CN106243309A - A kind of bio-based TPU film and preparation method thereof - Google Patents
A kind of bio-based TPU film and preparation method thereof Download PDFInfo
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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
- C08G18/6547—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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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
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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
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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Abstract
The present invention relates to a kind of bio-based TPU film and preparation method thereof, described bio-based TPU film, contains following components by weight: bio-based diisocyanate 20 40 parts, biopolyol 45 75 parts, alkyl chain extender 48 parts, antioxidant 0.2 1 parts, function graphene oxide 0.2 0.5 parts and modified potassium permanganate solution 12 parts；Wherein, described biopolyol is formulated by the mass ratio of 5 9:1 5:3 7 by castor oil-base polyhydric alcohol, rice husk polylol and megasse polylol.The bio-based TPU film that the present invention provides has thermostability and the biodegradable of excellence, can be widely applied in packaging for foodstuff, medical facilities and medical apparatus and instruments or textile material.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of bio-based TPU film and preparation method thereof.
Background technology
Along with constantly consuming of the fossil resource such as oil, natural gas and being further exacerbated by of problem of environmental pollution, find
A kind of environmental protection, reproducible new forms of energy have become as the main task of researcher current research.The main component of biomass
It is cellulose, hemicellulose and lignin, is a kind of unique reproducible carbon source, the solid-state of routine, liquid can be changed into gentle
State fuel.Polyhydric alcohol is one of primary raw material of organic synthesis, is mainly derived from the derivant of fossil resource.Biomass are necessarily
Under the conditions of liquefaction can prepare the biomass-based polyhydric alcohol with certain reactivity, thus alleviate and fossil resource depended on
Rely, for biomass further with having widened road.
At present, industry profit may all be affected due to propylene and the fluctuation of anisidine value, volatility polyhydric alcohol and MDI price
Profit.It addition, the use of harmful material can be caused new challenge by strict environmental regulation.Each major company is just investing and developing bio-based
TPU film market, is expected to offset crude oil price fluctuation, it helps reduce carbon emission.Some companies, such as A Kema, Du Pont,
Pu Liwan and Mai Jinsha has turned one's attention to biological TPU film market.
Therefore, how to prepare a kind of bio-based TPU film, and the performance making it have excellence has become the most urgently to be resolved hurrily
Problem.
Summary of the invention
For solving above-mentioned technical problem, the invention provides a kind of bio-based TPU film and preparation method thereof, the present invention carries
The bio-based TPU film of confession has thermostability and the biodegradability of excellence, can be widely applied to packaging for foodstuff, medical facilities
With in medical apparatus and instruments or textile material.
For reaching this purpose, present invention employs techniques below scheme:
First aspect, the invention provides a kind of bio-based TPU film, and it contains following components by weight:
Bio-based diisocyanate 20-40 part, biopolyol 45-75 part, alkyl chain extender 4-8 part, antioxidant
0.2-1 part, function graphene oxide 0.2-0.5 part and modified potassium permanganate solution 1-2 part；
Wherein, described biopolyol is pressed by castor oil-base polyhydric alcohol, rice husk polylol and megasse polylol
The mass ratio of 5-9:1-5:3-7 is formulated.
The present invention is by using biopolyol and bio-based diisocyanate, and the two plays synergism, makes preparation
The bio-based TPU film obtained has the best thermostability, can extensively apply packaging for foodstuff, medical facilities and medical apparatus and instruments or
In textile material.
The present invention, by increasing function graphene oxide and modified potassium permanganate solution in raw material components, which creates association
Same-action, it is provided that the thermostability of bio-based TPU film prepared by the present invention, and make it have the biodegradable of excellence.
The source of biopolyol has been carried out preferably by the present invention, uses castor oil-base polyhydric alcohol, rice husk polylol
It is also prepared by combination with megasse polylol by the mass ratio of 5-9:1-5:3-7, and three plays synergism, energy
Enough thermostability and biodegradables farthest strengthening TPU film.
In the present invention, the content of described bio-based diisocyanate is 20-40 part, such as 20,22,25,28,30,32,
35,38 or 40 parts；The content of described biopolyol is 45-75 part, such as 45,48,49,52,55,58,60,65,70 or
75 parts；The content of described alkyl chain extender is 4-8 part, such as 4,5,6,7,7.5 or 8 parts；The content of described antioxidant is
0.2-1 part, such as 0.2,0.3,0.4,0.5,0.6,0.7 or 1 part；The content of described function graphene oxide is 0.2-0.5 part,
Such as 0.2,0.3,0.4,0.45 or 0.5 part；The content of described modified potassium permanganate solution is 1-2 part, such as 1,1.1,1.2,
1.5,1.6,1.7 or 2 parts.
