CN112266456A - Biodegradable carbon dioxide-based polyurethane elastomer and preparation method thereof - Google Patents
Biodegradable carbon dioxide-based polyurethane elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a biodegradable carbon dioxide-based polyurethane elastomer and a preparation method thereof, wherein the biodegradable carbon dioxide-based polyurethane elastomer is prepared from the following raw materials: 60-110 parts of carbon dioxide-based polyol, 22-35 parts of aliphatic diisocyanate, 0.002-0.01 part of catalyst, 0.1-0.8 part of antioxidant, 0.2-0.8 part of sulfonate-containing dihydroxy compound and 3.5-18 parts of chain extender. The invention greatly improves the hydrophilicity of the polyurethane elastomer material by introducing the sulfonate of the strong hydrophilic group, enhances the hydrolyzability of the polyurethane elastomer material and greatly improves the biodegradability. The polyurethane elastomer has a number average molecular weight of 5.8-8.2 ten thousand, a weight average molecular weight of 7.6-11.5 ten thousand, a tensile strength of 14-25 MPa, and an elongation at break of 650-820%. The composting test shows that: the polyurethane elastomer material begins to disintegrate in 30 days; after 90 days, the degradation rate exceeds 70 percent; after 180 days, the degradation rate reaches 92 percent.
Description
Technical Field
The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a biodegradable carbon dioxide-based polyurethane elastomer and a preparation method thereof.
Background
Polyurethane is a bulk material which is produced by thousands of tons every year in China, has many advantages such as high strength, tear resistance, abrasion resistance and the like, is developed rapidly since development and research of Otto Bayer and the like in I.G. Farbe laboratories in 1937, and becomes a high polymer material with excellent performance and wide application. With the wider application field and larger consumption of the material, a large amount of polyurethane waste is generated to the environment. The harmless treatment of the wastes is always an important direction in the research field of polyurethane, and the burying, burning and recovery by various physical or chemical means are the treatment methods which are currently applied or researched more. However, these methods cannot really solve the ecological treatment of polyurethane from the source, and nowadays, the methods focus on environmental protection, energy saving and low consumption, and the biochemical technology of degrading, converting or digesting and absorbing polyurethane by using the metabolic process of microorganisms and using the polyurethane as a carbon source is more and more focused on.
Biodegradable poly (. epsilon. -caprolactone), polycaprolactone and polyester polyols have been extensively studied as important raw materials for the preparation of polyurethanes in the soft segment. K. Mohammad et al [ J.Polym.Sci.,2006, 44(9):2990-3000] synthesizes biodegradable aliphatic thermoplastic polyurethane by using poly (epsilon-caprolactone) (PCL) diol as a soft segment. The material guide B, 2014, 28(2):54-57 of the patent application et al uses lysine diisocyanate and polycaprolactone diol as raw materials to synthesize the medical degradable polyurethane by a bulk polymerization method. As is well known, the core of the biodegradation process of polyurethane is a hydrolysis process of urethane bonds, i.e., a biological enzymolysis process, esterase secreted by microorganisms attacks the urethane bonds first to cause hydrolytic cleavage of the urethane bonds, and simultaneously hydrolyzes the urethane bonds to destroy the high polymer chains of the polyurethane material to generate low molecular weight compounds, and then the urethane segments are further cleaved to finally complete the biodegradation process. The surface hydrophilicity of the material is important, and the reported materials have certain biodegradability, however, the hydrophilicity is poor, so that the final biodegradation performance is not ideal. In order to improve hydrophilicity, polyethylene glycol (PEG) having a hydrophilic group is introduced into a polyurethane synthesis process, and has also been studied in a large amount. Tian et al (chemical precursors and Polymeric Materials, 2013, 11(3): 85-88) prepared various contents of PEG-based biodegradable polyurethane using PEG as an initiator found that the mechanical properties of polyurethane are decreased as the content of PEG is increased, while the hydrophilic properties and degradation rate are increased. CN1191289 reports a synthesis method of biodegradable polyurethane elastomer, which takes PEG and polycaprolactone as soft segments and 2, 6-hexamethylene diisocyanate as raw materials to prepare the polyurethane elastomer. Li xing et al (science and engineering of high molecular materials, 2017, 33 (8): 17-26) PEG as an initiator and stannous octoate as a catalyst, and the L-lactide is subjected to ring-opening polymerization to prepare a polylactide-polyethylene glycol-polylactide triblock prepolymer, and then the polylactide-polyethylene glycol-polylactide triblock prepolymer is subjected to prepolymerization with 2, 6-hexamethylene diisocyanate, and chain extension with butanediol to prepare the biodegradable polyurethane. PEG is introduced into a polyurethane main chain structure, although the hydrophilicity of the material is increased, the group of the ether structure of polyethylene glycol cannot be degraded at all, the hydrophilicity of the PEG is hydrophilic through an ethoxy group, and for a high polymer material of a polyurethane elastomer, the higher the content of the PEG is, the poorer the degradation performance is.
