CN112143210A - Amphiphilic biodegradable thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
Amphiphilic biodegradable thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN112143210A CN112143210A CN202010887419.9A CN202010887419A CN112143210A CN 112143210 A CN112143210 A CN 112143210A CN 202010887419 A CN202010887419 A CN 202010887419A CN 112143210 A CN112143210 A CN 112143210A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/06—Biodegradable
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Abstract
The invention relates to an amphiphilic biodegradable thermoplastic polyurethane elastomer and a preparation method thereof. The invention creatively adds the starch nanocrystal grafted by the polystyrene into the thermoplastic polyurethane, wherein the starch nanocrystal grafted by the polystyrene is a biodegradable nontoxic macromolecule and is matched with the biodegradable thermoplastic polyurethane, so that the final product has very good biodegradability and very advantageous mechanical properties.
Description
Technical Field
The invention belongs to the technical field of biodegradable materials, particularly relates to a thermoplastic polyurethane elastomer and a preparation method thereof, and particularly relates to an amphiphilic biodegradable thermoplastic polyurethane elastomer and a preparation method thereof.
Background
Polyurethane is a general name of macromolecular compounds containing repeated urethane groups on main chains, has excellent characteristics of wear resistance, oil resistance, tearing resistance, chemical corrosion resistance and the like, and is widely applied to various fields. However, how to make the polyurethane material have better biodegradable performance is always a key difficulty, which also limits the polyurethane material to be widely applied to the field of biological medicine.
CN106084748A discloses a biodegradable TPU film, which comprises the following components in parts by weight: 100 parts of polyether type TPU particles, 5-20 parts of hydrolysis-resistant stabilizer, 0.1-5 parts of antioxidant, 0.1-5 parts of photodecomposition agent and 0.1-5 parts of phosphorus pentoxide, wherein the hydrolysis-resistant stabilizer is a mixture of N, N' -bis (2, 6-diisopropylphenyl) carbodiimide and mono 2-oxazoline in a molar ratio of 1 (0.3-2). The TPU film provided by the invention still keeps good mechanical property and hydrolysis resistance under the degradable condition.
CN105482058A discloses a biodegradable polyurethane elastomer and a preparation method thereof. The method comprises the following raw materials: the double-hydroxyl-terminated biodegradable polyester, isocyanate, a chain extender and an auxiliary agent. The dihydroxy terminated biodegradable polyester is one or more of dihydroxy terminated polybutylene succinate, dihydroxy terminated polybutylene adipate and dihydroxy terminated polybutylene terephthalate. The polyurethane elastomer has good mechanical property and excellent processing property, has biocompatibility and biodegradability, and can be applied to the fields of mulching films, shopping bags and the like.
The starch is a renewable, biodegradable and nonhazardous natural polymer, and the advantages enable the starch to occupy more and more important positions in the field of synthetic materials. However, there are few reports on how to apply starch materials to polyurethane materials in the prior art, and therefore, it is very meaningful to develop a product combining starch with polyurethane elastomer.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a thermoplastic polyurethane elastomer and a preparation method thereof, in particular to an amphiphilic biodegradable thermoplastic polyurethane elastomer and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides an amphiphilic biodegradable thermoplastic polyurethane elastomer comprising a biodegradable thermoplastic polyurethane and polystyrene grafted starch nanocrystals.
The invention creatively adds the starch nanocrystal grafted by the polystyrene into the thermoplastic polyurethane, wherein the starch nanocrystal grafted by the polystyrene is a biodegradable nontoxic macromolecule and is matched with the biodegradable thermoplastic polyurethane, so that the final product has very good biodegradability and very advantageous mechanical properties. The mechanical property depends on a plurality of factors, wherein the most important is the dispersion level and the interface strength, the natural starch particles have a large amount of hydrophilic hydroxyl, high polarity and large particle size, so the compatibility with thermoplastic polyurethane is poor, and the uniform dispersion is difficult.
Preferably, the mass ratio of the biodegradable thermoplastic polyurethane to the polystyrene grafted starch nanocrystals is (3-8: 1, e.g., 3:1, 4:1, 5:1, 6:1, 7:1, or 8:1, etc., preferably (6-8: 1).
The mass ratio of the biodegradable thermoplastic polyurethane to the polystyrene grafted starch nanocrystal is specifically selected from (3-8):1, so that the product can be ensured to have good biodegradability and mechanical property at the same time, wherein (6-8):1 is a range with better effect.
In the invention, the raw materials for preparing the biodegradable thermoplastic polyurethane comprise diisocyanate, caprolactone, glycolide, an initiator, a catalyst and a chain extender.
