CN112266475B - Carbon dioxide polyester polyol, full-biodegradable carbon dioxide-based polyurethane and preparation method thereof - Google Patents
Carbon dioxide polyester polyol, full-biodegradable carbon dioxide-based polyurethane and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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Abstract
A carbon dioxide polyester polyol, a full-biodegradable carbon dioxide-based polyurethane and a preparation method thereof. The invention provides a carbon dioxide polyester polyol and a preparation method thereof, wherein the carbon dioxide polyester polyol is prepared from the following raw materials in parts by weight: 800-2300 parts of poly (carbonate-ether) polyol, 3.5-20 parts of dibasic acid (ester) containing sodium sulfonate, 35-52 parts of dicarboxylic acid and 0.12-1.6 parts of catalyst; the dibasic acid (ester) containing sodium sulfonate is one or more selected from isophthalic acid-5-sodium sulfonate, terephthalic acid-2-sodium sulfonate, dioctyl sodium sulfonate succinate, diethyl sodium sulfonate, dimethyl 1, 3-phthalate-5-sodium sulfonate and diisobutyl sodium sulfonate succinate. According to the invention, the poly (carbonate-ether) polyol is modified to prepare the carbon dioxide-based polymer polyol containing sodium sulfonate, so that the ester bond content is increased, and the degradation performance is improved; the introduction of the sulfonate can also improve the biodegradability of the polyurethane material, thereby preparing the fully biodegradable polyurethane material.
Description
Technical Field
The invention belongs to biodegradable polyurethane materials, and particularly relates to carbon dioxide polyester polyol, fully biodegradable carbon dioxide-based polyurethane and a preparation method thereof.
Background
Polyurethane materials are widely applied in the fields of adhesives, coatings, foams and the like, and millions of tons of waste are generated every year, so that the recovery of the polyurethane materials is researched greatly at home and abroad. Among them, the design and synthesis of biodegradable polyurethanes from raw materials for preparing polyurethanes are important means for chemical recovery in this field, and biodegradable polyurethanes have become an important trend in recent years for the development of polyurethane materials.
The polyester polyurethane material becomes an important scheme for preparing biodegradable polyurethane due to the hydrolysis of the soft segment of the polyester polymer, K.Mohammad et al [ J.Polym.Sci.,2006, 44(9): 2990-3000 ] synthesize poly (epsilon-caprolactone) (PCL) based biodegradable polyurethane, and the material guide B, 2014, 28(2):54-57 report polycaprolactone diol based biodegradable polyurethane. In order to improve the biodegradation efficiency, Tian et al [ Chemical precursors and Polymeric Materials, 2013, 11(3):85-88] and patent CN1191289 et al introduce hydrophilic polyethylene glycol into the main chain structure of polyurethane, and improve the hydrophilicity to improve the biodegradation performance of the polyurethane material, however, polyethylene glycol is not biodegradable, and thus, a real biodegradable polyurethane material cannot be obtained at all. CN105482093, CN105482385 and CN102675620 report that carbon dioxide-based polymer has excellent biodegradation performance, and degradation products are completely nontoxic and easy to absorb, but the biodegradation rate is reduced by the hydrophobicity of carbonate and a small amount of ether bond in the structure.
Disclosure of Invention
In view of the above, the present invention aims to provide a carbon dioxide polyester polyol, a fully biodegradable carbon dioxide-based polyurethane and a preparation method thereof, wherein the polyurethane has excellent biodegradability.
The invention provides carbon dioxide polyester polyol which is prepared from the following raw materials in parts by weight:
800-2300 parts by mass of poly (carbonate-ether) polyol, 3.5-20 parts by mass of dibasic acid (ester) containing sodium sulfonate, 35-52 parts by mass of dicarboxylic acid and 0.12-1.6 parts by mass of catalyst;
the dibasic acid (ester) containing sodium sulfonate is one or more selected from isophthalic acid-5-sodium sulfonate, terephthalic acid-2-sodium sulfonate, dioctyl sodium sulfonate succinate, diethyl sodium sulfonate, dimethyl 1, 3-phthalate-5-sodium sulfonate and diisobutyl sodium sulfonate succinate.
Preferably, the poly (carbonate-ether) polyol has a molecular weight of 1000 to 5000g/mol and a carbonate content of 30 to 80 wt%.
Preferably, the dicarboxylic acid is selected from one or more of 1, 3-malonic acid, 1, 4-succinic acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecanedioic acid, and 1, 12-dodecanedioic acid.