Disclosure of Invention
In view of the above, the present invention aims to provide a biodegradable carbon dioxide-based polyurethane elastomer and a preparation method thereof, wherein the polyurethane elastomer has excellent biodegradability.
The invention provides a biodegradable carbon dioxide-based polyurethane elastomer which is prepared from the following raw materials in parts by weight:
60-110 parts of carbon dioxide-based polyol, 22-35 parts of aliphatic diisocyanate, 0.002-0.01 part of catalyst, 0.1-0.8 part of antioxidant, 0.2-0.8 part of sulfonate-containing dihydroxy compound and 3.5-18 parts of chain extender.
Preferably, the sulfonate-containing dihydroxy compound is selected from one or more of sodium N, N- (2-hydroxyethyl) -2-aminoethanesulfonate, sodium 2, 5-dihydroxybenzenesulfonate, sodium 2, 3-dihydroxynaphthalene-6-sulfonate, sodium 1, 4-dihydroxy-2-butanesulfonate, sodium 2, 8-dihydroxynaphthalene-6-sulfonate, sodium 2-dihydroxy-3-monopropanesulfonate, and sodium 1, 4-dihydroxybutane-2-sulfonate.
Preferably, the molecular weight of the carbon dioxide-based polyol is 1000-30000 g/mol; the content of the carbonic ester chain segment is 30-80 wt%.
Preferably, the aliphatic diisocyanate is selected from one or more of 1, 6-hexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate.
Preferably, the antioxidant is selected from one or more of IRGANOX1010, IRGANOX1076, IRGANOX1035, IRGANOX245, IRGANOX1098, IRGANOX1135, and IRGANOX 1520;
the chain extender is selected from one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 7-heptanediol, 1, 8-octanediol and 1, 4-cyclohexanediol;
the catalyst is selected from one or more of stannous octoate, dibutyltin dilaurate, bismuth neodecanoate, bismuth laurate, bismuth isooctanoate or bismuth naphthenate.
Preferably, the biodegradable carbon dioxide-based polyurethane elastomer comprises the following components:
60 parts of carbon dioxide-based polyol, 22 parts of 1, 6-hexamethylene diisocyanate, 0.002 part of stannous octoate, 0.1 part of IRGANOX1010, 0.2 part of N, N- (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 3.5 parts of 1, 4-butanediol;
or 110 parts of carbon dioxide-based polyol, 35 parts of methylcyclohexyl diisocyanate, 0.01 part of dibutyltin dilaurate, 0.8 part of IRGANOX1076, 0.8 part of sodium 1, 4-dihydroxy-2-butanesulfonate and 18 parts of 1, 2-butanediol;
or comprises 80 parts of carbon dioxide-based polyol, 28 parts of dicyclohexylmethane diisocyanate, 0.006 part of bismuth neodecanoate, 0.3 part of IRGANOX1035, 0.4 part of 2, 3-dihydroxy naphthalene-6-sodium sulfonate and 5.2 parts of 1, 7-heptanediol;
or comprises 100 parts of carbon dioxide-based polyol, 30 parts of isophorone diisocyanate, 0.005 part of bismuth laurate, 0.6 part of IRGANOX245, 0.3 part of 2, 8-dihydroxy naphthalene-6-sodium sulfonate and 7.2 parts of 1, 8-octanediol;
or 105 parts of carbon dioxide-based polyol, 29.5 parts of 1, 6-hexamethylene diisocyanate, 0.007 part of bismuth isooctanoate, 0.65 part of IRGANOX1098, 0.55 part of sodium 1, 4-dihydroxybutane-2-sulfonate and 10.5 parts of 1, 4-cyclohexanediol;
or comprises 75 parts of carbon dioxide-based polyol, 28 parts of isophorone diisocyanate, 0.008 part of bismuth naphthenate, 0.45 part of IRGANOX1520, 0.6 part of 1, 4-dihydroxy butane-2-sodium sulfonate and 12.5 parts of 1, 4-butanediol.