The thermoplastic polyurethane uses diisocyanate, caprolactone and glycolide as raw materials, and due to the fact that the degradation rate of polycaprolactone is low, and the degradation rate of polyglycolide is high, the combination of caprolactone and glycolide not only maintains the degradation capability of polycaprolactone, but also can improve the mechanical property of polycaprolactone.
Preferably, the preparation raw materials of the biodegradable thermoplastic polyurethane comprise, by weight, 15-75 parts of diisocyanate, 10-50 parts of caprolactone, 1 part of glycolide, 1-5 parts of an initiator, 1-15 parts of a catalyst and 10-50 parts of a chain extender.
The number of the diisocyanate is 15, 20, 30, 40, 55, 65 or 75, and other specific values in the range can be selected, and are not repeated herein.
The parts of the caprolactone can be 10 parts, 20 parts, 30 parts, 40 parts, 50 parts and the like, and other specific point values in the range can be selected, so that the descriptions are omitted.
The initiator can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts and the like, and other specific point values in the range can be selected, so that the repeated description is omitted.
The parts of the catalyst can be 1 part, 3 parts, 5 parts, 7 parts, 10 parts, 12 parts or 15 parts, and other specific point values in the range can be selected, and are not repeated.
The parts of the chain extender can be 10 parts, 20 parts, 30 parts, 40 parts, 50 parts and the like, and other specific point values in the range can be selected, so that the description is omitted.
Preferably, the diisocyanate comprises any one of or a combination of at least two of L-lysine ethyl ester diisocyanate, diphenylmethane-4, 4-diisocyanate or isophorone diisocyanate, preferably L-lysine ethyl ester diisocyanate. The combination of at least two of the above-mentioned compounds, for example, the combination of L-lysine ethyl ester diisocyanate and diphenylmethane-4, 4-diisocyanate, the combination of diphenylmethane-4, 4-diisocyanate and isophorone diisocyanate, etc., may be selected in any combination manner, and thus, the details are not repeated herein.
The type of the diisocyanate is preferably L-lysine ethyl ester diisocyanate because the ethyl ester side group in the molecular chain makes the diisocyanate have hydrolyzability, and meanwhile, the hydrolysis product has no toxicity and good biocompatibility.
Preferably, the initiator comprises any one of ethylene glycol, ethylenediamine, 1, 3-propanediol, 1, 4-butanediol, hexanediol, diethylene glycol or 1, 5-pentanediol or a combination of at least two thereof; the combination of at least two of the above-mentioned compounds, such as the combination of ethylene glycol and ethylenediamine, the combination of hexanediol and diethylene glycol, etc., can be selected in any other combination manner, and thus, the details are not repeated herein.
Preferably, the catalyst comprises any one of stannous octoate, dibutyltin dioctoate or dibutyltin dilaurate or a combination of at least two of the foregoing; the combination of at least two of the foregoing combinations, for example, a combination of stannous octoate and dibutyltin dioctoate, a combination of dibutyltin dioctoate and dibutyltin dilaurate, a combination of stannous octoate and dibutyltin dilaurate, and the like, and any other combination modes are not described in detail herein.
Preferably, the chain extender comprises any one of ethylene glycol, ethylenediamine, 1, 3-propanediol, 1, 4-butanediol, hexanediol, diethylene glycol or 1, 5-pentanediol or a combination of at least two thereof; the combination of at least two of the foregoing, for example, a combination of ethylene glycol and ethylenediamine, a combination of 1, 3-propanediol and 1, 4-butanediol, a combination of 1, 4-butanediol, hexanediol and diethylene glycol, and the like, and any other combination method is not described in detail. A combination of 1, 4-butanediol, hexanediol and diethylene glycol is preferred.
In the invention, the raw materials for preparing the polystyrene grafted starch nanocrystal comprise the starch nanocrystal, styrene, potassium persulfate and an emulsifier.
Preferably, the molar ratio of the starch nanocrystal to the styrene is (1-3):1, for example, 1:1, 2:1 or 3:1, and other specific values within the range can be selected, and are not described in detail herein.
The mol ratio of the starch nanocrystal to the styrene is specifically selected from (1-3) to 1, so that the mechanical property and the biodegradation property of the product can be further improved.
Preferably, the mass of the potassium persulfate is 0.3% -0.6% of the mass of the styrene, such as 0.3%, 0.4%, 0.5% or 0.6%, and other specific values within the range can be selected, and are not repeated herein.
Preferably, the emulsifier comprises sodium dodecylbenzene sulfonate.