According to the present invention, described biopolyol is by castor oil-base polyhydric alcohol, rice husk polylol and megasse Quito
It is formulated that the mass ratio of 5-9:1-5:3-7 pressed by unit's alcohol, such as 5:3:5,6:1:4,7:2:6,8:3:4,7:5:6,7:4:5,5:
3:7 or 7:3:5.
Bio-based TPU film in the present invention, it preferably comprises following components by weight: bio-based diisocyanate
22-38 part, biopolyol 48-72 part, alkyl chain extender 5-8 part, antioxidant 0.2-0.5 part, function graphene oxide
0.3-0.5 part and modified potassium permanganate solution 1-1.5 part；
Wherein, described biopolyol is pressed by castor oil-base polyhydric alcohol, rice husk polylol and megasse polylol
The mass ratio of 6-9:3-5:3-6 is formulated.
According to the present invention, described alkyl chain extender be BDO, 1,3-PD, Isosorbide-5-Nitrae-cyclohexanediol, new penta 2
At least one in alcohol, 1,6-HD.
According to the present invention, described antioxidant is 2,6-di-tert-butyl-4-methy phenol, four (4-hydroxyl-3,5-tert-butyl benzenes
Base propanoic acid) pentaerythritol ester, at least one in 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester.
Second aspect, present invention also offers the preparation method of a kind of bio-based TPU film as described in relation to the first aspect, institute
The method of stating comprises the following steps:
(1) biopolyol and antioxidant are added in reactor by a certain percentage, keep reactor pressure be-
0.098～-0.1MPa, temperature is 90-95 DEG C, reacts 1-4h at this temperature；
(2) after bio-based diisocyanate and alkyl diol chain extender being preheated to 50-55 DEG C respectively, with step (1)
Entering double screw extruder after product and catalyst mix homogeneously, the reaction of extrusion limit, limit prepares thermoplastic polyurethane bullet
Gonosome；
(3) function graphene oxide, modified potassium permanganate solution are carried out with the Polyurethane Thermoplastic Elastomer of step (2)
Mixing, by this mixture through film-forming machine, to extrude or film forming in the way of blown film, obtains described bio-based TPU film.
According to the present invention, the castor oil-base polyhydric alcohol in described biopolyol, adopt and prepare with the following method:
1) Oleum Ricini, formic acid, phosphoric acid are added in reactor, then hydrogen peroxide is added in this system, at 55-70 DEG C
6-9h it is incubated under reaction temperature；Then stratification, washes with water, then neutralizes with alkali, after stratification, removes subnatant, takes out
Vacuum dehydration；
2) by step 1) Oleum Ricini that obtains, hydroxylating agent add in reactor, protect under the reaction temperature of 60-75 DEG C
Temperature 3-5h, carries out hydroxylating, prepares castor oil-base biological multielement alcohol.
Preferably, described phosphoric acid consumption is the 3-5% of Oleum Ricini quality；Described formic acid consumption is the 20-of Oleum Ricini quality
60%；Described hydrogen peroxide consumption is 2-3 times of Oleum Ricini quality.
According to the present invention, the rice husk polylol in described biopolyol, adopt and prepare with the following method:
With concentrated sulphuric acid as catalyst, at 130-190 DEG C, by powdered rice hulls raw material according to liquid-solid ratio (3-9): 1 joins liquid
Reacting 30-150min in agent, add acetone solution after cooling, addition sodium hydroxide regulation pH is to neutral, and decompression is distilled off
Acetone and water, obtain rice husk polylol；Wherein, described powdered rice hulls raw material be vacuum drying particle diameter be the granule of 60-80 mesh；Institute
State liquefier be Polyethylene Glycol be the solution that 6-8:1-5 mixes with n-octyl alcohol according to mass ratio.
According to the present invention, the megasse polylol in described biopolyol, adopt and prepare with the following method:
1) megasse is crushed and screened take 30-70 mesh；
2) ethylene glycol and the ethylene carbonate of 100-160 weight portion are added by the liquefaction solvent of the proportions of 1-5:3-9
Enter reactor, be subsequently added 10-20 weight portion step 1) megasse of pulverizing prepared, microwave heating to 130-150 DEG C, reaction
40-60min, reaction cools down with cold water immediately after terminating, obtains megasse polylol.
