CN110627985A - Polylactic acid-based thermoplastic polyurethane elastomer material and preparation method thereof - Google Patents
Polylactic acid-based thermoplastic polyurethane elastomer material 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/428—Lactides
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G2350/00—Acoustic or vibration damping material
Abstract
The invention relates to a polylactic acid-based thermoplastic polyurethane elastomer material and a preparation method thereof. The invention discloses a polylactic acid-based thermoplastic polyurethane elastomer material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) removing water from the polylactic acid dihydric alcohol in a vacuum stirring and heating environment; (2) heating, adding diisocyanate compounds, catalysts and solvents into the dried polylactic acid for stable copolymerization to obtain a prepolymer; (3) and adding micromolecular dihydric alcohol into the prepolymer, quickly stirring, taking out, curing in an oven, and removing the solvent to obtain the polylactic acid-based thermoplastic polyurethane elastomer. The polyurethane prepared by the method has the advantages of transparency, good elasticity, high damping factor and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a thermoplastic polyurethane elastomer material, in particular to a thermoplastic polylactic acid-based polyurethane elastic material and a preparation method thereof.
Background
The progress development of science and technology drives social progress, the high-speed, high-efficiency and automatic process of mechanical equipment is accelerated, and meanwhile, the problems of vibration, noise and the like are more and more serious. Vibration and noise reduce the performance of mechanical equipment, pollute the environment and harm physical and psychological health, so vibration and noise reduction are problems to be solved urgently, and a damping technology is the most important means for the vibration and noise reduction. The ability to dissipate kinetic or acoustic energy is commonly referred to as damping, with the higher the damping, the shorter the time required for the system to return to its original state. The polymer damping material converts mechanical energy into heat energy or other forms of energy consumption, and plays roles in damping vibration attenuation and noise reduction. The polymer damping material has been widely applied to various fields because of its shock absorption and noise reduction properties, and is a research hotspot of the damping material.
Rubber is a viscoelastic medium that has both elastic solid and viscous fluid properties. In the process of sound energy and vibration propagation, mechanical energy or sound energy is converted into random motion of molecular chain segments, and finally the random motion is converted into heat energy to be dissipated, so that the effects of sound absorption and noise reduction are achieved. In order to meet the actual use requirements, the rubber is often required to be modified, and common methods include copolymerization, blending, interpenetrating network (IPN) modification and the like. When rubber is blended, the performance of the composite material is often deteriorated due to poor compatibility of different rubber matrixes, which is also a main defect of the traditional rubber.
The polyurethane is a polymer containing repeated carbamate (-NH-COO-) chain segments in macromolecular chains, the polyurethane elastomer is a special elastomer, the hardness range of the polyurethane elastomer is very wide, the hardness of the polyurethane elastomer is as low as a low-modulus rubber below Shore A10, the hardness of the polyurethane elastomer is as high as a high-modulus impact-resistant elastic material of Shore D90, the elastic modulus of the polyurethane elastomer can reach hundreds of megapascals, and the elastic modulus of the polyurethane elastomer is greatly higher than that of other rubbers (0.2-10 MPa). Polyurethane is suitable for damping materials due to its special microphase separation structure, strong intermolecular interaction force and molecular polarity. As a novel rubber, the polyurethane can directly regulate and control various performances of a final product through designing the raw material ratio, simultaneously keeps better comprehensive performance, and has the advantage that the traditional rubber cannot surpass.
Xiabin Jing et al (polylactic-based polyurethane and its shape-memory behavior [ J ]. European Polymer Journal,2006,42(6): 1240-: hexamethylene diisocyanate: the 1, 4-butanediol polylactic acid polyurethane elastomers have the molar ratio of 1:2:1, 1:5:4 and 1:7:6, the Tg of the elastomers is 33-53 ℃, the molecular weight is 40000-140000, the tensile strength is more than 40MPa, the elongation at break is less than 250%, and the elastomers have good shape memory performance. Xiaobin knotting et al (Shape monomer) -based polyurethanes with differential hardnesses [ J ]. Polymer International,2007,56(7): 840) -846.) prepare polylactic acid diol with a molecular weight of 3200 by lactide ring-opening polymerization, react with three diisocyanates, namely 4,4' -diphenylmethane diisocyanate (MDI), 2, 4-Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI), and synthesize a series of polylactic acid-based polyurethanes by chain extension with 1, 4-butanediol. The Tg of the materials is 49-63 ℃, so at room temperature, the materials are in glassy state, belong to plastics, have tensile strength of more than 40MPa, but have elongation at break of less than 25% and molecular weight of 40000-120000. Among them, MDI-based polyurethane has the highest Tg, the maximum tensile strength and restoring force, TDI-based polyurethane has the lowest Tg, and IPDI-based polyurethane has the highest tensile modulus and elongation at break.