In a second aspect, the present invention provides a process for preparing an amphiphilic biodegradable thermoplastic polyurethane elastomer as described above, said process comprising: and respectively preparing biodegradable thermoplastic polyurethane and polystyrene grafted starch nanocrystals, mixing and extruding to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Preferably, the preparation method of the biodegradable thermoplastic polyurethane comprises the following steps:
(1) mixing caprolactone, glycolide, an initiator and a catalyst, and reacting under the protection of protective gas to obtain a double-end hydroxyl prepolymer;
(2) and (2) mixing the double-end hydroxyl prepolymer obtained in the step (1) with diisocyanate, carrying out primary reaction under the protection of protective gas, and then adding a chain extender and a catalyst to carry out secondary reaction to obtain the biodegradable thermoplastic polyurethane.
Preferably, the reaction temperature in step (1) is 120-.
Preferably, after the reaction in the step (1) is completed, the product is added into n-hexane for precipitation, and the precipitate is dried.
Preferably, the temperature of the first reaction in step (2) is 70-90 ℃, for example, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, and the like, and the time is 1-3h, for example, 1h, 2h or 3h, and other specific values in the range can be selected, and are not repeated herein.
Preferably, the temperature of the secondary reaction in the step (2) is 85-100 ℃, for example, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, and the like, and the time is 8-12h, for example, 8h, 9h, 10h, 11h or 12h, and other specific values in the range can be selected, which is not described herein again.
Preferably, after the secondary reaction in the step (2) is completed, adding the product into n-hexane for precipitation, and drying the precipitate.
Preferably, the preparation method of the polystyrene grafted starch nanocrystal comprises the following steps:
(1) preparing starch nanocrystals;
(2) and (2) mixing the starch nanocrystals prepared in the step (1) with styrene, potassium persulfate and an emulsifier, then carrying out emulsion polymerization under the protection of protective gas, demulsifying after the reaction is finished, and carrying out centrifugal separation to obtain the polystyrene grafted starch nanocrystals.
Preferably, the method for preparing starch nanocrystals according to step (1) comprises: the corn starch is subjected to acidolysis with a sulfuric acid solution, washed, adjusted to pH 4 to 6 (e.g., pH 4, pH 5, pH 6, etc.), and washed to neutrality.
Preferably, the concentration of the sulfuric acid solution is 2-4mol/L, such as 2mol/L, 3mol/L or 4mol/L, and other specific values within the range can be selected, and are not repeated herein.
Preferably, the temperature of the acid hydrolysis is 40-50 ℃, such as 40 ℃, 42 ℃, 45 ℃, 48 ℃ or 50 ℃, and the like, the time is 5-10 days, such as 5 days, 6 days, 7 days, 8 days or 10 days, and other specific values in the range can be selected, and are not repeated herein.
Preferably, the temperature of the emulsion polymerization reaction in the step (2) is 60-80 ℃, for example 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, and the like, and the time is 8-12h, for example 8h, 9h, 10h, 11h or 12h, and other specific values in the range can be selected, and are not repeated herein.
Preferably, acetone is used for demulsification in the step (2).
Preferably, the mixing temperature is 120-.
Preferably, the mixing time is 1-5h, for example, 1h, 2h, 3h, 4h or 5h, and other specific values within the range can be selected, which is not described herein again.
As a preferred technical scheme of the invention, the preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
(1) preparing starch nanocrystals: performing acidolysis on corn starch with 2-4mol/L sulfuric acid solution at 40-50 deg.C for 5-10 days, washing, adjusting pH to 4-6, washing to neutrality, adding a small amount of chloroform, and magnetically stirring to prevent agglomeration of particles;
(2) mixing the starch nanocrystals prepared in the step (1) with styrene, potassium persulfate and sodium dodecyl benzene sulfonate, carrying out emulsion polymerization reaction for 8-12h at 60-80 ℃ under the protection of protective gas, demulsifying with acetone after the reaction is finished, carrying out centrifugal separation, washing with toluene, and washing with distilled water to obtain the polystyrene grafted starch nanocrystals; the mol ratio of the starch nanocrystal to the styrene is (1-3):1, and the mass of the potassium persulfate is 0.3-0.6% of that of the styrene;
(3) mixing caprolactone, glycolide, an initiator and a catalyst, and reacting for 18-30h at the temperature of 120-130 ℃ under the protection of protective gas to obtain a double-end hydroxyl prepolymer; adding the product into n-hexane for precipitation, and drying the precipitate;
(4) mixing the double-end hydroxyl prepolymer obtained in the step (3) with diisocyanate, carrying out primary reaction for 1-3h at 70-90 ℃ under the protection of protective gas, then adding a chain extender and a catalyst to carry out secondary reaction for 8-12h at 85-100 ℃, adding a product into n-hexane for precipitation, and drying the precipitate to obtain the biodegradable thermoplastic polyurethane;
(5) mixing the polystyrene grafted starch nanocrystal prepared in the step (2) with the biodegradable thermoplastic polyurethane prepared in the step (4), mixing for 1-5h at the temperature of 120-150 ℃, and extruding to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Compared with the prior art, the invention has the following beneficial effects:
the invention creatively adds the starch nanocrystal grafted by the polystyrene into the thermoplastic polyurethane, wherein the starch nanocrystal grafted by the polystyrene is a biodegradable nontoxic macromolecule and is matched with the biodegradable thermoplastic polyurethane, so that the final product has very good biodegradability and very advantageous mechanical properties.
