A kind of bio-based polyester polyurethane film and preparation method thereof

Abstract

The invention relates to a bio-based polyester polyurethane film and a preparation method thereof. 5-15 parts of straw powder, 3-5 parts of acid catalyst and 40-75 parts of polyol liquefaction agent are liquefied at 100-150°C for 90~ 130 min, dilute, wash, and filter to remove the organic solvent to obtain straw liquefaction; under nitrogen atmosphere, the polyester monomer, straw liquefaction and catalyst are subjected to ring-opening polymerization at a temperature of 100-140°C to prepare bio-based polyester Diol: react straw liquefied product, isocyanate and catalyst at 60-100°C, add bio-based polyester diol, continue the reaction to obtain a casting solution, lay a film, and cure to obtain a bio-based polyester polyurethane film. The bio-based polyester diol prepared by the present invention is brown at normal temperature, and can be dissolved into a uniform and transparent solution by heating etc., can expand the application range of biomass liquefaction.

Description

technical field

[0001] The invention relates to the field of polymer materials, in particular to a bio-based polyester polyurethane film and a preparation method thereof. Background technique

[0002] The lack of biodegradability of polyether polyol-based polyurethanes (PUs) has prompted researchers to develop PUs using polyester polyols. So far, the commercial polyols used in the synthesis of polyester materials are mainly derived from petrochemical derivatives. Under normal pressure and mild conditions (< 250 °C), the acid-catalyzed liquefaction of crop straw waste is converted into hydroxyl-rich, reactive liquid products. The liquefied product is used as a renewable platform raw material compound instead of petroleum-based chemicals to prepare bio-based polyester diol and bio-based polyester polyurethane, which can alleviate the resource shortage caused by non-renewable petroleum resources and the non-degradable petrochemical-based polymers environmental pollution pr...

Examples

Embodiment 1

[0031] (1) Put 20 g of polyethylene glycol (molecular weight 400) and 5 g of glycerin into a three-necked flask and mix them, place them in an oil bath at 140 °C, add 1.75 g of concentrated sulfuric acid (98%) and 5 g of straw powder ( 50 mesh), stirred and reacted for 120 min. After the reaction, the reaction mixture was diluted with absolute ethanol, washed, filtered through a Buchner funnel to remove the residue, and the filtrate was removed by rotary evaporation (0.5 mbar, 65 ℃, 1 h). water ethanol to obtain straw liquefaction;

[0032] (2) Under a nitrogen atmosphere, take 2 g of straw liquefaction, 18 g ε -caprolactone and 0.4g stannous isooctanoate (40% mixed in a closed reaction flask, stirred and reacted at 120 °C for 8 h, after the reaction was completed, the reaction solution was transferred to 65 °C oven for overnight placement after rotary steaming under reduced pressure, To remove unreacted volatile components to obtain bio-based polycaprolactone polyols;

[0...

Embodiment 2

[0035] (1) Put 20 g of polyethylene glycol (molecular weight 400) and 5 g of glycerin into a three-necked flask and mix them, place them in an oil bath at 140 °C, add 1.75 g of concentrated sulfuric acid (98%) and 5 g of straw powder ( 50 mesh), stirred and reacted for 120 min. After the reaction, the reaction mixture was diluted with absolute ethanol, washed, filtered through a Buchner funnel to remove the residue, and the filtrate was removed by rotary evaporation (0.5 mbar, 65 ℃, 1 h). water ethanol to obtain straw liquefaction;

[0036] (2) Under a nitrogen atmosphere, take 4 g of straw liquefaction, 16 g ε -Caprolactone and 0.4g stannous isooctanoate are mixed in a closed reaction flask, stirred and reacted at 120°C for 8 h, after the reaction, the reaction solution is decompressed and rotary evaporated and then transferred to a 65°C oven for overnight placement to remove Unreacted volatile components to obtain bio-based polycaprolactone polyols;

[0037] (3) Take 2 g ...