According to the technical scheme, the prepolymerization time is short when the polylactic acid-based polyurethane is prepared, so that the process is more biased to a one-step method, a large amount of toluene solvent is used in the preparation process, a large amount of ethanol and chloroform are used as washing extraction solvents, the glass transition temperature (Tg) of polylactic acid dihydric alcohol used in the prior art is 33-53 ℃, the prepared polylactic acid-based polyurethane belongs to a glass state at room temperature, the requirement of a room-temperature damping material cannot be met, the elongation at break of the product is not more than 250%, the elasticity is insufficient, and the diversified requirements in actual life cannot be met. Meanwhile, the molecular chain of the polyurethane elastomer prepared by the one-step method is generally disordered, and compared with a prepolymer method, the polyurethane elastomer is easy to generate defects and poor in performance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention uses polylactic acid dihydric alcohol and diisocyanate to generate a prepolymer with higher molecular weight by a prepolymer method, and uses micromolecular dihydric alcohol to carry out chain extension to prepare the thermoplastic polylactic acid-based polyurethane elastomer with higher number average molecular weight (about 30000-100000) and good damping performance. The GPC and infrared tests prove that the thermoplastic polylactic acid-based polyurethane elastomer with the molecular weight of more than 30000 is obtained, the DMA test proves that the thermoplastic polylactic acid-based polyurethane elastomer has good damping performance, and the mechanical performance test shows that the thermoplastic polylactic acid-based polyurethane elastomer has good mechanical performance.
One of the purposes of the invention is to provide a polylactic acid-based thermoplastic polyurethane elastomer, wherein the soft segment of the polyurethane elastomer is polylactic acid dihydric alcohol, the hard segment of the polyurethane elastomer comprises diisocyanate compounds and micromolecular dihydric alcohol, and the molar ratio of the diisocyanate compounds to the micromolecular dihydric alcohol in the hard segment is 1.5: 1-3: 1.
Wherein the diisocyanate compound is at least one selected from toluene diisocyanate, 4 '-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dimethyl diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, p-phenylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate;
the micromolecular dihydric alcohol is at least one selected from 1, 4-butanediol, ethylene glycol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 2, 3-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-1, 3-hexanediol and N-methyldiethanolamine.
The second object of the present invention is to provide a method for preparing the polyurethane elastomer, comprising the steps of: mixing and copolymerizing polylactic acid dihydric alcohol and diisocyanate compounds to obtain a diisocyanate-terminated polylactic acid-based polyurethane prepolymer; then adding micromolecular dihydric alcohol for chain extension to obtain the polylactic acid-based thermoplastic polyurethane elastomer. The method comprises the following specific steps:
step one, adding polylactic acid dihydric alcohol and diisocyanate compounds into a reaction container, adding a catalyst A and a solvent B, and reacting and copolymerizing to obtain a diisocyanate-terminated polylactic acid-based polyurethane prepolymer;
wherein the catalyst A is an organic tin catalyst, preferably at least one of stannous octoate, dibutyltin diacetate, dibutyltin dilaurate and dibutyltin didodecyl sulfide;
the solvent B is selected from organic solvents, preferably at least one of tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide;
adding micromolecular dihydric alcohol under the stirring condition, and carrying out chain extension reaction to obtain a polylactic acid-based polyurethane precursor;
and step three, heating and curing the polyurethane precursor obtained in the step two to obtain the polylactic acid-based thermoplastic polyurethane elastomer.
Wherein the number average molecular weight of the polylactic acid dihydric alcohol in the step one is 500-1000, preferably 1000-3000; the molar ratio of the polylactic acid dihydric alcohol to the diisocyanate compound is 1: 1-1: 3, preferably 1: 1.5-1: 2.5; the dosage of the catalyst A is 0.01-0.2 wt% of the total mass of the polylactic acid dihydric alcohol, the diisocyanate and the micromolecular dihydric alcohol, and preferably 0.02-0.05 wt%; the volume of the solvent B is 0-0.4 mL/g, preferably 0.1-0.2 mL/g of the total mass of the polylactic acid dihydric alcohol, the diisocyanate compound and the micromolecular dihydric alcohol; the copolymerization reaction is carried out at the normal pressure of 60-90 ℃.