According to the invention, starch is modified to prepare an amphiphilic starch derivative, namely the polystyrene grafted starch nanocrystal, and due to the fact that a lipophilic macromolecular chain is grafted and copolymerized in a nanometer starch macromolecule, the hydrophilicity of the material is ensured, the hydrophobicity of the material is improved, the hydrophobic macromolecular chain is stretched, and the compatibility with a polyurethane interface is ensured.
The biodegradable thermoplastic polyurethane uses diisocyanate, caprolactone and glycolide as raw materials, because the degradation rate of polycaprolactone is slow, and the degradation rate of polyglycolide is fast, the combination of caprolactone and glycolide not only maintains the degradation capability of polycaprolactone, but also can improve the mechanical property of polycaprolactone.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
The reagents referred to in the following examples include:
caprolactone: purchasing Aladdin, adding calcium hydride before use, stirring for 12h, and distilling under reduced pressure;
glycolide: purchased from Zhengzhou Akmm chemical Co., Ltd, and recrystallized twice with ethyl acetate before use;
diethylene glycol: purchased from Nanjing reagent, analyzed and purified, added with metal sodium before use, stirred for 12 hours and then distilled under reduced pressure;
1, 4-butanediol: purchased from Nanjing reagent, analyzed and purified, added with metal sodium before use, stirred for 12 hours and then distilled under reduced pressure;
stannous octoate: purchased from Aladdin, distilled under reduced pressure before use;
dibutyltin dilaurate: purchased from Aladdin for direct use;
tetrahydrofuran: purchasing Aladdin, stirring and refluxing for 12h by using calcium hydride under the protection of nitrogen, and distilling at normal pressure to collect 70 ℃ fractions;
n-hexane: purchased from Guangzhou chemical reagent factory, adding calcium hydride before use, stirring for 12h, distilling at normal pressure and collecting 68 ℃ fraction;
l-lysine ethyl ester diisocyanate: purchased from Aladdin for direct use;
isophorone diisocyanate: purchased from Aladdin for direct use;
diphenylmethane-4, 4-diisocyanate: purchased from Aladdin for immediate use.
Example 1
The biodegradable thermoplastic polyurethane is prepared by the following steps:
(1) mixing 40 parts of caprolactone, 1 part of glycolide, 3 parts of diethylene glycol and 2 parts of stannous octoate, reacting for 24 hours at 125 ℃ under the protection of nitrogen, adding the product into n-hexane for precipitation, and drying the precipitate to obtain a double-end hydroxyl prepolymer;
(2) and (2) mixing the double-end hydroxyl prepolymer obtained in the step (1) with 50 parts of L-lysine ethyl ester diisocyanate, carrying out primary reaction for 2h at 80 ℃ under the protection of nitrogen, then adding 20 parts of 1, 4-butanediol and 3 parts of dibutyltin dilaurate, carrying out secondary reaction for 10h at 90 ℃, adding the product into n-hexane for precipitation, and drying the precipitate to obtain the biodegradable thermoplastic polyurethane.
Example 2
The biodegradable thermoplastic polyurethane is prepared by the following steps:
(1) mixing 20 parts of caprolactone, 1 part of glycolide, 5 parts of diethylene glycol and 5 parts of stannous octoate, reacting for 30 hours at 120 ℃ under the protection of nitrogen, adding a product into n-hexane for precipitation, and drying the precipitate to obtain a double-end hydroxyl prepolymer;
(2) and (2) mixing the double-end hydroxyl prepolymer obtained in the step (1) with 20 parts of L-lysine ethyl ester diisocyanate, carrying out primary reaction for 3h at 70 ℃ under the protection of nitrogen, then adding 20 parts of 1, 4-butanediol and 5 parts of dibutyltin dilaurate, carrying out secondary reaction for 12h at 85 ℃, adding the product into n-hexane for precipitation, and drying the precipitate to obtain the biodegradable thermoplastic polyurethane.
