in regathering methane-generating pit
Methane liquid and be centrifugally separating to obtain upper liquid, during the upper liquid of above-mentioned lignin deposit quality 10% then added into fermentation tank,
Sealing tank mouth is fermented 1~3 day at 35~45 DEG C, is separated by filtration after fermentation ends and is obtained filter residue, and filter residue is put into baking oven,
1~2h is dried at 40~50 DEG C and obtains modifying agent；Count by weight, weigh 60~75 parts of PLAs, 20~25 parts above-mentioned change
Property agent, 2~3 parts of castor oil and 1~3 part of Silane coupling agent KH550 are sequentially loaded into banbury, the banburying 10 at 185~190 DEG C
~15min, obtains polydactyl acid masterbatch；Extruded during above-mentioned polydactyl acid masterbatch finally is moved into twin-screw melt extruder
Granulation, high-toughness polylactic acid is can obtain after drying, and the condition of work of the twin-screw melt extruder extruding pelletization is：One area
130~150 DEG C, two 140~150 DEG C of areas, three 150~170 DEG C of areas, four 160~180 DEG C of areas, five 170~190 DEG C of areas, 6th area
170~190 DEG C, seven 165~185 DEG C of areas, 160~175 DEG C of head, screw speed is 300~500r/min, and extrusion pressure is 12
~15MPa.
Example 1
First in mass ratio it is 10:1, Luo Wang fruits and belt leather grape are sequentially placed into tissue pulverizer and crush 40min, will obtain
Crushed material move into ceramic pot, then to the pectase and the fiber of crushed material quality 2% that crushed material quality 1% is added in ceramic pot
Plain enzyme, tank mouth is sealed after stirring, and natural enzymolysis ferment 7 days at 40 DEG C；After after fermentation ends, by tunning with three layers
Filtered through gauze obtains filtrate, is in mass ratio 1 by tartaric acid solution that mass fraction is 40% and filtrate:Obtained after 3 stirring mixing
Mixed liquor；Collect black liquid and with above-mentioned mixed liquor by volume be 1:2, it is sequentially loaded into rustless steel container, to stainless steel
Container heating is until boiling, then naturally cools to 57 DEG C, and it is 0.5mol/L hydrochloric acid tune to continue to concentration is added in rustless steel container
Section pH to 3.0, insulation is centrifugally separating to obtain lignin deposit after standing 4h；Take above-mentioned lignin deposit, peach gum and cobweb
In mass ratio it is 2:1:It is transferred in fermentation tank after 1 mixing, regathers in methane-generating pit methane liquid and to be centrifugally separating to obtain upper liquid,
Then by the upper liquid addition fermentation tank of above-mentioned lignin deposit quality 10%, sealing tank mouth is fermented 3 days at 45 DEG C, is fermented
It is separated by filtration after end and obtains filter residue, filter residue is put into baking oven, drying 2h at 50 DEG C obtains modifying agent；By weight
Meter, weighs 75 parts of PLAs, 25 parts of above-mentioned modifying agent, 3 parts of castor oil and 3 parts of Silane coupling agent KH550s and is sequentially loaded into banbury
In, the banburying 15min at 190 DEG C obtains polydactyl acid masterbatch；Finally above-mentioned polydactyl acid masterbatch immigration twin-screw is melted
Melt extruding pelletization in extruder, high-toughness polylactic acid is can obtain after drying, the twin-screw melt extruder extruding pelletization
Condition of work is：One 150 DEG C of area, two 150 DEG C of areas, three 170 DEG C of areas, four 180 DEG C of areas, five 190 DEG C of areas, six 190 DEG C of areas, 7th area