The small molecular diol in the step two is at least one selected from 1, 4-butanediol, ethylene glycol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 2, 3-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-1, 3-hexanediol and N-methyldiethanolamine; the micromolecular dihydric alcohol is added according to the molar ratio of the polylactic acid dihydric alcohol to the micromolecular dihydric alcohol of 1: 0.5-1: 2, preferably 1: 0.5-1: 1.5; the chain extension reaction is carried out at the normal pressure of 75-90 ℃.
And the curing condition in the third step is that the curing is complete at 100-140 ℃. The state of the sample is observed during curing, and after curing, vacuum is applied for removing a small amount of solvent B in the polyurethane.
Dehydrating the polylactic acid dihydric alcohol in the step one before the copolymerization reaction; and (4) stirring and dehydrating at the temperature of 100-130 ℃ in a vacuum state until no bubbles appear during stirring.
The polylactic acid-based thermoplastic polyurethane elastomer prepared by the preparation method has the number average molecular weight of 30000-100000, the molecular weight distribution (PDI) of 1.2-1.9, the glass transition temperature Tg of-15-2 ℃, and the loss factor tan delta max of 0.45-1.1.
The invention provides a preparation method of a polylactic acid-based thermoplastic polyurethane elastomer, which takes polylactic acid dihydric alcohol (PLA) with different molecular weights as soft segments and diisocyanate and micromolecular dihydric alcohol as hard segments, changes the molar ratio of the two segments, and prepares a series of thermoplastic polylactic acid polyurethane by a prepolymer method. The number average molecular weight of the synthesized thermoplastic polylactic acid polyurethane is 30000-100000, PDI is 1.2-1.9, the glass transition temperature (Tg) is-15-2 ℃, and the loss factor tan delta max is 0.45-1.1.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the prior art which uses a large amount of toluene solvent to ensure that the whole system is in a solution state and more organic tin catalysts, the invention uses less solvent (only adding a small amount of solvent to improve the viscosity of the system, and the system is always in a viscous fluid) and less organic tin catalysts;
2. various properties of the material can be directly controlled by regulating and controlling the proportion of raw materials, a series of thermoplastic polylactic acid-based polyurethane elastomers are prepared by taking polylactic acid diols (PLA) with different molecular weights as soft sections and diisocyanate and micromolecule diols as hard sections and changing the molar ratio of the two, the molecular weight distribution of the synthesized thermoplastic polylactic acid polyurethane is narrower, the number average molecular weight is 30000-100000, the PDI is 1.2-1.9, the glass transition temperature (Tg) is-15-2 ℃, the loss factor tan delta max is 0.45-1.1, the tensile strength is 1-15 MPa, and the elongation at break is 250-920%;
3. the polylactic acid-based polyurethane elastomer provided by the invention can be used as a green room temperature damping material, and the prepared polylactic acid-based polyurethane elastomer belongs to a thermoplastic material, can be repeatedly processed, improves the utilization rate of resources and reduces waste.
Drawings
FIG. 1 is an IR spectrum, 2270cm, of example 1-3(PU-1 to PU-3)-1There was no absorption peak, confirming that the-NCO group reaction was complete.
FIG. 2 is a DSC curve of examples 1-3, which shows that the Tg of the sample is in the range of-8 to-12 ℃, the soft segment is not crystallized, and the hard segment gradually shows a melting absorption peak with the increase of the content.
FIG. 3 is a DMA curve for examples 1-3, in which the Tg of the sample varies regularly from-4 to-1 ℃ and the damping temperature range (tan. delta. >0.3) is 17 to 26 ℃ and tan. delta. max is 0.8 at the highest and 0.48 at the lowest. The loss factor may reflect the ability of the material to dissipate external energy, i.e., the damping ability.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
And (3) infrared testing: the prepared self-repairing elastomer is analyzed by using a TENSOR 27 type Fourier transform infrared spectrum of Bruker company, and the test range is 4000--1. The chemical structure of the polyurethane elastomer is tested by adopting an ATR-IR mode, and the preparation method of the sample comprises the following steps: shearing 3X 1cm3The elastomer sample is dried in an infrared oven and then directly tested.
DSC test: differential Scanning Calorimetry (DSC) analysis was performed using the STARe system of Mettler Toledo, Switzerland, the temperature increase and decrease rates were set to 10K/min, the mass of the sample was about 10mg, and N was used2And (4) protecting atmosphere, wherein the temperature scanning range is 193-353K.
And (3) testing mechanical properties: the tensile strength and elongation at break of the polyurethane elastomers were tested according to GB/T528-2009 on a universal tensile testing machine, model Instron5567 from Instron corporation, USA. Dumbbell-shaped specimens of 25 mm. times.6 mm. times.1 mm were cut out with a cutter and tested at room temperature. The stretching rate was set at 500mm/min and at least 5 bars were tested under the same conditions for each sample.