Example 3
The biodegradable thermoplastic polyurethane is prepared by the following steps:
(1) mixing 40 parts of caprolactone, 1 part of glycolide, 5 parts of diethylene glycol and 7 parts of stannous octoate, reacting for 18 hours at 130 ℃ under the protection of nitrogen, adding the product into n-hexane for precipitation, and drying the precipitate to obtain a double-end hydroxyl prepolymer;
(2) and (2) mixing the double-end hydroxyl prepolymer obtained in the step (1) with 70 parts of L-lysine ethyl ester diisocyanate, carrying out primary reaction for 1h at 90 ℃ under the protection of nitrogen, then adding 40 parts of 1, 4-butanediol and 7 parts of dibutyltin dilaurate to carry out secondary reaction for 8h at 95 ℃, adding the product into n-hexane for precipitation, and drying the precipitate to obtain the biodegradable thermoplastic polyurethane.
Example 4
This example prepares a biodegradable thermoplastic polyurethane, which differs from example 1 only in that L-lysine ethyl ester diisocyanate is replaced by isophorone diisocyanate, and the other conditions are maintained.
Example 5
This example prepares a biodegradable thermoplastic polyurethane, which differs from example 1 only in that L-lysine ethyl ester diisocyanate is replaced by diphenylmethane-4, 4-diisocyanate, and the other conditions are maintained.
Example 6
This example prepares a biodegradable thermoplastic polyurethane which differs from that of example 1 only in that it does not contain glycolide and in that 41 parts of caprolactone, all other conditions remaining unchanged.
Example 7
This example prepares a biodegradable thermoplastic polyurethane, which differs from example 1 only in 30 parts caprolactone and 11 parts glycolide, all other conditions remaining unchanged.
Example 8
This example prepares a polystyrene grafted starch nanocrystal, whose preparation method is as follows:
(1) preparing starch nanocrystals: carrying out acidolysis on corn starch by using a 3mol/L sulfuric acid solution at 45 ℃ for 7 days, washing, adjusting the pH value to 5, washing to be neutral, adding a small amount of chloroform, and magnetically stirring to prevent particle agglomeration;
(2) and (2) mixing the starch nanocrystal prepared in the step (1) with styrene, potassium persulfate, sodium dodecyl benzene sulfonate and sodium carbonate, then carrying out emulsion polymerization reaction for 10 hours at 70 ℃ under the protection of nitrogen, demulsifying with acetone after the reaction is finished, carrying out centrifugal separation, washing with toluene, and washing with distilled water to obtain the polystyrene grafted starch nanocrystal. Wherein the molar ratio of the starch nanocrystal to the styrene is 2:1, the mass of the potassium persulfate is 0.5 percent of the mass of the styrene, the concentration of the sodium dodecyl benzene sulfonate is 10mol/L, and the mass of the sodium carbonate is 5 percent of the mass of the starch nanocrystal.
Example 9
This example prepares a polystyrene grafted starch nanocrystal, whose preparation method is as follows:
(1) preparing starch nanocrystals: performing acidolysis on corn starch by using a 2mol/L sulfuric acid solution at 40 ℃ for 10 days, washing, adjusting the pH value to 4.5, washing to be neutral, adding a small amount of chloroform, and magnetically stirring to prevent particle agglomeration;
(2) and (2) mixing the starch nanocrystal prepared in the step (1) with styrene, potassium persulfate, sodium dodecyl benzene sulfonate and sodium carbonate, then carrying out emulsion polymerization reaction for 10 hours at 70 ℃ under the protection of nitrogen, demulsifying with acetone after the reaction is finished, carrying out centrifugal separation, washing with toluene, and washing with distilled water to obtain the polystyrene grafted starch nanocrystal. Wherein the molar ratio of the starch nanocrystal to the styrene is 1:1, the mass of the potassium persulfate is 0.3 percent of the mass of the styrene, the concentration of the sodium dodecyl benzene sulfonate is 10mol/L, and the mass of the sodium carbonate is 5 percent of the mass of the starch nanocrystal.