The invention provides a preparation method of a biodegradable carbon dioxide-based polyurethane elastomer, which comprises the following steps:
1) heating the carbon dioxide-based polyol to 85-105 ℃, decompressing for 1-2 hours, adding aliphatic diisocyanate, and reacting for 1-3 hours;
2) adding a catalyst, an antioxidant and a dihydroxy compound containing sulfonate into the reaction product obtained in the step 1) and continuously reacting for 0.5-1.5 hours;
3) heating the reaction product obtained in the step 2) to 120-150 ℃, adding a chain extender, and reacting for 1-3 hours to obtain the biodegradable carbon dioxide-based polyurethane elastomer.
The invention provides a biodegradable carbon dioxide-based polyurethane elastomer which is prepared from the following raw materials in parts by weight: 60-110 parts of carbon dioxide-based polyol, 22-35 parts of aliphatic diisocyanate, 0.002-0.01 part of catalyst, 0.1-0.8 part of antioxidant, 0.2-0.8 part of sulfonate-containing dihydroxy compound and 3.5-18 parts of chain extender. The invention greatly improves the hydrophilicity of the polyurethane elastomer material by introducing the sulfonate of the strong hydrophilic group, enhances the hydrolyzability of the obtained elastomer material and greatly improves the biodegradation performance. The experimental results show that: the number average molecular weight of the polyurethane elastomer reaches 5.8-8.2 ten thousand, the weight average molecular weight reaches 7.6-11.5 ten thousand, the tensile strength is 14-25 MPa, and the elongation at break is 650-820%. The result of the composting test shows that: the hydrophilic modified polyurethane elastomer material begins to disintegrate within 30 days; after 90 days, the degradation rate exceeds 70 percent; after 180 days, the degradation rate reaches 92 percent. And without hydrophilic groups, disintegration began only 90 days; after 180 days, the highest degradation rate reaches 18 percent; the highest degradation rate of the product reaches 67 percent in 360 days.
Detailed Description
The invention provides a biodegradable carbon dioxide-based polyurethane elastomer which is prepared from the following raw materials in parts by weight:
60-110 parts of carbon dioxide-based polyol, 22-35 parts of aliphatic diisocyanate, 0.002-0.01 part of catalyst, 0.1-0.8 part of antioxidant, 0.2-0.8 part of sulfonate-containing dihydroxy compound and 3.5-18 parts of chain extender.
Compared with the prior art, the biodegradable carbon dioxide-based polyurethane elastomer provided by the invention has the following beneficial effects: 1. according to the invention, the sulfonate with a strong hydrophilic group is introduced, so that the hydrophilicity of the polyurethane elastomer material is greatly improved, the hydrolyzability of the obtained elastomer material is enhanced, the biodegradation performance is greatly improved, and the fully biodegradable polyurethane elastomer is obtained. 2. Although the structure of the carbon dioxide-based polyol contains a small amount of ether groups which are difficult to degrade, because the adjacent carbonate bonds can form hydrogen bond action between the ether bonds, the dissociation of the ether bonds is greatly promoted along with the degradation of the carbonate bonds, and the aim of biodegradation is fulfilled. 3. The content of introduced sulfonate groups is very low, and the sulfonate groups do not influence soil and environment after being ionized in soil, so that the method belongs to an environment-friendly solution for biodegradable polyurethane elastomers.