According to the present invention, described bio-based diisocyanate can use following methods to be prepared:
Employing corn straw is raw material, produces 1, 4-succinic acid through biofermentation, then is urged with ammonia by 1, 4-succinic acid
Change, ammonification and hydrogenation obtain Putriscine, then obtain bio-based diisocyanate through gas phase phosgenation reaction.
Specifically, the preparation method of heretofore described bio-based diisocyanate is document: " biomass-based Isosorbide-5-Nitrae-fourth two
The preparation of isocyanates and application in medical polyurethane material thereof ", Zhang Yong shakes, polyurethane industrial, and 2013 are the 6th interim
The method provided, does not repeats at this, it is possible to use other bio-based diisocyanate, does not do particular determination at this.
According to the present invention, described function graphene oxide is adopted and is prepared with the following method:
1) with crystalline flake graphite as raw material, the hummers method improved is utilized to prepare graphene oxide；
2) being added to reaction vessel by DMF, be subsequently adding graphene oxide, ultrasonic 10-15min obtains the oxygen of homogenization
Functionalized graphene suspension；Then isoflurane chalcone diisocyanate is added, under nitrogen protection stirring reaction 22-26h, finally will
Product dichloromethane and DMF wash 3-5 time, obtain function graphene oxide.
According to the present invention, described modified potassium permanganate solution is adopted and is prepared with the following method:
1) it is that polymethyl hydrogen siloxane, zinc stearate are mixed homogeneously by 1-3:1-3:100 with potassium permanganate in mass ratio,
React 20～40min at 130～150 DEG C, obtain modified potassium permanganate；
2) take 0.15-0.75g modification potassium permanganate to be dissolved in 20-50mL N-N dimethylformamide, ultrasonic disperse 10-
30min, obtains modified potassium permanganate solution.
In the present invention for step (3) described by mixture through film-forming machine, to extrude or film forming in the way of blown film, it is concrete
Technique uses technology well known in the art, does not do particular determination at this.
The third aspect, present invention also offers described bio-based TPU film at packaging for foodstuff, medical facilities and Medical treatment device
Application in tool or textile material.
Compared with prior art, the present invention at least has the advantages that
The present invention is by using biopolyol and bio-based diisocyanate, and the two plays synergism, makes preparation
The bio-based TPU film obtained has the best thermostability and biodegradable, can extensively apply packaging for foodstuff, medical treatment to set
Grant in medical apparatus and instruments or textile material.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described enforcement
Example only help understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
A kind of bio-based TPU film, contains following components: bio-based diisocyanate 31 parts, bio-based are many by weight
Unit's alcohol 48 parts, 1,4-butanediol 8 parts, 2,6 di tert butyl 4 methyl phenol 0.5 part, function graphene oxide 0.5 part and modification
Potassium permanganate solution 2 parts.
Described biopolyol is pressed 8:3:3 by castor oil-base polyhydric alcohol, rice husk polylol and megasse polylol
Mass ratio formulated.
The preparation method of described bio-based TPU film, comprises the following steps:
(1) by biopolyol and 2,6-di-tert-butyl-4-methy phenol adds in reactor, keeps reactor pressure
For-0.098MPa, temperature is 95 DEG C, reacts 1h at this temperature；
(2) after bio-based diisocyanate and BDO being preheated to 55 DEG C respectively, with the product of step (1)
With entrance double screw extruder after catalyst mix homogeneously, the reaction of extrusion limit, limit prepares Polyurethane Thermoplastic Elastomer；
(3) function graphene oxide, modified potassium permanganate solution are carried out with the Polyurethane Thermoplastic Elastomer of step (2)
Mixing, by this mixture through film-forming machine, to extrude or film forming in the way of blown film, obtains described bio-based TPU film.