Example 10
This example prepares a polystyrene grafted starch nanocrystal, whose preparation method is as follows:
(1) preparing starch nanocrystals: carrying out acidolysis on corn starch by using a 4mol/L sulfuric acid solution at 50 ℃ for 5 days, washing, adjusting the pH value to 5.5, washing to be neutral, adding a small amount of chloroform, and magnetically stirring to prevent particle agglomeration;
(2) and (2) mixing the starch nanocrystal prepared in the step (1) with styrene, potassium persulfate, sodium dodecyl benzene sulfonate and sodium carbonate, then carrying out emulsion polymerization reaction for 8 hours at 80 ℃ under the protection of nitrogen, demulsifying with acetone after the reaction is finished, carrying out centrifugal separation, washing with toluene, and washing with distilled water to obtain the polystyrene grafted starch nanocrystal. Wherein the molar ratio of the starch nanocrystal to the styrene is 3:1, the mass of the potassium persulfate is 0.6 percent of the mass of the styrene, the concentration of the sodium dodecyl benzene sulfonate is 10mol/L, and the mass of the sodium carbonate is 5 percent of the mass of the starch nanocrystal.
Example 11
This example prepared a polystyrene grafted starch nanocrystal, which was prepared by a method different from that of example 8 only in that the molar ratio of the starch nanocrystal to styrene in step (2) was specified to be 5: 1.
Application example 1
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
the starch nanocrystals grafted with polystyrene prepared in example 8 and the biodegradable thermoplastic polyurethane prepared in example 1 were mixed in a mass ratio of 1:7, and then kneaded at 120 ℃ for 5 hours, and extruded to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Application example 2
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
the starch nanocrystals grafted with polystyrene prepared in example 8 and the biodegradable thermoplastic polyurethane prepared in example 1 were mixed in a mass ratio of 1:5, and then kneaded at 120 ℃ for 5 hours, and extruded to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Application example 3
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
the starch nanocrystals grafted with polystyrene prepared in example 8 and the biodegradable thermoplastic polyurethane prepared in example 1 were mixed in a mass ratio of 1:2, and then kneaded at 120 ℃ for 5 hours, and extruded to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Application example 4
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
and mixing the polystyrene grafted starch nanocrystal prepared in the example 9 with the biodegradable thermoplastic polyurethane prepared in the example 1, then mixing for 5 hours at 120 ℃, and extruding to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Application example 5
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
and mixing the polystyrene grafted starch nanocrystal prepared in the example 10 with the biodegradable thermoplastic polyurethane prepared in the example 1, then mixing for 5 hours at 120 ℃, and extruding to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Application example 6
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
the starch nanocrystals grafted with polystyrene prepared in example 11 and the biodegradable thermoplastic polyurethane prepared in example 1 were mixed, kneaded at 120 ℃ for 5 hours, and extruded to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Application example 7
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
and mixing the polystyrene grafted starch nanocrystal prepared in the embodiment 8 with the biodegradable thermoplastic polyurethane prepared in the embodiment 2, then mixing for 5 hours at 120 ℃, and extruding to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Application example 8
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
and mixing the polystyrene grafted starch nanocrystal prepared in the embodiment 8 with the biodegradable thermoplastic polyurethane prepared in the embodiment 3, then mixing for 5 hours at 120 ℃, and extruding to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Application example 9
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
and mixing the polystyrene grafted starch nanocrystal prepared in the embodiment 8 with the biodegradable thermoplastic polyurethane prepared in the embodiment 4, then mixing for 5 hours at 120 ℃, and extruding to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Application example 10
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
and mixing the polystyrene grafted starch nanocrystal prepared in the embodiment 8 with the biodegradable thermoplastic polyurethane prepared in the embodiment 5, then mixing for 5 hours at 120 ℃, and extruding to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Application example 11
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
and mixing the polystyrene grafted starch nanocrystal prepared in the embodiment 8 with the biodegradable thermoplastic polyurethane prepared in the embodiment 6, then mixing for 5 hours at 120 ℃, and extruding to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Application example 12
The preparation method of the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises the following steps:
and mixing the polystyrene grafted starch nanocrystal prepared in the example 8 with the biodegradable thermoplastic polyurethane prepared in the example 7, then mixing for 5 hours at 120 ℃, and extruding to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
Identification test:
(1) the polyurethane material obtained in example 1 was analyzed by infrared chromatography, and the results are shown in Table 1:
TABLE 1
From the above table, it can be seen that biodegradable thermoplastic polyurethanes have been successfully synthesized.