The biodegradable carbon dioxide-based polyurethane elastomer provided by the invention comprises 60-110 parts of carbon dioxide-based polyol; in specific examples, the carbon dioxide based polyol is used in an amount of 60 parts, 75 parts, 80 parts, 100 parts, 105 parts, or 110 parts. The molecular weight of the carbon dioxide-based polyol is 1000-30000 g/mol; the content of the carbonic ester chain segment is 30-80 wt%; in specific embodiments, the molecular weight of the carbon dioxide-based polyol is 1000g/mol, and the content of the carbonate segment is 30 wt%; or a molecular weight of 30000g/mol and a carbonate segment content of 80 wt%; or a molecular weight of 2000g/mol and a carbonate segment content of 40 wt%; or the molecular weight is 3000g/mol, and the content of the carbonic ester chain segment is 35 wt%; or a molecular weight of 2200g/mol and a carbonate segment content of 60 wt%; or a molecular weight of 5000g/mol and a carbonate segment content of 65% by weight.
The biodegradable carbon dioxide-based polyurethane elastomer provided by the invention comprises 22-35 parts of aliphatic diisocyanate; in specific embodiments, the aliphatic diisocyanate is used in an amount of 22 parts, 25 parts, 28 parts, 29.5 parts, 30 parts, or 35 parts. The aliphatic diisocyanate is selected from one or more of 1, 6-hexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate.
The biodegradable carbon dioxide-based polyurethane elastomer provided by the invention comprises 0.002-0.01 part of catalyst; in specific examples, the catalyst is used in an amount of 0.002 parts, 0.005 parts, 0.006 parts, 0.007 parts, 0.008 parts, or 0.01 parts. The catalyst is selected from one or more of stannous octoate, dibutyltin dilaurate, bismuth neodecanoate, bismuth laurate, bismuth isooctanoate or bismuth naphthenate.
The biodegradable carbon dioxide-based polyurethane elastomer provided by the invention comprises 0.1-0.8 part of antioxidant; in specific embodiments, the antioxidant is used in an amount of 0.45 parts, 0.65 parts, 0.6 parts, 0.3 parts, 0.8 parts or 0.1 parts. The antioxidant is selected from one or more of IRGANOX1010, IRGANOX1076, IRGANOX1035, IRGANOX245, IRGANOX1098, IRGANOX1135, and IRGANOX 1520.
The biodegradable carbon dioxide-based polyurethane elastomer provided by the invention comprises 0.2-0.8 part of dihydroxy compound containing sulfonate; in specific examples, the sulfonate-containing dihydroxy compound is used in an amount of 0.2 parts, 0.3 parts, 0.4 parts, 0.55 parts, 0.6 parts, or 0.8 parts. The sulfonate-containing dihydroxy compound is selected from one or more of N, N- (2-hydroxyethyl) -2-aminoethyl sulfonate, 2, 5-dihydroxy benzene sodium sulfonate, 2, 3-dihydroxy naphthalene-6-sodium sulfonate, 1, 4-dihydroxy-2-butane sodium sulfonate, 2, 8-dihydroxy naphthalene-6-sodium sulfonate, 2-dihydroxy-3-propane sodium sulfonate and 1, 4-dihydroxy butane-2-sodium sulfonate. The invention introduces a dihydroxy component containing sulfonate of a strong hydrophilic group into the main chain structure of the biodegradable carbon dioxide-based polyurethane elastomer, the component plays a role of a chain extender in synthesizing the polyurethane elastomer, the use amount of the component can effectively regulate and control the performance of the elastomer material, simultaneously the hydrophilicity of the polyurethane elastomer is greatly improved, the hydrolyzability of the material is improved, and the biodegradable polyurethane elastomer material is obtained. In the present invention, the sodium 1, 4-dihydroxybutane-2-sulfonate is prepared according to the general methods of yellow book et al, "chinese adhesives, 2012, 21 (7): 16-18' of the above-mentioned base; sodium 2-dihydroxy-3-propanesulfonate according to "zingiber et al, polyurethane industry, 2012, 27 (4): 39-42' of the above-mentioned base; sodium 1, 4-dihydroxybutane-2-sulfonate according to yellow book et al, "chinese adhesives, 2012, 21 (7): 16-18 "by the method described in the above paragraph.