Wherein, the preparation method of described castor oil-base polyhydric alcohol is:
1) Oleum Ricini, formic acid, phosphoric acid are added in reactor, then hydrogen peroxide is added in this system, anti-at 60 DEG C
8h it is incubated at a temperature of Ying；Then stratification, washes with water, then neutralizes with alkali, after stratification, removes subnatant, evacuation
Dehydration；
2) by step 1) Oleum Ricini that obtains, hydroxylating agent add in reactor, it be incubated under the reaction temperature of 65 DEG C
4h, carries out hydroxylating, prepares castor oil-base biological multielement alcohol；Described phosphoric acid consumption is the 4% of Oleum Ricini quality；Institute
State that formic acid consumption is Oleum Ricini quality 20%；Described hydrogen peroxide consumption is 3 times of Oleum Ricini quality；
Wherein, the preparation method of described rice husk polylol is:
With concentrated sulphuric acid as catalyst, at 135 DEG C, the powdered rice hulls raw material that particle diameter is 60 mesh is added according to liquid-solid ratio 3:1
Reacting 50min in liquefier, add acetone solution after cooling, addition sodium hydroxide regulation pH is to neutral, and decompression is distilled off
Acetone and water, obtain rice husk polylol；Described liquefier be Polyethylene Glycol with n-octyl alcohol according to mass ratio be 6:1 mix molten
Liquid；
Wherein, the preparation method of described megasse polylol is:
1) megasse is crushed and screened take 60 mesh；
2) liquefaction solvent of the proportions that ethylene glycol and the ethylene carbonate of 100 weight portions are pressed 1:9 adds reactor,
It is subsequently added 12 weight portion steps 1) megasse of pulverizing prepared, microwave heating to 130 DEG C, reacts 50min, after reaction terminates
Cool down with cold water immediately, obtain megasse polylol；
Wherein, described function graphene oxide is adopted and is prepared with the following method:
1) with crystalline flake graphite as raw material, the hummers method improved is utilized to prepare graphene oxide；
2) being added to reaction vessel by DMF, be subsequently adding graphene oxide, ultrasonic 10min obtains the oxidation of homogenization
Graphene suspension；Then isoflurane chalcone diisocyanate is added, under nitrogen protection stirring reaction 22h, finally by product
Wash 3 times with dichloromethane and DMF, obtain function graphene oxide；
Wherein, described modified potassium permanganate solution is adopted and is prepared with the following method:
1) it is that polymethyl hydrogen siloxane, zinc stearate are mixed homogeneously by 1:2:100 with potassium permanganate in mass ratio, 150 DEG C
Lower reaction 40min, obtains modified potassium permanganate；
2) take 0.75g modification potassium permanganate to be dissolved in 50mL N-N dimethylformamide, ultrasonic disperse 15min, changed
Property potassium permanganate solution.
Embodiment 2
A kind of bio-based TPU film, contains following components: bio-based diisocyanate 25 parts, bio-based are many by weight
Unit alcohol 56 parts, 1,3-propylene glycol 7 parts, 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester 0.7 part, function graphene oxide 0.3
Part and modified potassium permanganate solution 1 part.
Described biopolyol is pressed 9:5:4 by castor oil-base polyhydric alcohol, rice husk polylol and megasse polylol
Mass ratio formulated.
The preparation method of described bio-based TPU film, comprises the following steps:
(1) by biopolyol and 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester adds in reactor, keeps anti-
Answering still pressure is-0.099MPa, and temperature is 90 DEG C, reacts 2h at this temperature；
(2) after bio-based diisocyanate and 1,3-PD being preheated to 52 DEG C respectively, with the product of step (1)
With entrance double screw extruder after catalyst mix homogeneously, the reaction of extrusion limit, limit prepares Polyurethane Thermoplastic Elastomer；
(3) function graphene oxide, modified potassium permanganate solution are carried out with the Polyurethane Thermoplastic Elastomer of step (2)
Mixing, by this mixture through film-forming machine, to extrude or film forming in the way of blown film, obtains described bio-based TPU film.
Wherein, the preparation method of described castor oil-base polyhydric alcohol is:
1) Oleum Ricini, formic acid, phosphoric acid are added in reactor, then hydrogen peroxide is added in this system, anti-at 70 DEG C
6h it is incubated at a temperature of Ying；Then stratification, washes with water, then neutralizes with alkali, after stratification, removes subnatant, evacuation
Dehydration；
2) by step 1) Oleum Ricini that obtains, hydroxylating agent add in reactor, it be incubated under the reaction temperature of 62 DEG C
4h, carries out hydroxylating, prepares castor oil-base biological multielement alcohol；Described phosphoric acid consumption is the 5% of Oleum Ricini quality；Institute
State that formic acid consumption is Oleum Ricini quality 50%；Described hydrogen peroxide consumption is 2 times of Oleum Ricini quality；
Wherein, the preparation method of described rice husk polylol is:
With concentrated sulphuric acid as catalyst, at 160 DEG C, the powdered rice hulls raw material that particle diameter is 70 mesh is added according to liquid-solid ratio 8:1
Reacting 100min in liquefier, add acetone solution after cooling, addition sodium hydroxide regulation pH is to neutral, and decompression is distilled off
Acetone and water, obtain rice husk polylol；Described liquefier be Polyethylene Glycol with n-octyl alcohol according to mass ratio be 7:3 mix molten
Liquid；
Wherein, the preparation method of described megasse polylol is:
1) megasse is crushed and screened take 30 mesh；
2) liquefaction solvent of the proportions that ethylene glycol and the ethylene carbonate of 160 weight portions are pressed 1:3 adds reactor,
It is subsequently added 20 weight portion steps 1) megasse of pulverizing prepared, microwave heating to 145 DEG C, reacts 40min, after reaction terminates
Cool down with cold water immediately, obtain megasse polylol；
Wherein, described function graphene oxide is adopted and is prepared with the following method:
1) with crystalline flake graphite as raw material, the hummers method improved is utilized to prepare graphene oxide；
2) being added to reaction vessel by DMF, be subsequently adding graphene oxide, ultrasonic 12min obtains the oxidation of homogenization
Graphene suspension；Then isoflurane chalcone diisocyanate is added, under nitrogen protection stirring reaction 25h, finally by product
Wash 3 times with dichloromethane and DMF, obtain function graphene oxide；
Wherein, described modified potassium permanganate solution is adopted and is prepared with the following method:
1) it is that polymethyl hydrogen siloxane, zinc stearate are mixed homogeneously by 1:2:100 with potassium permanganate in mass ratio, 150 DEG C
Lower reaction 40min, obtains modified potassium permanganate；
2) take 0.75g modification potassium permanganate to be dissolved in 50mL N-N dimethylformamide, ultrasonic disperse 15min, changed
Property potassium permanganate solution.