(2) The infrared chromatographic analysis of the polystyrene grafted starch nanocrystals obtained in example 8 showed the results shown in table 2:
TABLE 2
| Wave number (cm)-1) | Attribution |
| 3380-3420 | O-H stretching vibration |
| 3000 | C-H stretching vibration |
| 1550-1590 | C-O stretching vibration |
| 1420、1370 | O-H in-plane bending vibration |
| 1280、1260、1220 | C-H bending vibration |
| 3030 | Benzene ring stretching vibration |
| 1450-1650 | Vibration of benzene ring skeleton |
| 698 | Aromatic C-H out-of-plane vibration |
As can be seen from the above table, the polystyrene grafted starch nanocrystals were successfully synthesized.
Performance evaluation test:
(1) the amphiphilic biodegradable thermoplastic polyurethane elastomers prepared in examples 1-12 were subjected to mechanical property measurement using GB/T1040-:
TABLE 3
| Group of | Tensile strength MPa | Elongation at break% | Hardness of | Tear Strength kN/m |
| Application example 1 | 22.16 | 586.86 | 72 | 31.43 |
| Application example 2 | 21.11 | 556.17 | 69 | 30.62 |
| Application example 3 | 19.78 | 536.83 | 66 | 29.86 |
| Application example 4 | 22.51 | 558.96 | 75 | 31.07 |
| Application example 5 | 21.51 | 523.38 | 67 | 28.47 |
| Application example 6 | 18.47 | 439.57 | 55 | 25.36 |
| Application example 7 | 21.72 | 577.19 | 75 | 30.13 |
| Application example 8 | 22.58 | 542.30 | 77 | 28.79 |
| Application example 9 | 23.79 | 602.51 | 71 | 32.52 |
| Application example 10 | 22.31 | 584.46 | 74 | 29.27 |
| Application example 11 | 22.45 | 579.35 | 69 | 30.15 |
| Applications ofExample 12 | 21.46 | 553.06 | 72 | 24.36 |
As can be seen from the data in Table 3: the amphiphilic biodegradable thermoplastic polyurethane elastomer has good mechanical properties, wherein the proportion of the prepared raw material styrene to the starch microcrystal, the proportion of the biodegradable thermoplastic polyurethane to the polystyrene grafted starch nanocrystal and the like influence the mechanical properties.
(2) In the test, a QCM-D method is adopted to research the degradation rate of the amphiphilic biodegradable thermoplastic polyurethane elastomer prepared in application examples 1-12 under the action of Pseudomonas cepacia lipase (PS), the change relation of frequency (delta f, Hz) along with time (h) is detected, the delta f gradually rises along with the time until the polyurethane elastomer is stable, if the rising speed is higher, the degradation rate is higher, and the results are shown in Table 4:
TABLE 4
| Group of | 0h | 2h | 4h | 8h |
| Application example 1 | 0 | 210 | 356 | 358 |
| Application example 2 | 0 | 205 | 371 | 370 |
| Application example 3 | 0 | 202 | 357 | 362 |
| Application example 4 | 0 | 215 | 374 | 377 |
| Application example 5 | 0 | 208 | 368 | 365 |
| Application example 6 | 0 | 192 | 306 | 357 |
| Application example 7 | 0 | 211 | 353 | 356 |
| Application example 8 | 0 | 210 | 358 | 360 |
| Application example 9 | 0 | 155 | 246 | 353 |
| Application example 10 | 0 | 172 | 249 | 348 |
| Application example 11 | 0 | 122 | 185 | 326 |
| Application example 12 | 0 | 296 | 366 | 373 |
From the data in table 4, it can be seen that: the amphiphilic biodegradable thermoplastic polyurethane elastomer has good biodegradability, wherein the degradability of the diisocyanate, the existence of caprolactone and the proportion of the caprolactone to the glycolide, and the like, which are used as raw materials, can be influenced.
The applicant states that the present invention is illustrated by the above examples of an amphiphilic biodegradable thermoplastic polyurethane elastomer and a method for preparing the same, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. An amphiphilic biodegradable thermoplastic polyurethane elastomer, characterized in that the amphiphilic biodegradable thermoplastic polyurethane elastomer comprises biodegradable thermoplastic polyurethane and polystyrene grafted starch nanocrystals.
2. The amphiphilic biodegradable thermoplastic polyurethane elastomer according to claim 1, wherein the mass ratio of the biodegradable thermoplastic polyurethane to the polystyrene grafted starch nanocrystals is (3-8):1, preferably (6-8): 1.
3. The amphiphilic biodegradable thermoplastic polyurethane elastomer according to claim 1 or 2, wherein the biodegradable thermoplastic polyurethane is prepared from raw materials comprising diisocyanate, caprolactone, glycolide, an initiator, a catalyst and a chain extender;
preferably, the preparation raw materials of the biodegradable thermoplastic polyurethane comprise, by weight, 15-75 parts of diisocyanate, 10-50 parts of caprolactone, 1 part of glycolide, 1-5 parts of an initiator, 1-15 parts of a catalyst and 10-50 parts of a chain extender.