The biodegradable carbon dioxide-based polyurethane elastomer provided by the invention comprises 3.5-18 parts of chain extender. The chain extender is selected from one or more of 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 of the present invention, the biodegradable carbon dioxide-based polyurethane elastomer comprises the following components:
60 parts of carbon dioxide-based polyol, 22 parts of 1, 6-hexamethylene diisocyanate, 0.002 part of stannous octoate, 0.1 part of IRGANOX1010, 0.2 part of N, N- (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 3.5 parts of 1, 4-butanediol;
or 110 parts of carbon dioxide-based polyol, 35 parts of methylcyclohexyl diisocyanate, 0.01 part of dibutyltin dilaurate, 0.8 part of IRGANOX1076, 0.8 part of sodium 1, 4-dihydroxy-2-butanesulfonate and 18 parts of 1, 2-butanediol;
or comprises 80 parts of carbon dioxide-based polyol, 28 parts of dicyclohexylmethane diisocyanate, 0.006 part of bismuth neodecanoate, 0.3 part of IRGANOX1035, 0.4 part of 2, 3-dihydroxy naphthalene-6-sodium sulfonate and 5.2 parts of 1, 7-heptanediol;
or comprises 100 parts of carbon dioxide-based polyol, 30 parts of isophorone diisocyanate, 0.005 part of bismuth laurate, 0.6 part of IRGANOX245, 0.3 part of 2, 8-dihydroxy naphthalene-6-sodium sulfonate and 7.2 parts of 1, 8-octanediol;
or 105 parts of carbon dioxide-based polyol, 29.5 parts of 1, 6-hexamethylene diisocyanate, 0.007 part of bismuth isooctanoate, 0.65 part of IRGANOX1098, 0.55 part of sodium 1, 4-dihydroxybutane-2-sulfonate and 10.5 parts of 1, 4-cyclohexanediol;
or comprises 75 parts of carbon dioxide-based polyol, 28 parts of isophorone diisocyanate, 0.008 part of bismuth naphthenate, 0.45 part of IRGANOX1520, 0.6 part of 1, 4-dihydroxy butane-2-sodium sulfonate and 12.5 parts of 1, 4-butanediol.
The invention provides a preparation method of a biodegradable carbon dioxide-based polyurethane elastomer, which comprises the following steps:
1) heating the carbon dioxide-based polyol to 85-105 ℃, decompressing for 1-2 hours, adding aliphatic diisocyanate, and reacting for 1-3 hours;
2) adding a catalyst, an antioxidant and a dihydroxy compound containing sulfonate into the reaction product obtained in the step 1) and continuously reacting for 0.5-1.5 hours;
3) heating the reaction product obtained in the step 2) to 120-150 ℃, adding a chain extender, and reacting for 1-3 hours to obtain the biodegradable carbon dioxide-based polyurethane elastomer.
According to the invention, the carbon dioxide-based polyol is heated to 85-105 ℃, the pressure is reduced for 1-2 h, and the aliphatic diisocyanate is added to react for 1-3 h. In specific embodiments, the heating temperature is 85 ℃, 105 ℃, 90 ℃, 92 ℃, 95 ℃ or 100 ℃; the decompression time is 2h, 1h or 1.5 h; the reaction time is specifically 1h, 1.5h, 2h, 2.5h or 3 h.
Adding a catalyst, an antioxidant and a dihydroxy compound containing sulfonate into the reaction product obtained in the step 1) and continuously reacting for 0.5-1.5 hours. In specific embodiments, the specific reaction time is 0.1h, 1h, or 2 h.
Heating the reaction product obtained in the step 2) to 120-150 ℃, adding a chain extender, and reacting for 1-3 hours to obtain the biodegradable carbon dioxide-based polyurethane elastomer. In the present invention, the reaction product obtained in step 2) is heated to 120 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃. The reaction time after adding the chain extender is specifically 1h, 2h, 2.5h or 3 h.