185 DEG C, 175 DEG C of head, screw speed is 500r/min, and extrusion pressure is 15MPa.
After testing, the high-toughness polylactic acid heat distortion temperature that prepared by the present invention is 82 DEG C, and tensile strength reaches 75.9MPa,
Elongation at break reaches 19.8%, and notch impact strength is 7.2kJ/m2, unnotched impact strength is 62.8kJ/m2。
Example 2
First in mass ratio it is 10:1, Luo Wang fruits and belt leather grape are sequentially placed into tissue pulverizer and crush 30min, will obtain
Crushed material move into ceramic pot, then to the pectase and the fiber of crushed material quality 2% that crushed material quality 1% is added in ceramic pot
Plain enzyme, tank mouth is sealed after stirring, and natural enzymolysis ferment 5 days at 30 DEG C；After after fermentation ends, by tunning with three layers
Filtered through gauze obtains filtrate, is in mass ratio 1 by tartaric acid solution that mass fraction is 40% and filtrate:Obtained after 3 stirring mixing
Mixed liquor；Collect black liquid and with above-mentioned mixed liquor by volume be 1:2, it is sequentially loaded into rustless steel container, to stainless steel
Container heating is until boiling, then naturally cools to 53 DEG C, and it is 0.5mol/L hydrochloric acid tune to continue to concentration is added in rustless steel container
Section pH to 2.5, insulation is centrifugally separating to obtain lignin deposit after standing 2h；Take above-mentioned lignin deposit, peach gum and cobweb
In mass ratio it is 2:1:It is transferred in fermentation tank after 1 mixing, regathers in methane-generating pit methane liquid and to be centrifugally separating to obtain upper liquid,
Then by the upper liquid addition fermentation tank of above-mentioned lignin deposit quality 10%, sealing tank mouth is fermented 1 day at 35 DEG C, is fermented
It is separated by filtration after end and obtains filter residue, filter residue is put into baking oven, drying 1h at 40 DEG C obtains modifying agent；By weight
Meter, weighs 60 parts of PLAs, 20 parts of above-mentioned modifying agent, 2 parts of castor oil and 1 part of Silane coupling agent KH550 and is sequentially loaded into banbury
In, the banburying 10min at 185 DEG C obtains polydactyl acid masterbatch；Finally above-mentioned polydactyl acid masterbatch immigration twin-screw is melted
Melt extruding pelletization in extruder, high-toughness polylactic acid is can obtain after drying, the twin-screw melt extruder extruding pelletization
Condition of work is：One 130 DEG C of area, two 140 DEG C of areas, three 150 DEG C of areas, four 160 DEG C of areas, five 170 DEG C of areas, six 170 DEG C of areas, 7th area
165 DEG C, 160 DEG C of head, screw speed is 300r/min, and extrusion pressure is 12MPa.
After testing, the high-toughness polylactic acid heat distortion temperature that prepared by the present invention is 79 DEG C, and tensile strength reaches 78.5MPa,
Elongation at break reaches 20.1%, and notch impact strength is 6.5kJ/m2, unnotched impact strength is 57.8kJ/m2。
Example 3
First in mass ratio it is 10:1, Luo Wang fruits and belt leather grape are sequentially placed into tissue pulverizer and crush 35min, will obtain
Crushed material move into ceramic pot, then to the pectase and the fiber of crushed material quality 2% that crushed material quality 1% is added in ceramic pot
Plain enzyme, tank mouth is sealed after stirring, and natural enzymolysis ferment 6 days at 35 DEG C；After after fermentation ends, by tunning with three layers
Filtered through gauze obtains filtrate, is in mass ratio 1 by tartaric acid solution that mass fraction is 40% and filtrate:Obtained after 3 stirring mixing
Mixed liquor；Collect black liquid and with above-mentioned mixed liquor by volume be 1:2, it is sequentially loaded into rustless steel container, to stainless steel
Container heating is until boiling, then naturally cools to 55 DEG C, and it is 0.5mol/L hydrochloric acid tune to continue to concentration is added in rustless steel container
The section insulations of pH to 2.7 are centrifugally separating to obtain lignin deposit after standing 3h；Take above-mentioned lignin deposit, peach gum and cobweb by
Mass ratio is 2:1:It is transferred in fermentation tank after 1 mixing, regathers in methane-generating pit methane liquid and to be centrifugally separating to obtain upper liquid, with
Afterwards by the upper liquid addition fermentation tank of above-mentioned lignin deposit quality 10%, sealing tank mouth is fermented 2 days at 40 DEG C, fermentation knot
It is separated by filtration after beam and obtains filter residue, filter residue is put into baking oven, drying 2h at 45 DEG C obtains modifying agent；Count by weight,
70 parts of PLAs, 22 parts of above-mentioned modifying agent, 2 parts of castor oil and 2 parts of Silane coupling agent KH550s are weighed to be sequentially loaded into banbury,
The banburying 12min at 187 DEG C, obtains polydactyl acid masterbatch；Above-mentioned polydactyl acid masterbatch is finally moved into twin-screw melting
Extruding pelletization in extruder, high-toughness polylactic acid, the work of the twin-screw melt extruder extruding pelletization are can obtain after drying
It is as condition：One 135 DEG C of area, two 145 DEG C of areas, three 160 DEG C of areas, four 170 DEG C of areas, five 180 DEG C of areas, six 180 DEG C of areas, seven areas 170
DEG C, 170 DEG C of head, screw speed is 400r/min, and extrusion pressure is 13MPa.