Preferably, the catalyst is selected from one or more of p-toluenesulfonic acid, isopropyl titanate, N-butyl titanate, ethylene glycol titanium, antimony trioxide, antimony acetate, ethylene glycol antimony, germanium dioxide, dibutyltin laurate, 1-methyl-2-pyrrolidone p-toluenesulfonate, N-methylimidazole p-toluenesulfonate and 1- (3-sulfonic acid) propyl-3-methylimidazole p-toluenesulfonate.
Preferably, the acid value of the carbon dioxide polyester polyol is less than 0.8mg KOH/g.
The invention provides a preparation method of carbon dioxide polyester polyol, which comprises the following steps:
1) mixing poly (carbonate-ether) polyol, dibasic acid (ester) containing sodium sulfonate and dicarboxylic acid, raising the temperature to 110-160 ℃ under the protection of nitrogen, and preserving the heat for 1-3 hours;
2) heating the reaction product obtained in the step 1) to 180-260 ℃, adding a catalyst, vacuumizing the system to 1.0KPa, and continuously reacting for 2-5 h to obtain the carbon dioxide polyester polyol.
The invention provides full-biodegradable carbon dioxide-based polyurethane which is prepared from the following raw materials:
80-150 parts of carbon dioxide polyester polyol, 25-40 parts of aliphatic diisocyanate, 0.01-0.05 part of catalyst, 0.15-1.1 part of antioxidant and 2.4-6.5 parts of chain extender;
the carbon dioxide polyester polyol is the carbon dioxide polyester polyol in the technical scheme or the carbon dioxide polyester polyol prepared by the preparation method in the technical scheme.
Preferably, the aliphatic diisocyanate is selected from one or more of 1, 6-hexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate;
the catalyst is selected from one or more of stannous octoate, dibutyltin dilaurate, bismuth neodecanoate, bismuth laurate, bismuth isooctanoate and bismuth naphthenate;
the antioxidant is selected from one or more of 2, 6-di-tert-butyl-4-methylphenol, triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine;
the chain extender is one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 7-heptanediol, 1, 8-octanediol and 1, 4-cyclohexanediol.
The invention provides a preparation method of full-biodegradable carbon dioxide-based polyurethane, which comprises the following steps:
a) heating carbon dioxide polyester polyol to 90-120 ℃, decompressing for 1-2 hours, adding aliphatic diisocyanate, and reacting for 1-3 hours;
b) adding a catalyst and an antioxidant into the reaction product obtained in the step a), and continuously reacting for 1-2 hours;
c) heating the reaction product obtained in the step b) to 150-180 ℃, adding a chain extender, and reacting for 2-5 hours to obtain the fully biodegradable carbon dioxide-based polyurethane.
The invention provides carbon dioxide polyester polyol which is prepared from the following raw materials in parts by weight: 800-2300 parts of poly (carbonate-ether) polyol, 3.5-20 parts of dibasic acid (ester) containing sodium sulfonate, 35-52 parts of dicarboxylic acid and 0.12-1.6 parts of catalyst; the dibasic acid (ester) containing sodium sulfonate is one or more selected from isophthalic acid-5-sodium sulfonate, terephthalic acid-2-sodium sulfonate, dioctyl sodium sulfonate succinate, diethyl sodium sulfonate, dimethyl 1, 3-phthalate-5-sodium sulfonate and diisobutyl sodium sulfonate succinate. According to the invention, the poly (carbonate-ether) polyol is modified to prepare the carbon dioxide-based polymer polyol containing sodium sulfonate, so that the ester bond content is increased, and the degradation performance is improved; the introduction of the sulfonate improves the hydrophilicity, so that the biodegradability of the obtained polyurethane material is further improved, and the fully biodegradable polyurethane material is further prepared.
Detailed Description
The invention provides carbon dioxide polyester polyol which is prepared from the following raw materials in parts by weight:
800-2300 parts of poly (carbonate-ether) polyol, 3.5-20 parts of dibasic acid (ester) containing sodium sulfonate, 35-52 parts of dicarboxylic acid and 0.12-1.6 parts of catalyst;
the dibasic acid (ester) containing sodium sulfonate is one or more selected from isophthalic acid-5-sodium sulfonate, terephthalic acid-2-sodium sulfonate, dioctyl sodium sulfonate succinate, diethyl sodium sulfonate, dimethyl 1, 3-phthalate-5-sodium sulfonate and diisobutyl sodium sulfonate succinate.
According to the invention, the poly (carbonate-ether) polyol is modified to prepare the carbon dioxide-based polymer polyol containing sodium sulfonate, so that the ester bond content is increased, and the degradation performance is improved; the introduction of the sulfonate improves the hydrophilicity, so that the biodegradability of the obtained polyurethane material is further improved, and the fully biodegradable polyurethane material is further prepared.