Embodiment 3

[0039] (1) Put 20 g of polyethylene glycol (molecular weight 400) and 5 g of glycerin into a three-necked flask and mix them, place them in an oil bath at 140 °C, add 1.75 g of concentrated sulfuric acid (98%) and 5 g of straw powder ( 50 mesh), stirred and reacted for 120 min. After the reaction, the reaction mixture was diluted with absolute ethanol, washed, filtered through a Buchner funnel to remove the residue, and the filtrate was removed by rotary evaporation (0.5 mbar, 65 ℃, 1 h). water ethanol to obtain straw liquefaction;

[0040] (2) Under a nitrogen atmosphere, take 6 g of straw liquefaction, 14 g ε -Caprolactone and 0.4g stannous isooctanoate are mixed in a closed reaction flask, stirred and reacted at 120°C for 8 h, after the reaction, the reaction solution is decompressed and rotary evaporated and then transferred to a 65°C oven for overnight placement to remove Unreacted volatile components to obtain bio-based polycaprolactone polyols;

[0041] (3) Take 2 g of...

technical field

[0001] The invention relates to the field of polymer materials, in particular to a bio-based polyester polyurethane film and a preparation method thereof. Background technique

[0002] The lack of biodegradability of polyether polyol-based polyurethanes (PUs) has prompted researchers to develop PUs using polyester polyols. So far, the commercial polyols used in the synthesis of polyester materials are mainly derived from petrochemical derivatives. Under normal pressure and mild conditions (< 250 °C), the acid-catalyzed liquefaction of crop straw waste is converted into hydroxyl-rich, reactive liquid products. The liquefied product is used as a renewable platform raw material compound instead of petroleum-based chemicals to prepare bio-based polyester diol and bio-based polyester polyurethane, which can alleviate the resource shortage caused by non-renewable petroleum resources and the non-degradable petrochemical-based polymers environmental pollution pr...

Examples

Embodiment 1

[0031] (1) Put 20 g of polyethylene glycol (molecular weight 400) and 5 g of glycerin into a three-necked flask and mix them, place them in an oil bath at 140 °C, add 1.75 g of concentrated sulfuric acid (98%) and 5 g of straw powder ( 50 mesh), stirred and reacted for 120 min. After the reaction, the reaction mixture was diluted with absolute ethanol, washed, filtered through a Buchner funnel to remove the residue, and the filtrate was removed by rotary evaporation (0.5 mbar, 65 ℃, 1 h). water ethanol to obtain straw liquefaction;

[0032] (2) Under a nitrogen atmosphere, take 2 g of straw liquefaction, 18 g ε -caprolactone and 0.4g stannous isooctanoate (40% mixed in a closed reaction flask, stirred and reacted at 120 °C for 8 h, after the reaction was completed, the reaction solution was transferred to 65 °C oven for overnight placement after rotary steaming under reduced pressure, To remove unreacted volatile components to obtain bio-based polycaprolactone polyols;

[0...

Embodiment 2

[0035] (1) Put 20 g of polyethylene glycol (molecular weight 400) and 5 g of glycerin into a three-necked flask and mix them, place them in an oil bath at 140 °C, add 1.75 g of concentrated sulfuric acid (98%) and 5 g of straw powder ( 50 mesh), stirred and reacted for 120 min. After the reaction, the reaction mixture was diluted with absolute ethanol, washed, filtered through a Buchner funnel to remove the residue, and the filtrate was removed by rotary evaporation (0.5 mbar, 65 ℃, 1 h). water ethanol to obtain straw liquefaction;

[0036] (2) Under a nitrogen atmosphere, take 4 g of straw liquefaction, 16 g ε -Caprolactone and 0.4g stannous isooctanoate are mixed in a closed reaction flask, stirred and reacted at 120°C for 8 h, after the reaction, the reaction solution is decompressed and rotary evaporated and then transferred to a 65°C oven for overnight placement to remove Unreacted volatile components to obtain bio-based polycaprolactone polyols;

[0037] (3) Take 2 g ...

Embodiment 3

[0039] (1) Put 20 g of polyethylene glycol (molecular weight 400) and 5 g of glycerin into a three-necked flask and mix them, place them in an oil bath at 140 °C, add 1.75 g of concentrated sulfuric acid (98%) and 5 g of straw powder ( 50 mesh), stirred and reacted for 120 min. After the reaction, the reaction mixture was diluted with absolute ethanol, washed, filtered through a Buchner funnel to remove the residue, and the filtrate was removed by rotary evaporation (0.5 mbar, 65 ℃, 1 h). water ethanol to obtain straw liquefaction;

[0040] (2) Under a nitrogen atmosphere, take 6 g of straw liquefaction, 14 g ε -Caprolactone and 0.4g stannous isooctanoate are mixed in a closed reaction flask, stirred and reacted at 120°C for 8 h, after the reaction, the reaction solution is decompressed and rotary evaporated and then transferred to a 65°C oven for overnight placement to remove Unreacted volatile components to obtain bio-based polycaprolactone polyols;

[0041] (3) Take 2 g of...

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