In order to further illustrate the present invention, the following examples are provided to describe a biodegradable carbon dioxide-based polyurethane elastomer and a preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention.
Example 1 preparation of biodegradable carbon dioxide-based polyurethane elastomer
Step one, 60g of carbon dioxide-based polyol (molecular weight is 1000g/mol, and the content of a carbonic ester chain segment is 30 wt%) is weighed and put into a reaction kettle, the temperature is heated to 85 ℃, the pressure is reduced for 2 hours, 22g of 1, 6-hexamethylene diisocyanate is added, and the reaction lasts for 3 hours.
And step two, adding 0.002g of stannous octoate, 0.1g of IRGANOX1010 and 0.2g of N, N- (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt into the reaction kettle to continue the reaction for 1.5 hours.
And step three, raising the temperature of the reaction kettle to 120 ℃, adding 3.5g of 1, 4-butanediol, reacting for 3 hours, and discharging to obtain the fully biodegradable polyurethane elastomer.
Example 2 preparation of biodegradable carbon dioxide-based polyurethane elastomer
Step one, weighing 110g of carbon dioxide-based polyol (the molecular weight is 30000g/mol, the content of a carbonic ester chain segment is 80 wt%) and putting the carbon dioxide-based polyol into a reaction kettle, heating the mixture to 105 ℃, decompressing the mixture for 1 hour, adding 35g of methylcyclohexyl diisocyanate, and reacting the mixture for 1 hour.
Step two, adding 0.01g of dibutyltin dilaurate, 0.8g of IRGANOX1076 and 0.8g of sodium 1, 4-dihydroxy-2-butanesulfonate into the reaction kettle, and continuing to react for 0.5 hour.
And step three, raising the temperature of the reaction kettle to 150 ℃, adding 18g of 1, 2-propylene glycol, reacting for 1 hour, and discharging to obtain the fully biodegradable polyurethane elastomer.
Example 3 preparation of biodegradable carbon dioxide-based polyurethane elastomer
Step one, 80g of carbon dioxide-based polyol (molecular weight is 2000g/mol, and the content of a carbonic ester chain segment is 40 wt%) is weighed and placed into a reaction kettle, the temperature is heated to 90 ℃, the pressure is reduced for 1.5 hours, 28g of dicyclohexylmethane diisocyanate is added, and the reaction lasts for 1.5 hours.
Step two, adding 0.006g of bismuth neodecanoate, 0.3g of IRGANOX1035 and 0.4g of sodium 2, 3-dihydroxynaphthalene-6-sulfonate into the reaction kettle, and continuing to react for 1 hour.
And step three, raising the temperature of the reaction kettle to 130 ℃, adding 5.2g of 1, 7-heptanediol, reacting for 2 hours, and discharging to obtain the fully biodegradable polyurethane elastomer.
Example 4 preparation of biodegradable carbon dioxide-based polyurethane elastomer
Step one, 100g of carbon dioxide-based polyol (with the molecular weight of 3000g/mol and the content of a carbonic ester chain segment of 35 wt%) is weighed and placed into a reaction kettle, the temperature is heated to 95 ℃, the pressure is reduced for 1.5 hours, 30g of isophorone diisocyanate is added, and the reaction lasts for 2.5 hours.
Step two, adding 0.005g of bismuth laurate, 0.6g of IRGANOX245 and 0.3g of sodium 2, 8-dihydroxynaphthalene-6-sulfonate into the reaction kettle to continue to react for 1 hour.
And step three, raising the temperature of the reaction kettle to 140 ℃, adding 7.2g of 1, 8-octanediol, reacting for 2 hours, and discharging to obtain the fully biodegradable polyurethane elastomer.
Example 5 preparation of biodegradable carbon dioxide-based polyurethane elastomer
Step one, 105g of carbon dioxide-based polyol (molecular weight is 2200g/mol, and the content of a carbonic ester chain segment is 60 wt%) is weighed and put into a reaction kettle, the temperature is heated to 92 ℃, the pressure is reduced for 1 hour, 29.5g of 1, 6-hexamethylene diisocyanate is added, and the reaction lasts for 2 hours.