The preparation raw material of the carbon dioxide polyester polyol comprises 800-2300 parts of poly (carbonate-ether) polyol; the poly (carbonate-ether) polyol is not particularly limited in source, and can be prepared by referring to Chinese patent CN107868239A, wherein the molecular weight is 1000-5000 g/mol, and the carbonate content is 30-80 wt%. In a specific embodiment, the poly (carbonate-ether) polyol has a molecular weight of 1000g/mol and a carbonate content of 30 wt%; or a molecular weight of 5000g/mol and a carbonate content of 80 wt%; or a molecular weight of 2000g/mol and a carbonate content of 40 wt.%; or a molecular weight of 3000g/mol, a carbonate content of 50 wt%; or a molecular weight of 3500g/mol and a carbonate content of 60 wt.%.
The raw materials for preparing the carbon dioxide polyester polyol provided by the invention comprise 3.5-20 parts of dibasic acid (ester) containing sodium sulfonate; the dibasic acid (ester) containing sodium sulfonate is one or more selected from isophthalic acid-5-sodium sulfonate, terephthalic acid-2-sodium sulfonate, dioctyl sodium sulfonate succinate, diethyl sodium sulfonate, dimethyl 1, 3-phthalate-5-sodium sulfonate and diisobutyl sodium sulfonate succinate.
The raw materials for preparing the carbon dioxide polyester polyol comprise 35-52 parts of dicarboxylic acid; the dicarboxylic acid is selected from one or more of 1, 3-malonic acid, 1, 4-succinic acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecane dicarboxylic acid and 1, 12-dodecane dicarboxylic acid.
The raw materials for preparing the carbon dioxide polyester polyol comprise 0.12-1.6 parts of catalyst; the catalyst is selected from one or more of p-toluenesulfonic acid, isopropyl titanate, N-butyl titanate, ethylene glycol titanium, antimony trioxide, antimony acetate, ethylene glycol antimony, germanium dioxide, dibutyltin laurate, 1-methyl-2-pyrrolidone p-toluenesulfonate, N-methylimidazole p-toluenesulfonate and 1- (3-sulfonic acid) propyl-3-methylimidazole p-toluenesulfonate.
In the present invention, the acid value of the carbon dioxide polyester polyol is less than 0.8mg KOH/g. In specific examples, the acid value of the carbon dioxide polyester polyol is 0.45mg KOH/g, 0.7mg KOH/g, 0.4mg KOH/g, 0.5mg KOH/g, or 0.3mg KOH/g.
In a specific embodiment, the raw materials for preparing the carbon dioxide polyester polyol comprise:
800 parts of (carbonate-ether) polyol, 3.5 parts of isophthalic acid-5-sodium sulfonate, 35 parts of 1, 4-succinic acid and 0.12 part of p-toluenesulfonic acid;
or comprises 2300 parts of poly (carbonate-ether) polyol, 20 parts of sodium terephthalate-2-sulfonate, 52 parts of 1, 6-adipic acid and 1.6 parts of isopropyl titanate;
or 1100 parts of poly (carbonate-ether) polyol, 6.2 parts of sodium diethylsulfosuccinate, 41 parts of 1, 8-octanedioic acid and 0.14 part of n-butyl titanate;
or 1400 parts of poly (carbonate-ether) polyol, 10.2 parts of 1, 3-dimethyl phthalate-5-sodium sulfonate, 45 parts of 1, 10-sebacic acid and 0.15 part of antimony acetate;
or 2000 parts of poly (carbonate-ether) polyol, 15 parts of dioctyl sodium sulfosuccinate, 48 parts of 1, 3-malonic acid and 0.14 part of N-methylimidazole p-toluenesulfonate.
The invention provides a preparation method of carbon dioxide polyester polyol, which comprises the following steps:
1) adding poly (carbonate-ether) polyol, dibasic acid (ester) containing sodium sulfonate and dicarboxylic acid into a reaction kettle, raising the temperature to 110-160 ℃ under the protection of nitrogen, and preserving the temperature for 1-3 hours;
2) heating the reaction product obtained in the step 1) to 180-260 ℃, adding a catalyst, vacuumizing the system to 1.0KPa, and continuously reacting for 2-5 h to obtain the carbon dioxide polyester polyol.
The preparation method comprises the steps of mixing poly (carbonate-ether) polyol, dibasic acid (ester) containing sodium sulfonate and dicarboxylic acid, raising the temperature to 110-160 ℃ under the protection of nitrogen, and preserving the temperature for 1-3 hours. In specific embodiments, the temperature is raised to 110 ℃, 160 ℃, 120 ℃, 150 ℃ or 135 ℃; the heat preservation time is 3h, 1h, 2h, 1.5h or 2.5 h.