4. The amphiphilic biodegradable thermoplastic polyurethane elastomer according to claim 3, wherein the diisocyanate comprises any one or a combination of at least two of L-lysine ethyl ester diisocyanate, diphenylmethane-4, 4-diisocyanate or isophorone diisocyanate, preferably L-lysine ethyl ester diisocyanate;
preferably, the initiator comprises any one of ethylene glycol, ethylenediamine, 1, 3-propanediol, 1, 4-butanediol, hexanediol, diethylene glycol or 1, 5-pentanediol or a combination of at least two thereof;
preferably, the catalyst comprises any one of stannous octoate, dibutyltin dioctoate or dibutyltin dilaurate or a combination of at least two of the foregoing;
preferably, the chain extender comprises any one of ethylene glycol, ethylene diamine, 1, 3-propanediol, 1, 4-butanediol, hexanediol, diethylene glycol or 1, 5-pentanediol or a combination of at least two thereof.
5. The amphiphilic biodegradable thermoplastic polyurethane elastomer according to any one of claims 1 to 4, wherein the polystyrene-grafted starch nanocrystal is prepared from the raw materials comprising starch nanocrystal, styrene, potassium persulfate, and emulsifier;
preferably, the molar ratio of the starch nanocrystals to styrene is (1-3): 1;
preferably, the mass of the potassium persulfate is 0.3-0.6% of that of the styrene;
preferably, the emulsifier comprises sodium dodecylbenzene sulfonate.
6. The process for the preparation of amphiphilic biodegradable thermoplastic polyurethane elastomers according to any one of claims 1 to 5, characterized in that it comprises: and respectively preparing biodegradable thermoplastic polyurethane and polystyrene grafted starch nanocrystals, mixing and extruding to obtain the amphiphilic biodegradable thermoplastic polyurethane elastomer.
7. The method of preparing an amphiphilic biodegradable thermoplastic polyurethane elastomer according to claim 6, wherein the method of preparing the biodegradable thermoplastic polyurethane comprises the steps of:
(1) mixing caprolactone, glycolide, an initiator and a catalyst, and reacting under the protection of protective gas to obtain a double-end hydroxyl prepolymer;
(2) and (2) mixing the double-end hydroxyl prepolymer obtained in the step (1) with diisocyanate, carrying out primary reaction under the protection of protective gas, and then adding a chain extender and a catalyst to carry out secondary reaction to obtain the biodegradable thermoplastic polyurethane.
8. The method for preparing amphiphilic biodegradable thermoplastic polyurethane elastomer as claimed in claim 7, wherein the temperature of the reaction in the step (1) is 120-130 ℃ and the time is 18-30 h;
preferably, after the reaction in the step (1) is finished, adding the product into n-hexane for precipitation, and drying the precipitate;
preferably, the temperature of the first reaction in the step (2) is 70-90 ℃ and the time is 1-3 h;
preferably, the temperature of the secondary reaction in the step (2) is 85-100 ℃, and the time is 8-12 h;
preferably, after the secondary reaction in the step (2) is completed, adding the product into n-hexane for precipitation, and drying the precipitate.
9. The method of preparing amphiphilic biodegradable thermoplastic polyurethane elastomer according to claim 6, wherein the method of preparing the polystyrene grafted starch nanocrystal comprises the steps of:
(1) preparing starch nanocrystals;
(2) mixing the starch nanocrystals prepared in the step (1) with styrene, potassium persulfate and an emulsifier, then carrying out emulsion polymerization reaction under the protection of protective gas, demulsifying after the reaction is finished, and carrying out centrifugal separation to obtain the polystyrene grafted starch nanocrystals;
preferably, the method for preparing starch nanocrystals according to step (1) comprises: carrying out acidolysis and washing on corn starch by using a sulfuric acid solution, adjusting the pH value to 4-6, and then washing to be neutral;
preferably, the concentration of the sulfuric acid solution is 2-4 mol/L;
preferably, the acidolysis temperature is 40-50 ℃, and the time is 5-10 days;
preferably, the temperature of the emulsion polymerization reaction in the step (2) is 60-80 ℃, and the time is 8-12 h;
preferably, acetone is used for demulsification in the step (2).
10. The method for preparing amphiphilic biodegradable thermoplastic polyurethane elastomer as claimed in any one of claims 6 to 9, wherein the mixing temperature is 120-150 ℃;
preferably, the mixing time is 1-5 h.
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