Step two, adding 0.007g of bismuth isooctanoate, 0.65g of IRGANOX1098 and 0.55g of 1, 4-dihydroxy butane-2-sodium sulfonate into the reaction kettle to continue to react for 1.5 hours.
And step three, raising the temperature of the reaction kettle to 135 ℃, adding 10.5g of 1, 4-cyclohexanediol, reacting for 2.5 hours, and discharging to obtain the fully biodegradable polyurethane elastomer.
Example 6 preparation of biodegradable carbon dioxide-based polyurethane elastomer
Step one, 75g of carbon dioxide-based polyol (with the molecular weight of 5000g/mol and the content of a carbonic ester chain segment of 65 wt%) is weighed and put into a reaction kettle, the temperature is heated to 100 ℃, the pressure is reduced for 1.5 hours, 28g of isophorone diisocyanate is added, and the reaction lasts for 2 hours.
And step two, adding 0.008g of bismuth naphthenate, 0.45g of IRGANOX1520 and 0.6g of 1, 4-dihydroxy butane-2-sodium sulfonate into the reaction kettle, and continuing to react for 1 hour.
And step three, raising the temperature of the reaction kettle to 145 ℃, adding 12.5g of 1, 4-butanediol, reacting for 2.5 hours, and discharging to obtain the fully biodegradable polyurethane elastomer.
Comparative example 1
The synthesis was performed as in example 1, except that sodium N, N- (2-hydroxyethyl) -2-aminoethanesulfonate was removed in step two.
Comparative example 2
The synthesis was performed as in example 2, except that sodium 1, 4-dihydroxy-2-butanesulfonate was removed in step two.
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%. The compost container was placed in a test environment at (58. + -. 2). degree.C.and the test was carried out at (58. + -. 2). degree.C.by aerating the test system with humidity-saturated air without CO2 at a flow rate of 0.05L/min. 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 test results of examples 1-6 and comparative examples 1-2
From the above examples, the invention provides a biodegradable carbon dioxide-based polyurethane elastomer, which is prepared from the following raw materials in parts by weight: 60-110 parts of carbon dioxide-based polyol, 22-35 parts of aliphatic diisocyanate, 0.002-0.01 part of catalyst, 0.1-0.8 part of antioxidant, 0.2-0.8 part of sulfonate-containing dihydroxy compound and 3.5-18 parts of chain extender. The invention greatly improves the hydrophilicity of the polyurethane elastomer material by introducing the sulfonate of the strong hydrophilic group, enhances the hydrolyzability of the obtained elastomer material and greatly improves the biodegradation performance. The experimental results show that: the number average molecular weight of the polyurethane elastomer reaches 5.8-8.2 ten thousand, the weight average molecular weight reaches 7.6-11.5 ten thousand, the tensile strength is 14-25 MPa, and the elongation at break is 650-820%. The result of the composting test shows that: the hydrophilic modified polyurethane elastomer material begins to disintegrate within 30 days; after 90 days, the degradation rate exceeds 70 percent; after 180 days, the degradation rate reaches 92 percent. And without hydrophilic groups, disintegration began only 90 days; after 180 days, the highest degradation rate reaches 18 percent; the highest degradation rate of the product reaches 67 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 (7)
1. The biodegradable carbon dioxide-based polyurethane elastomer is prepared from the following raw materials in parts by weight:
60-110 parts of carbon dioxide-based polyol, 22-35 parts of aliphatic diisocyanate, 0.002-0.01 part of catalyst, 0.1-0.8 part of antioxidant, 0.2-0.8 part of sulfonate-containing dihydroxy compound and 3.5-18 parts of chain extender.