Heating the reaction product obtained in the step 1) to 180-260 ℃, adding a catalyst, vacuumizing the system to 1.0KPa, and continuously reacting for 2-5 h to obtain the carbon dioxide polyester polyol.
In the specific embodiment, the temperature of the reaction product in the step 1) is increased to 240 ℃, 220 ℃,200 ℃, 260 ℃ or 180 ℃; the reaction is continued for 2h, 3h, 5h, 4.5h or 2.5 h.
In the invention, the reaction product obtained in the step 2) is cooled after the acid value is less than 0.8mg KOH/g, so as to obtain the carbon dioxide polyester polyol. Preferably, the mixture is discharged after being cooled to 100 ℃, so as to obtain the carbon dioxide polyester polyol.
The invention provides full-biodegradable carbon dioxide-based polyurethane which is prepared from the following raw materials in parts by weight:
80-150 parts of carbon dioxide polyester polyol, 25-40 parts of aliphatic diisocyanate, 0.01-0.05 part of catalyst, 0.15-1.1 part of antioxidant and 2.4-6.5 parts of chain extender.
The preparation raw materials of the full-biodegradable carbon dioxide-based polyurethane provided by the invention comprise 80-150 parts of carbon dioxide polyester polyol; the carbon dioxide polyester polyol is the carbon dioxide polyester polyol in the technical scheme or the carbon dioxide polyester polyol prepared by the preparation method in the technical scheme. In specific embodiments, the carbon dioxide polyester polyol is used in an amount of 80 parts, 100 parts, 150 parts, 135 parts, 120 parts, or 125 parts.
The preparation raw material of the full-biodegradable carbon dioxide-based polyurethane comprises 25-40 parts of aliphatic diisocyanate; the aliphatic diisocyanate is selected from one or more of 1, 6-hexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate.
The preparation raw material of the full-biodegradable carbon dioxide-based polyurethane comprises 0.01-0.05 part of catalyst; the catalyst is selected from one or more of stannous octoate, dibutyltin dilaurate, bismuth neodecanoate, bismuth laurate, bismuth isooctanoate and bismuth naphthenate; in specific embodiments, the aliphatic diisocyanate is used in an amount of 25 parts, 40 parts, 31 parts, 34 parts, or 37 parts.
The preparation raw materials of the full-biodegradable carbon dioxide-based polyurethane provided by the invention comprise 0.15-1.1 parts of antioxidant; the antioxidant is selected from one or more of 2, 6-di-tert-butyl-4-methylphenol, triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine.
The preparation raw material of the full-biodegradable carbon dioxide-based polyurethane provided by the invention comprises 2.4-6.5 parts of chain extender; the chain extender is one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 7-heptanediol, 1, 8-octanediol and 1, 4-cyclohexanediol.
In a specific embodiment, the fully biodegradable carbon dioxide-based polyurethane comprises 80 parts of carbon dioxide polyester polyol, 25 parts of 1, 6-hexamethylene diisocyanate, 0.01 part of stannous octoate, 0.15 part of 2, 6-di-tert-butyl-4-methylphenol and 2.4 parts of 1, 2-propylene glycol;
or comprises 150 parts of a carbondioxide polyester polyol, 40 parts of isophorone diisocyanate, 0.05 part of dibutyltin dilaurate, and 1.1 part of triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate and 6.5 parts of 1, 4-butanediol;
or comprises 100 parts of carbon dioxide polyester polyol, 31 parts of 1, 6-hexamethylene diisocyanate, 0.03 part of bismuth neodecanoate, 0.22 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 3.2 parts of 1, 4-butanediol;
or comprises 120 parts of carbon dioxide polyester polyol, 34 parts of isophorone diisocyanate, 0.03 part of bismuth laurate, 0.55 part of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 3.5 parts of 1, 8-octanediol;
or 135 parts of carbon dioxide polyester polyol, 34 parts of dicyclohexylmethane diisocyanate, 0.04 part of bismuth isooctanoate, 0.85 part of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 5.4 parts of 1, 4-cyclohexanediol;
or comprises 125 parts of carbon dioxide polyester polyol, 37 parts of isophorone diisocyanate, 0.04 part of dibutyltin dilaurate, 0.85 part of 2, 6-di-tert-butyl-4-methylphenol and 6.1 parts of 1, 4-butanediol.