Embodiment 3
A kind of bio-based TPU film, contains following components: bio-based diisocyanate 33 parts, bio-based are many by weight
Unit's alcohol 46 parts, 1,6-HD 8 parts, four (4-hydroxyl-3,5-tert-butyl-phenyl propanoic acid) pentaerythritol ester 0.5 part, function oxidation
Graphene 0.5 part and modified potassium permanganate solution 2 parts.
Described biopolyol is pressed 5:1:4 by castor oil-base polyhydric alcohol, rice husk polylol and megasse polylol
Mass ratio formulated.
The preparation method of described bio-based TPU film, comprises the following steps:
(1) biopolyol and four (4-hydroxyl-3,5-tert-butyl-phenyl propanoic acid) pentaerythritol ester are added reactor
In, keeping reactor pressure is-0.1MPa, and temperature is 95 DEG C, reacts 1h at this temperature；
(2) by bio-based diisocyanate and 1, after 6-hexanediol is preheated to 52 DEG C respectively, with the product of step (1)
With entrance double screw extruder after catalyst mix homogeneously, the reaction of extrusion limit, limit prepares Polyurethane Thermoplastic Elastomer；
(3) function graphene oxide, modified potassium permanganate solution are carried out with the Polyurethane Thermoplastic Elastomer of step (2)
Mixing, by this mixture through film-forming machine, to extrude or film forming in the way of blown film, obtains described bio-based TPU film.
Wherein, the preparation method of described castor oil-base polyhydric alcohol is:
1) Oleum Ricini, formic acid, phosphoric acid are added in reactor, then hydrogen peroxide is added in this system, anti-at 60 DEG C
8h it is incubated at a temperature of Ying；Then stratification, washes with water, then neutralizes with alkali, after stratification, removes subnatant, evacuation
Dehydration；
2) by step 1) Oleum Ricini that obtains, hydroxylating agent add in reactor, it be incubated under the reaction temperature of 65 DEG C
4h, carries out hydroxylating, prepares castor oil-base biological multielement alcohol；Described phosphoric acid consumption is the 4.5% of Oleum Ricini quality；
Described formic acid consumption is the 60% of Oleum Ricini quality；Described hydrogen peroxide consumption is 3 times of Oleum Ricini quality；
Wherein, the preparation method of described rice husk polylol is:
With concentrated sulphuric acid as catalyst, at 135 DEG C, the powdered rice hulls raw material that particle diameter is 60 mesh is added according to liquid-solid ratio 3:1
Reacting 50min in liquefier, add acetone solution after cooling, addition sodium hydroxide regulation pH is to neutral, and decompression is distilled off
Acetone and water, obtain rice husk polylol；Described liquefier be Polyethylene Glycol with n-octyl alcohol according to mass ratio be 6:1 mix molten
Liquid；
Wherein, the preparation method of described megasse polylol is:
1) megasse is crushed and screened take 60 mesh；
2) liquefaction solvent of the proportions that ethylene glycol and the ethylene carbonate of 135 weight portions are pressed 5:7 adds reactor,
It is subsequently added 12 weight portion steps 1) megasse of pulverizing prepared, microwave heating to 130 DEG C, reacts 50min, after reaction terminates
Cool down with cold water immediately, obtain megasse polylol；
Wherein, described function graphene oxide is adopted and is prepared with the following method:
1) with crystalline flake graphite as raw material, the hummers method improved is utilized to prepare graphene oxide；
2) being added to reaction vessel by DMF, be subsequently adding graphene oxide, ultrasonic 15min obtains the oxidation of homogenization
Graphene suspension；Then isoflurane chalcone diisocyanate is added, under nitrogen protection stirring reaction 26h, finally by product
Wash 3 times with dichloromethane and DMF, obtain function graphene oxide；
Wherein, described modified potassium permanganate solution is adopted and is prepared with the following method:
1) it is that polymethyl hydrogen siloxane, zinc stearate are mixed homogeneously by 3:1:100 with potassium permanganate in mass ratio, 150 DEG C
Lower reaction 40min, obtains modified potassium permanganate；
2) take 0.35g modification potassium permanganate to be dissolved in 30mL N-N dimethylformamide, ultrasonic disperse 20min, changed
Property potassium permanganate solution.