Gel permeation chromatography analysis: the solvent was tetrahydrofuran, the standard was polystyrene, and equipped with a differential refractometer detector and three chromatography columns (Styragel HT3, 4, and 5), with a maximum flow rate of 22.5mL, and the retention time of the polymer in the chromatography columns was tested.
And DMA test: the used type is GABO500 dynamic thermomechanical analysis (DMA) was tested using the following conditions: strain 1%, frequency 1Hz, heating rate 3 deg.C/min-1The tensile mode was tested at a temperature range of-70-100 ℃.
The polylactic acid diol is purchased from Shenzhen Guanghua Wei Co., Ltd, the hexamethylene diisocyanate, the dibutyltin dilaurate, the 1, 4-butanediol and the N, N-dimethylformamide are purchased from Shanghai Aladdin Co., Ltd, the 1, 5-pentanediol is purchased from adamas Co., Ltd, and the 2-methyl-1, 3-propanediol is purchased from Sahn chemical technology (Shanghai) Co., Ltd,
example 1
The preparation method comprises the following steps of (1) designing PLA (mole ratio) HDI (hexamethylene diisocyanate): BDO (hexamethylene diisocyanate): 1:2:1 by using polylactic acid dihydric alcohol (PLA) with Mn being 1000 as a soft segment and Hexamethylene Diisocyanate (HDI) and 1, 4-butanediol as hard segments, and preparing the thermoplastic polylactic acid-based polyurethane elastomer by a prepolymer method:
(1) 50g of polylactic acid diol (Mn 1000) was dewatered under-0.095 MPa at 120 ℃ for 1.5h with mechanical stirring at 90r/min, and this step removed water from the starting material.
(2) After the temperature of the system is reduced to 60 ℃, 16g of hexamethylene diisocyanate, 0.02g of dibutyltin dilaurate serving as a catalyst and 25mL of N, N-dimethylformamide serving as a solvent are added, the rotating speed is adjusted to 150r/min, the temperature of the system is raised to 75 ℃ and then the reaction is carried out for 3h, so that the polyisocyanate-terminated polylactic acid-based polyurethane prepolymer is obtained.
(3) Adding 4g of chain extender 1, 4-butanediol under mechanical stirring at the speed of 400r/min to ensure that the molar ratio of-NCO: -OH in a system is 1:1, reacting for 3min at the temperature of 90 ℃, taking out a product, placing the product in an oven at the temperature of 120 ℃ for 15h (in this step, the state of a sample needs to be observed, and vacuumizing the oven after curing is used for removing a small amount of N, N-dimethylformamide existing in polyurethane), thus obtaining the finished polylactic acid-based thermoplastic polyurethane.
(4) The material produced was tested to yield the following data: the number average molecular weight was 37000, PDI was 1.42, tensile strength was 9.03MPa, elongation at break was 547%, tan. delta. max was 0.48, and Tg was-1.19 ℃.
Example 2
The preparation method comprises the following steps of (1) designing PLA (mole ratio) of HDI (hexamethylene diisocyanate): BDO (hexamethylene diisocyanate): 1:2:1 by using polylactic acid dihydric alcohol (PLA) with Mn being 2000 as a soft segment and Hexamethylene Diisocyanate (HDI) and 1, 4-butanediol as hard segments, and preparing the thermoplastic polylactic acid-based polyurethane elastomer by a prepolymer method:
(1) 57g of polylactic acid diol (Mn ═ 2000) was dewatered under mechanical stirring at 120 ℃ and 120 ℃ under-0.095 MPa for 2h, and the water content in the starting material was removed.
(2) After the temperature is reduced to 60 ℃, 9.5g of hexamethylene diisocyanate, 0.02g of dibutyltin dilaurate serving as a catalyst and 10mL of N, N-dimethylformamide serving as a solvent are added, the rotating speed is adjusted to 120r/min, the temperature is raised to be stable to 77 ℃, and then the reaction is carried out for 3h, so that the polyisocyanate-terminated polylactic acid-based polyurethane prepolymer is obtained.
(3) Adding 2.5g of chain extender 1, 4-butanediol under mechanical stirring at 300r/min, ensuring that the molar ratio of-NCO: -OH in a system is 1:1, reacting for 9min at 90 ℃, taking out a product, placing the product in an oven at 100 ℃ for 12h (in the step, the state of a sample needs to be observed, and vacuumizing the oven after curing for removing a small amount of N, N-dimethylformamide existing in polyurethane), thus obtaining the polylactic acid-based thermoplastic polyurethane finished product.