After testing, the high-toughness polylactic acid heat distortion temperature that prepared by the present invention is 80 DEG C, and tensile strength reaches 76.2MPa,
Elongation at break reaches 18.4%, and notch impact strength is 6.8kJ/m2, unnotched impact strength is 59.2kJ/m2。
Claims (1)
1. a kind of method that utilization black liquid prepares high-toughness polylactic acid, it is characterised in that specifically preparation process is：
（1）In mass ratio it is 10:1, Luo Wang fruits and belt leather grape are sequentially placed into tissue pulverizer and crush 30~40min, will
The crushed material for obtaining is moved into ceramic pot, then to the pectase and crushed material quality 2% that crushed material quality 1% is added in ceramic pot
Cellulase, tank mouth is sealed after stirring, and natural enzymolysis ferment 5~7 days at 30~40 DEG C；
（2）After after fermentation ends, tunning is obtained into filtrate with three layers of filtered through gauze, by the tartaric acid that mass fraction is 40%
Solution and filtrate are 1 in mass ratio:Mixed liquor is obtained after 3 stirring mixing；
（3）Collect black liquid and with above-mentioned mixed liquor by volume be 1:2, it is sequentially loaded into rustless steel container, to stainless steel
Container heating is until boiling, then naturally cools to 53~57 DEG C, and it is 0.5mol/L salt to continue to concentration is added in rustless steel container
To 2.5~3.0, insulation is centrifugally separating to obtain lignin deposit to acid for adjusting pH after standing 2~4h；
（4）It is 2 to take above-mentioned lignin deposit, peach gum and cobweb in mass ratio:1:It is transferred in fermentation tank after 1 mixing, then is received
Methane liquid is obtained in collection methane-generating pit and upper liquid is centrifugally separating to obtain, then added the upper liquid of above-mentioned lignin deposit quality 10%
Enter in fermentation tank, sealing tank mouth is fermented 1~3 day at 35~45 DEG C, is separated by filtration after fermentation ends and is obtained filter residue, and filter residue is put
Enter in baking oven, dry 1~2h obtains modifying agent at 40~50 DEG C；
（5）Count by weight, weigh 60~75 parts of PLAs, 20~25 parts of above-mentioned modifying agent, 2~3 parts of castor oil and 1~3
Part Silane coupling agent KH550 is sequentially loaded into banbury, and 10~15min of banburying, obtains polydactyl acid at 185~190 DEG C
Masterbatch；
（6）By extruding pelletization in above-mentioned polydactyl acid masterbatch immigration twin-screw melt extruder, high-ductility is can obtain after drying
Property PLA, the condition of work of the twin-screw melt extruder extruding pelletization is：One 130~150 DEG C of area, two areas 140~150
DEG C, three 150~170 DEG C of areas, four 160~180 DEG C of areas, five 170~190 DEG C of areas, six 170~190 DEG C of areas, seven areas 165~185
DEG C, 160~175 DEG C of head, screw speed is 300~500r/min, and extrusion pressure is 12~15MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163524A (en) * | 2017-06-07 | 2017-09-15 | 常州建轩纺织品有限公司 | A kind of preparation method of high-toughness polylactic acid composite |
| CN110372883A (en) * | 2019-08-14 | 2019-10-25 | 南京工业大学 | Method for extracting lignin and silicic acid from black liquor |
| CN111777979A (en) * | 2020-07-16 | 2020-10-16 | 江苏明天胶业有限公司 | High-strength weather-resistant modified silane sealant and preparation process thereof |
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| CN111777979A (en) * | 2020-07-16 | 2020-10-16 | 江苏明天胶业有限公司 | High-strength weather-resistant modified silane sealant and preparation process thereof |
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