Embodiment 4
A kind of bio-based TPU film, contains following components: bio-based diisocyanate 20 parts, bio-based are many by weight
Unit alcohol 70 parts, 1,4-butanediol 7 parts, 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester 0.5 part, function graphene oxide 0.5
Part and modified potassium permanganate solution 2 parts.
Described biopolyol is pressed 6:2:3 by castor oil-base polyhydric alcohol, rice husk polylol and megasse polylol
Mass ratio formulated.
The preparation method of described bio-based TPU film, comprises the following steps:
(1) by biopolyol and 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester adds in reactor, keeps anti-
Answering still pressure is-0.098MPa, and temperature is 95 DEG C, reacts 1h at this temperature；
(2) after bio-based diisocyanate and BDO being preheated to 50 DEG C respectively, with the product of step (1)
With entrance double screw extruder after catalyst mix homogeneously, the reaction of extrusion limit, limit prepares Polyurethane Thermoplastic Elastomer；
(3) function graphene oxide, modified potassium permanganate solution are carried out with the Polyurethane Thermoplastic Elastomer of step (2)
Mixing, by this mixture through film-forming machine, to extrude or film forming in the way of blown film, obtains described bio-based TPU film.
Wherein, the preparation method of described castor oil-base polyhydric alcohol is:
1) Oleum Ricini, formic acid, phosphoric acid are added in reactor, then hydrogen peroxide is added in this system, anti-at 70 DEG C
9h it is incubated at a temperature of Ying；Then stratification, washes with water, then neutralizes with alkali, after stratification, removes subnatant, evacuation
Dehydration；
2) by step 1) Oleum Ricini that obtains, hydroxylating agent add in reactor, it be incubated under the reaction temperature of 75 DEG C
5h, carries out hydroxylating, prepares castor oil-base biological multielement alcohol；Described phosphoric acid consumption is the 5% of Oleum Ricini quality；Institute
State that formic acid consumption is Oleum Ricini quality 20%；Described hydrogen peroxide consumption is 3 times of Oleum Ricini quality；
Wherein, the preparation method of described rice husk polylol is:
With concentrated sulphuric acid as catalyst, at 190 DEG C, the powdered rice hulls raw material that particle diameter is 60 mesh is added according to liquid-solid ratio 9:1
Reacting 50min in liquefier, add acetone solution after cooling, addition sodium hydroxide regulation pH is to neutral, and decompression is distilled off
Acetone and water, obtain rice husk polylol；Described liquefier be Polyethylene Glycol with n-octyl alcohol according to mass ratio be 8:5 mix molten
Liquid；
Wherein, the preparation method of described megasse polylol is:
1) megasse is crushed and screened take 70 mesh；
2) liquefaction solvent of the proportions that ethylene glycol and the ethylene carbonate of 100 weight portions are pressed 5:3 adds reactor,
It is subsequently added 20 weight portion steps 1) megasse of pulverizing prepared, microwave heating to 130 DEG C, reacts 50min, after reaction terminates
Cool down with cold water immediately, obtain megasse polylol；
Wherein, described function graphene oxide is adopted and is prepared with the following method:
1) with crystalline flake graphite as raw material, the hummers method improved is utilized to prepare graphene oxide；
2) being added to reaction vessel by DMF, be subsequently adding graphene oxide, ultrasonic 10min obtains the oxidation of homogenization
Graphene suspension；Then isoflurane chalcone diisocyanate is added, under nitrogen protection stirring reaction 25h, finally by product
Wash 5 times with dichloromethane and DMF, obtain function graphene oxide；
Wherein, described modified potassium permanganate solution is adopted and is prepared with the following method:
1) it is that polymethyl hydrogen siloxane, zinc stearate are mixed homogeneously by 1:3:100 with potassium permanganate in mass ratio, 130 DEG C
Lower reaction 40min, obtains modified potassium permanganate；
2) take 0.25g modification potassium permanganate to be dissolved in 50mL N-N dimethylformamide, ultrasonic disperse 30min, changed
Property potassium permanganate solution.