2. The biodegradable titanium dioxide-based polyurethane elastomer according to claim 1, wherein the sulfonate-containing dihydroxy compound is selected from one or more of sodium N, N- (2-hydroxyethyl) -2-aminoethanesulfonate, sodium 2, 5-dihydroxybenzenesulfonate, sodium 2, 3-dihydroxynaphthalene-6-sulfonate, sodium 1, 4-dihydroxy-2-butanesulfonate, sodium 2, 8-dihydroxynaphthalene-6-sulfonate, sodium 2-dihydroxy-3-monopropanesulfonate, and sodium 1, 4-dihydroxybutane-2-sulfonate.
3. The biodegradable titanium dioxide-based polyurethane elastomer according to claim 1, wherein the molecular weight of the carbon dioxide-based polyol is 1000 to 30000 g/mol; the content of the carbonic ester chain segment is 30-80 wt%.
4. The biodegradable titanium dioxide-based polyurethane elastomer 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.
5. The biodegradable titanium dioxide-based polyurethane elastomer according to claim 1, wherein the antioxidant is selected from one or more of IRGANOX1010, IRGANOX1076, IRGANOX1035, IRGANOX245, IRGANOX1098, IRGANOX1135, and IRGANOX 1520;
the chain extender is selected from one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 7-heptanediol, 1, 8-octanediol and 1, 4-cyclohexanediol;
the catalyst is selected from one or more of stannous octoate, dibutyltin dilaurate, bismuth neodecanoate, bismuth laurate, bismuth isooctanoate or bismuth naphthenate.
6. The biodegradable titanium dioxide-based polyurethane elastomer according to claim 1, wherein the biodegradable carbon dioxide-based polyurethane elastomer comprises the following components:
60 parts of carbon dioxide-based polyol, 22 parts of 1, 6-hexamethylene diisocyanate, 0.002 part of stannous octoate, 0.1 part of IRGANOX1010, 0.2 part of N, N- (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 3.5 parts of 1, 4-butanediol;
or 110 parts of carbon dioxide-based polyol, 35 parts of methylcyclohexyl diisocyanate, 0.01 part of dibutyltin dilaurate, 0.8 part of IRGANOX1076, 0.8 part of sodium 1, 4-dihydroxy-2-butanesulfonate and 18 parts of 1, 2-butanediol;
or comprises 80 parts of carbon dioxide-based polyol, 28 parts of dicyclohexylmethane diisocyanate, 0.006 part of bismuth neodecanoate, 0.3 part of IRGANOX1035, 0.4 part of 2, 3-dihydroxy naphthalene-6-sodium sulfonate and 5.2 parts of 1, 7-heptanediol;
or comprises 100 parts of carbon dioxide-based polyol, 30 parts of isophorone diisocyanate, 0.005 part of bismuth laurate, 0.6 part of IRGANOX245, 0.3 part of 2, 8-dihydroxy naphthalene-6-sodium sulfonate and 7.2 parts of 1, 8-octanediol;
or 105 parts of carbon dioxide-based polyol, 29.5 parts of 1, 6-hexamethylene diisocyanate, 0.007 part of bismuth isooctanoate, 0.65 part of IRGANOX1098, 0.55 part of sodium 1, 4-dihydroxybutane-2-sulfonate and 10.5 parts of 1, 4-cyclohexanediol;
or comprises 75 parts of carbon dioxide-based polyol, 28 parts of isophorone diisocyanate, 0.008 part of bismuth naphthenate, 0.45 part of IRGANOX1520, 0.6 part of 1, 4-dihydroxy butane-2-sodium sulfonate and 12.5 parts of 1, 4-butanediol.
7. A method for preparing the biodegradable carbon dioxide-based polyurethane elastomer according to any one of claims 1 to 6, comprising the following steps:
1) heating the carbon dioxide-based polyol to 85-105 ℃, decompressing for 1-2 hours, adding aliphatic diisocyanate, and reacting for 1-3 hours;
2) adding a catalyst, an antioxidant and a dihydroxy compound containing sulfonate into the reaction product obtained in the step 1) and continuously reacting for 0.5-1.5 hours;
3) heating the reaction product obtained in the step 2) to 120-150 ℃, adding a chain extender, and reacting for 1-3 hours to obtain the biodegradable carbon dioxide-based polyurethane elastomer.
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