The fully biodegradable carbon dioxide-based polyurethane prepared by the invention does not additionally contain non-degradable components, can achieve the result of full biodegradation, and belongs to an environment-friendly solution of the fully biodegradable polyurethane.
In a specific embodiment of the invention, the fully biodegradable polyurethane has a number average molecular weight of 58000 and a weight average molecular weight of 81200; or the number average molecular weight of the fully biodegradable polyurethane is 75000 and the weight average molecular weight is 112500; or the number average molecular weight of the fully biodegradable polyurethane is 62000, and the weight average molecular weight is 83700; or the number average molecular weight of the fully biodegradable polyurethane is 72000 and the weight average molecular weight is 92160; or the number average molecular weight of the fully biodegradable polyurethane is 81500, and the weight average molecular weight is 114100; or the fully biodegradable polyurethane has a number average molecular weight of 98000 and a weight average molecular weight of 122500.
The invention provides a preparation method of full-biodegradable carbon dioxide-based polyurethane, which comprises the following steps:
a) heating carbon dioxide polyester polyol to 90-120 ℃, decompressing for 1-2 hours, adding aliphatic diisocyanate, and reacting for 1-3 hours;
b) adding a catalyst and an antioxidant into the reaction product obtained in the step a), and continuously reacting for 1-2 hours;
c) heating the reaction product obtained in the step b) to 150-180 ℃, adding a chain extender, and reacting for 2-5 hours to obtain the fully biodegradable carbon dioxide-based polyurethane.
According to the invention, carbon dioxide polyester polyol is heated to 90-120 ℃, decompressed for 1-2 hours, added with aliphatic diisocyanate and reacted for 1-3 hours. In specific embodiments, the carbon dioxide polyester polyol is heated to 90 ℃, 120 ℃, 95 ℃, 105 ℃, 110 ℃ or 115 ℃; the decompression time is 2h, 1h and 1.5 h; the reaction time is 3h, 1h, 1.5h, 2h or 2.5 h.
Adding a catalyst and an antioxidant into the reaction product obtained in the step a), and continuously reacting for 1-2 hours. In specific examples, the reaction is continued for 2h, 1h or 1.5 h.
Heating the reaction product obtained in the step b) to 150-180 ℃, adding a chain extender, and reacting for 2-5 hours to obtain the fully biodegradable carbon dioxide-based polyurethane. In a specific embodiment, the temperature of the reaction product is raised to 165 ℃, 170 ℃, 160 ℃, 180 ℃ or 150 ℃; the reaction time is 4h, 3h, 3.5h, 2h or 5 h.
In order to further illustrate the present invention, the following examples are provided to describe in detail a carbon dioxide polyester polyol, a fully biodegradable carbon dioxide-based polyurethane and a method for preparing the same, which should not be construed as limiting the scope of the present invention.
Example 1 Synthesis of carbon dioxide polyester polyol
Firstly, adding 800g of poly (carbonate-ether) polyol (with the molecular weight of 1000g/mol and the carbonate content of 30 wt%), 3.5g of sodium m-phthalate-5-sulfonate and 35g of 1, 4-succinic acid into a reaction kettle, raising the temperature to 110 ℃ under the protection of nitrogen, and preserving the temperature for 3 hours;
secondly, heating the reaction kettle to 180 ℃, adding 0.12g of p-toluenesulfonic acid, vacuumizing the system to 1.0KPa, and continuing to react for 5 hours;
and thirdly, when the acid value of the reactant is 0.5mg KOH/g, cooling to 100 ℃, and discharging to obtain the product.
Example 2 Synthesis of carbon dioxide polyester polyol
Firstly, adding 2300g of poly (carbonate-ether) polyol (with the molecular weight of 5000g/mol and the carbonate content of 80 wt%), 20g of sodium terephthalate-2-sulfonate and 52g of 1, 6-adipic acid into a reaction kettle, raising the temperature to 160 ℃ under the protection of nitrogen, and preserving the temperature for 1 h;
secondly, heating the reaction kettle to 260 ℃, adding 1.6g of isopropyl titanate, vacuumizing the system to 1.0KPa, and continuing to react for 2 hours;
and thirdly, when the acid value of the reactant is less than 0.3mg KOH/g, cooling to 100 ℃, and discharging to obtain the product.
Example 3 Synthesis of carbon dioxide polyester polyol
Step one, 1100g of poly (carbonate-ether) polyol (molecular weight 2000g/mol, carbonate content 40 wt%), 6.2g of sodium diethylsulfosuccinate and 41g of 1, 8-octanedioic acid are added into a reaction kettle, the temperature is raised to 120 ℃ under the protection of nitrogen, and the temperature is kept for 2 hours;
secondly, heating the reaction kettle to 200 ℃, adding 0.14g of n-butyl titanate, vacuumizing the system to 1.0KPa, and continuing to react for 3 hours;
and thirdly, when the acid value of the reactant is 0.4mg KOH/g, cooling to 100 ℃, and discharging to obtain the product.