Comparative example 1
Compared with Example 1, except only add castor oil-base polyhydric alcohol as biopolyol in addition to, other is with embodiment 1
Identical.
Comparative example 2
Compared with Example 1, except only add rice husk polylol as biopolyol in addition to, other and embodiment 1 phase
With.
Comparative example 3
Compared with Example 1, except only add megasse polylol as biopolyol in addition to, other is with embodiment 1
Identical.
Comparative example 4
Compared with Example 1, in addition to without castor oil-base polyhydric alcohol, other is same as in Example 1.
Comparative example 5
Compared with Example 1, in addition to without rice husk polylol, other is same as in Example 1.
Comparative example 6
Compared with Example 1, in addition to without megasse polylol, other is same as in Example 1.
Comparative example 7
Compared with Example 1, in addition to without function graphene oxide, other is same as in Example 1.
Comparative example 8
Compared with Example 1, in addition to without modified potassium permanganate solution, other is same as in Example 1.
Comparative example 9
Compared with Example 1, in addition to the PTMG using number-average molecular weight to be 2200, other and embodiment
1 is identical.
Comparative example 10
Compared with Example 1, in addition to the polypropylene oxide glycol using number-average molecular weight to be 1500, other and embodiment 1
Identical.
Comparative example 11
Compared with Example 1, in addition to diisocyanate uses toluene di-isocyanate(TDI), other is same as in Example 1.
Comparative example 12
Compared with Example 1, except diisocyanate uses 4, outside 4-'-diphenylmethane diisocyanate, other and embodiment 1
Identical.
By the Polyurethane Thermoplastic Elastomer prepared by above-described embodiment 1-4 and comparative example 1-12, its heat resistance such as table
Shown in 1-2.
Wherein, measure glass transition temperature and use ASTM D-3417-99；The test method measuring fusing point is
ASTM D-3417-99；The test method measuring hardness is ASTM D-2240.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Glass transition temperature/DEG C | -25 | -28 | -26 | -27 | -37 | -36 | -35 |
| Fusing point/DEG C | 178 | 175 | 173 | 175 | 145 | 151 | 155 |
| Hardness (shore A) | 86A | 85A | 83A | 79A | 78A | 75A | 78A |
Table 2
As can be seen from Table 1, the present invention is by using biopolyol and the combination of bio-based diisocyanate and right
Biopolyol is optimized combination and optimizes its proportioning, and it mutually has synergism, so that the biology prepared
Base TPU has the best thermostability and biodegradable, can be widely applied to packaging for foodstuff, medical facilities and medical apparatus and instruments
Or in textile material.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention have to rely on above-mentioned in detail
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the present invention's
Within the scope of protection domain and disclosure.
Claims (9)
1. a bio-based TPU film, it is characterised in that it contains following components by weight:
Bio-based diisocyanate 20-40 part, biopolyol 45-75 part, alkyl chain extender 4-8 part, antioxidant 0.2-1
Part, function graphene oxide 0.2-0.5 part and modified potassium permanganate solution 1-2 part；
Wherein, described biopolyol is pressed 5-9 by castor oil-base polyhydric alcohol, rice husk polylol and megasse polylol:
The mass ratio of 1-5:3-7 is formulated.
2. bio-based TPU film as claimed in claim 1, it is characterised in that it contains following components by weight: bio-based
Diisocyanate 22-38 part, biopolyol 48-72 part, alkyl chain extender 5-8 part, antioxidant 0.2-0.5 part, function
Graphene oxide 0.3-0.5 part and modified potassium permanganate solution 1-1.5 part；
Wherein, described biopolyol is pressed 6-9 by castor oil-base polyhydric alcohol, rice husk polylol and megasse polylol:
The mass ratio of 3-5:3-6 is formulated.
3. bio-based TPU film as claimed in claim 1 or 2, it is characterised in that described alkyl chain extender is Isosorbide-5-Nitrae-fourth two
At least one in alcohol, 1,3-propylene glycol, 1,4-cyclohexanediol, neopentyl glycol, 1,6-HD；
Preferably, described antioxidant is 2,6-di-tert-butyl-4-methy phenol, four (4-hydroxyl-3,5-tert-butyl-phenyl propanoic acid)
At least one in pentaerythritol ester, 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester.