Example 4 Synthesis of carbon dioxide polyester polyol
Firstly, 1400 parts by mass of poly (carbonate-ether) polyol (with the molecular weight of 3000g/mol and the carbonate content of 50 wt%), 10.2g of sodium 1, 3-dimethyl phthalate-5-sulfonate and 45g of 1, 10-sebacic acid are added into a reaction kettle, the temperature is raised to 150 ℃ under the protection of nitrogen, and the temperature is kept for 1.5 hours;
secondly, heating the reaction kettle to 220 ℃, adding 0.15g of antimony acetate, vacuumizing the system to 1.0KPa, and continuing to react for 4.5 hours;
and thirdly, when the acid value of the reactant is 0.7mg KOH/g, cooling to 100 ℃, and discharging to obtain the product.
Example 5 Synthesis of carbon dioxide polyester polyol
Firstly, adding 2000g of poly (carbonate-ether) polyol (molecular weight is 3500g/mol, carbonate content is 60 wt%), 15g of sodium dioctyl sulfosuccinate and 48g of 1, 3-malonic acid into a reaction kettle, raising the temperature to 135 ℃ under the protection of nitrogen, and preserving the heat for 2.5 hours;
secondly, heating the reaction kettle to 240 ℃, adding 0.14g of N-methylimidazole p-toluenesulfonate, vacuumizing the system to 1.0KPa, and continuing to react for 2.5 hours;
and thirdly, when the acid value of the reactant is 0.45mg KOH/g, cooling to 100 ℃, and discharging to obtain the product.
Example 6 preparation of fully biodegradable carbon dioxide based polyurethane
Step one, 80g of carbon dioxide polyester polyol (prepared in example 1) is weighed and put into a reaction kettle, heated to 90 ℃, decompressed for 2 hours, added with 25g of 1, 6-hexamethylene diisocyanate and reacted for 3 hours.
And step two, adding 0.01g of stannous octoate and 0.15g of 2, 6-di-tert-butyl-4-methylphenol into the reaction kettle, and continuing to react for 2 hours.
And step three, raising the temperature of the reaction kettle to 150 ℃, adding 2.4g of 1, 2-propylene glycol, reacting for 5 hours, and discharging to obtain the fully biodegradable polyurethane with the number average molecular weight of 58000 and the weight average molecular weight of 81200.
Example 7 preparation of fully biodegradable carbon dioxide based polyurethane
Step one, 150g of carbon dioxide polyester polyol (the product prepared in example 2) is weighed and put into a reaction kettle, heated to 120 ℃, decompressed for 1 hour, added with 40g of isophorone diisocyanate and reacted for 1 hour.
Step two, 0.05g of dibutyltin dilaurate and 1.1g of triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate were added into the reaction kettle, and the reaction was continued for 1 hour.
And step three, raising the temperature of the reaction kettle to 180 ℃, adding 6.5g of 1, 4-butanediol, reacting for 2 hours, and discharging to obtain the fully biodegradable polyurethane with the number average molecular weight of 75000 and the weight average molecular weight of 112500.
Example 8 preparation of fully biodegradable carbon dioxide-based polyurethane
Step one, 100g of carbon dioxide polyester polyol (prepared in example 3) is weighed and placed into a reaction kettle, heated to 95 ℃, decompressed for 1.5 hours, added with 31g of 1, 6-hexamethylene diisocyanate, and reacted for 1.5 hours.
And step two, adding 0.03g of bismuth neodecanoate and 0.22g of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] into the reaction kettle, and continuing to react for 1.5 hours.
And step three, raising the temperature of the reaction kettle to 160 ℃, adding 3.2g of 1, 4-butanediol, reacting for 3 hours, and discharging to obtain the fully biodegradable polyurethane, wherein the number average molecular weight is 62000, and the weight average molecular weight is 83700.
Example 9 preparation of fully biodegradable carbon dioxide-based polyurethane
Step one, 120g of carbon dioxide polyester polyol (the product prepared in example 4) is weighed and put into a reaction kettle, heated to 105 ℃, decompressed for 1 hour, added with 34g of isophorone diisocyanate and reacted for 2 hours.
And step two, adding 0.03g of bismuth laurate and 0.55g of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate into the reaction kettle, and continuing to react for 1.5 hours.
And step three, raising the temperature of the reaction kettle to 170 ℃, adding 3.5g of 1, 8-octanediol, reacting for 3.5 hours, and discharging to obtain the fully biodegradable polyurethane with the number average molecular weight of 72000 and the weight average molecular weight of 92160.
Example 10 preparation of fully biodegradable carbon dioxide-based polyurethane
Step one, 135g of carbon dioxide polyester polyol (prepared in example 5) is weighed and put into a reaction kettle, heated to 110 ℃, decompressed for 2 hours, added with 34g of dicyclohexylmethane diisocyanate and reacted for 1.5 hours.
Step two, 0.04g of bismuth isooctanoate and 0.85g of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine were added to the reaction vessel, and the reaction was continued for 1.5 hours.
And step three, raising the temperature of the reaction kettle to 165 ℃, adding 5.4g of 1, 4-cyclohexanediol, reacting for 3 hours, and discharging to obtain the fully biodegradable polyurethane, wherein the number average molecular weight is 81500, and the weight average molecular weight is 114100.
Example 11 preparation of fully biodegradable carbon dioxide-based polyurethane
Step one, 125g of carbon dioxide polyester polyol (the product prepared in example 4) is weighed and put into a reaction kettle, heated to 115 ℃, decompressed for 1.5 hours, added with 37g of isophorone diisocyanate and reacted for 2.5 hours.
Step two, 0.04g of dibutyltin dilaurate and 0.85g of 2, 6-di-tert-butyl-4-methylphenol are added into the reaction kettle, and the reaction is continued for 1.5 hours.
And step three, raising the temperature of the reaction kettle to 165 ℃, adding 6.1g of 1, 4-butanediol, reacting for 4 hours, and discharging to obtain the fully biodegradable polyurethane with the number average molecular weight of 98000 and the weight average molecular weight of 122500.
Comparative example 1 preparation of biodegradable carbon dioxide-based polyurethane
Prepared according to the method of example 6, except that the carbon dioxide polyester polyol (product of example 1) was replaced with a poly (carbonate-ether) polyol (molecular weight 1000g/mol, carbonate content 30 wt%), number average molecular weight 53500, and weight average molecular weight 93620.
Comparative example 2 preparation of biodegradable carbon dioxide-based polyurethane
Prepared according to the method of example 7, except that the carbon dioxide polyester polyol (product of example 2) was replaced with a poly (carbonate-ether) polyol (molecular weight 5000g/mol, carbonate content 80 wt%), number average molecular weight 68200, and weight average molecular weight 117300.
Biodegradation test: the test is in accordance with GB/T19277.1-2011. The final aerobic biological decomposition and disintegration ability of biodegradable polyurethane elastomers under controlled composting conditions was investigated. In a 2L test system, the test mixture was aerated at a controlled rate with carbon dioxide free air using polyurethane elastomer as the organic carbon source. The degradation rate was determined by measuring the amount of carbon dioxide produced. 240g of culture soil was mixed with 40g of polyurethane according to the present invention (prepared as a 10 μm polyurethane film) and 40g of microcrystalline cellulose, and 240g of culture soil was used as a blank control, and distilled water was added to adjust the humidity of the mixture to about 50%. Placing the compost container in a test environment at (58 +/-2) DEG C and using CO-free2The test system was aerated at a flow rate of 0.05L/min with saturated air at a temperature of (58. + -. 2) ℃ and the test was carried out. The biodegradation rate of the test material was determined as the ratio of the amount of carbon dioxide actually produced by the test material during the test to the theoretical amount of carbon dioxide released from the test material.