4. the preparation method of the bio-based TPU film as described in one of claim 1-3, it is characterised in that described method includes
Following steps:
(1) biopolyol and antioxidant are added in reactor by a certain percentage, keep reactor pressure be-0.098～-
0.1MPa, temperature is 90-95 DEG C, reacts 1-4h at this temperature；
(2) after bio-based diisocyanate and alkyl diol chain extender being preheated to 50-55 DEG C respectively, with the reaction of step (1)
Entering double screw extruder after product and catalyst mix homogeneously, the reaction of extrusion limit, limit prepares thermoplastic polyurethane elastic
Body；
(3) function graphene oxide, modified potassium permanganate solution are mixed with the Polyurethane Thermoplastic Elastomer of step (2)
Close, by this mixture through film-forming machine, to extrude or film forming in the way of blown film, obtain described bio-based TPU film.
5. method as claimed in claim 4, it is characterised in that the castor oil-base polyhydric alcohol in described biopolyol, adopts
Prepare with the following method:
1) Oleum Ricini, formic acid, phosphoric acid are added in reactor, then hydrogen peroxide is added in this system, the reaction of 55-70 DEG C
At a temperature of be incubated 6-9h；Then stratification, washes with water, then neutralizes with alkali, after stratification, removes subnatant, evacuation
Dehydration；
2) by step 1) Oleum Ricini that obtains, hydroxylating agent add in reactor, is incubated 3-under the reaction temperature of 60-75 DEG C
5h, carries out hydroxylating, prepares castor oil-base biological multielement alcohol；
Preferably, described phosphoric acid consumption is the 3-5% of Oleum Ricini quality；Described formic acid consumption is the 20-60% of Oleum Ricini quality；
Described hydrogen peroxide consumption is 2-3 times of Oleum Ricini quality.
6. the method as described in claim 4 or 5, it is characterised in that the rice husk polylol in described biopolyol, adopts
Prepare with the following method:
With concentrated sulphuric acid as catalyst, at 130-190 DEG C, by powdered rice hulls raw material according to liquid-solid ratio (3-9): 1 joins liquefier
Middle reaction 30-150min, adds acetone solution after cooling, add sodium hydroxide regulation pH and acetone is distilled off to neutrality, decompression
And water, obtain rice husk polylol；Wherein, described powdered rice hulls raw material be vacuum drying particle diameter be the granule of 60-80 mesh；Described liquid
Agent be Polyethylene Glycol be the solution that 6-8:1-5 mixes with n-octyl alcohol according to mass ratio.
7. the method as described in one of claim 4-6, it is characterised in that the megasse Quito unit in described biopolyol
Alcohol, adopts and prepares with the following method:
1) megasse is crushed and screened take 30-70 mesh；
2) liquefaction solvent of the proportions that ethylene glycol and the ethylene carbonate of 100-160 weight portion are pressed 1-5:3-9 adds anti-
Answer device, be subsequently added 10-20 weight portion step 1) megasse of pulverizing prepared, microwave heating, to 130-150 DEG C, reacts 40-
60min, reaction cools down with cold water immediately after terminating, obtains megasse polylol.
8. the method as described in one of claim 4-7, it is characterised in that described function graphene oxide is adopted and made with the following method
For obtaining:
1) with crystalline flake graphite as raw material, the hummers method improved is utilized to prepare graphene oxide；
2) being added to reaction vessel by DMF, be subsequently adding graphene oxide, ultrasonic 10-15min obtains the oxidation stone of homogenization
Ink alkene suspension；Then isoflurane chalcone diisocyanate is added, under nitrogen protection stirring reaction 22-26h, finally by product
Wash 3-5 time with dichloromethane and DMF, obtain function graphene oxide；
Preferably, described modified potassium permanganate solution is adopted and is prepared with the following method:
1) be that polymethyl hydrogen siloxane, zinc stearate are mixed homogeneously by 1-3:1-3:100 with potassium permanganate in mass ratio, 130～
React 20～40min at 150 DEG C, obtain modified potassium permanganate；
2) take 0.15-0.75g modification potassium permanganate to be dissolved in 20-50mL N-N dimethylformamide, ultrasonic disperse 10-30min,
Obtain modified potassium permanganate solution.
9. the bio-based TPU film as described in one of claim 1-3 is in packaging for foodstuff, medical facilities and medical apparatus and instruments or weaving
Application in material.
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Application publication date: 20161221 |