TABLE 1 examples and comparative test results
From the above examples, the present invention provides a carbon dioxide polyester polyol, which is prepared from the following raw materials in parts by weight: 800-2300 parts of poly (carbonate-ether) polyol, 3.5-20 parts of dibasic acid (ester) containing sodium sulfonate, 35-52 parts of dicarboxylic acid and 0.12-1.6 parts of catalyst; the dibasic acid (ester) containing sodium sulfonate is one or more selected from isophthalic acid-5-sodium sulfonate, terephthalic acid-2-sodium sulfonate, dioctyl sodium sulfonate succinate, diethyl sodium sulfonate, dimethyl 1, 3-phthalate-5-sodium sulfonate and diisobutyl sodium sulfonate succinate. According to the invention, the poly (carbonate-ether) polyol is modified to prepare the carbon dioxide-based polymer polyol containing sodium sulfonate, so that the ester bond content is increased, and the degradation performance is improved; the introduction of the sulfonate improves the hydrophilicity, so that the biodegradability of the obtained polyurethane material is further improved, and the fully biodegradable polyurethane material is further prepared. The experimental results show that: the number average molecular weight of the carbon dioxide-based polyurethane reaches 7.8-9.6 ten thousand, the weight average molecular weight reaches 10.1-13.8 ten thousand, the tensile strength is 16-28 MPa, and the elongation at break is 880-1220%. The result of the composting test shows that: the hydrophilic modified polyurethane elastomer material begins to disintegrate within 20 days; after 90 days, the degradation rate exceeds 85 percent; after 180 days, the degradation rate reaches 96 percent. And without hydrophilic groups, disintegration began only 90 days; after 180 days, the highest degradation rate reaches 17 percent; the highest degradation rate of the product reaches 69 percent in 360 days.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. The full-biodegradable carbon dioxide-based polyurethane is prepared from the following raw materials in parts by weight:
80-150 parts of carbon dioxide polyester polyol, 25-40 parts of aliphatic diisocyanate, 0.01-0.05 part of catalyst, 0.15-1.1 part of antioxidant and 2.4-6.5 parts of chain extender;
the carbon dioxide polyester polyol is prepared from the following raw materials in parts by weight:
800-2300 parts of poly (carbonate-ether) polyol, 3.5-20 parts of dibasic acid containing sodium sulfonate or ester thereof, 35-52 parts of dicarboxylic acid and 0.12-1.6 parts of catalyst;
the molecular weight of the poly (carbonate-ether) polyol is 1000-5000 g/mol, and the carbonate content is 30-80 wt%;
the dibasic acid or the ester thereof containing sodium sulfonate is selected from one or more of 5-sodium sulfoisophthalate, 2-sodium sulfoterephthalate, dioctyl sodium sulfosuccinate, diethyl sodium sulfosuccinate, 1, 3-dimethyl phthalate-5-sodium sulfosuccinate and diisobutyl sodium sulfosuccinate;
the dicarboxylic acid in the raw materials of the carbon dioxide polyester polyol is selected from one or more of 1, 3-malonic acid, 1, 4-succinic acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecane dicarboxylic acid and 1, 12-dodecane dicarboxylic acid;
the catalyst in the raw materials of the carbon dioxide polyester polyol is selected from one or more of p-toluenesulfonic acid, isopropyl titanate, N-butyl titanate, ethylene glycol titanium, antimony trioxide, antimony acetate, ethylene glycol antimony, germanium dioxide, dibutyltin laurate, 1-methyl-2-pyrrolidone p-toluenesulfonate, N-methylimidazole p-toluenesulfonate and 1- (3-sulfonic acid) propyl-3-methylimidazole p-toluenesulfonate.
2. The fully biodegradable carbon dioxide-based polyurethane according to claim 1, wherein the carbon dioxide polyester polyol has an acid value of less than 0.8mg KOH/g.
3. The fully biodegradable carbon dioxide-based polyurethane according to any one of claims 1-2, wherein the preparation method of the carbon dioxide polyester polyol comprises the following steps:
1) mixing poly (carbonate-ether) polyol, dibasic acid containing sodium sulfonate or ester thereof and dicarboxylic acid, raising the temperature to 110-160 ℃ under the protection of nitrogen, and preserving the heat for 1-3 hours;
2) heating the reaction product obtained in the step 1) to 180-260 ℃, adding a catalyst, vacuumizing the system to 1.0KPa, and continuously reacting for 2-5 h to obtain the carbon dioxide polyester polyol.
4. The fully biodegradable carbon dioxide based polyurethane according to claim 1, wherein the aliphatic diisocyanate is selected from one or more of 1, 6-hexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate;
the catalyst is selected from one or more of stannous octoate, dibutyltin dilaurate, bismuth neodecanoate, bismuth laurate, bismuth isooctanoate and bismuth naphthenate;
the antioxidant is selected from one or more of 2, 6-di-tert-butyl-4-methylphenol, triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine;
the chain extender is one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 7-heptanediol, 1, 8-octanediol and 1, 4-cyclohexanediol.
5. A method for preparing the fully biodegradable carbon dioxide-based polyurethane according to any one of claims 1 to 4, comprising the following steps:
a) heating carbon dioxide polyester polyol to 90-120 ℃, decompressing for 1-2 hours, adding aliphatic diisocyanate, and reacting for 1-3 hours;
b) adding a catalyst and an antioxidant into the reaction product obtained in the step a), and continuously reacting for 1-2 hours;
c) heating the reaction product obtained in the step b) to 150-180 ℃, adding a chain extender, and reacting for 2-5 hours to obtain the fully biodegradable carbon dioxide-based polyurethane.
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