(4) The material produced was tested to yield the following data: the number average molecular weight was 48000, PDI was 1.54, tensile strength was 8.22MPa, elongation at break was 879%, tan. delta. max was 0.69, and Tg was-2.53 ℃.
Example 3
The preparation method comprises the following steps of (1) designing PLA (mole ratio) HDI (hexamethylene diisocyanate): BDO (hexamethylene diisocyanate): 1:2:1 by using polylactic acid dihydric alcohol (PLA) with Mn being 3000 as a soft segment and Hexamethylene Diisocyanate (HDI) and 1, 4-butanediol as hard segments, and preparing the thermoplastic polylactic acid-based polyurethane elastomer by a prepolymer method:
(1) 61g of polylactic acid diol (Mn. about.3000) was dewatered under-0.095 MPa at 120 ℃ for 2.5h with mechanical stirring at 90r/min, and this step removed water from the starting material.
(2) After the temperature of the system is reduced to 60 ℃, 6.7g of hexamethylene diisocyanate, 0.02g of dibutyltin dilaurate serving as a catalyst and 10mL of N, N-dimethylformamide serving as a solvent are added, the rotating speed is adjusted to 120r/min, the temperature is raised to be stable to 77 ℃, and then the reaction is carried out for 3h, so that the polyisocyanate-terminated polylactic acid-based polyurethane prepolymer is obtained.
(3) Adding 1.8g of chain extender 1, 4-butanediol under mechanical stirring of 500r/min, ensuring that the molar ratio of-NCO: -OH in a system is 1:1, reacting for 7min at 90 ℃, taking out a product, placing the product in an oven at 100 ℃ for 12h (in the step, the state of a sample needs to be observed, and vacuumizing the oven after curing for removing a small amount of N, N-dimethylformamide existing in polyurethane), thus obtaining the finished polylactic acid-based thermoplastic polyurethane.
(4) The material produced was tested to yield the following data: the number average molecular weight was 45000, PDI was 1.48, tensile strength was 7.91MPa, elongation at break was 816%, tan. delta. max was 0.8, Tg was-3.69 ℃.
Example 4
Using polylactic acid dihydric alcohol (PLA) with Mn being 2000 as a soft segment, using Hexamethylene Diisocyanate (HDI) and 1, 4-butanediol as hard segments, designing PLA: HDI: BDO being 1:1.5:0.5 (molar ratio), and preparing the thermoplastic polylactic acid-based polyurethane elastomer by a prepolymer method:
(1) 61g of polylactic acid diol (Mn 2000) was dewatered under-0.095 MPa at 120 ℃ for 1.5h with mechanical stirring at 90r/min, and this step removed water from the starting material.
(2) After the temperature of the system is reduced to 60 ℃, 7.5g of hexamethylene diisocyanate, 0.02g of dibutyltin dilaurate serving as a catalyst and 10mL of N, N-dimethylformamide serving as a solvent are added, the rotating speed is adjusted to 120r/min, the temperature is raised to be stable to 77 ℃, and then the reaction is carried out for 3h, so that the polyisocyanate-terminated polylactic acid-based polyurethane prepolymer is obtained.
(3) Adding 1.3g of chain extender 1, 4-butanediol under mechanical stirring at 400r/min, ensuring that the molar ratio of-NCO: -OH in a system is 1:1, reacting at 90 ℃ for 35min, taking out a product, placing the product in an oven at 140 ℃ for 12h (in this step, the state of a sample needs to be observed, and vacuumizing the oven after curing for removing a small amount of N, N-dimethylformamide existing in polyurethane), thus obtaining the finished polylactic acid-based thermoplastic polyurethane.
(4) The material produced was tested to yield the following data: the number average molecular weight was 32000, PDI was 1.51, tensile strength was 0.8MPa, elongation at break was 364%, tan. delta. max was 0.97, and Tg was-4.2 ℃.
Example 5
The preparation method comprises the following steps of (1) designing PLA (molar ratio) HDI (hexamethylene diisocyanate): BDO (hexamethylene diisocyanate): 1:2.5:1.5 by using polylactic acid dihydric alcohol (PLA) with Mn being 1000 as a soft segment and Hexamethylene Diisocyanate (HDI) and 1, 4-butanediol as hard segments, and preparing the thermoplastic polylactic acid-based polyurethane elastomer by a prepolymer method:
(1) 45g of polylactic acid diol (Mn 1000) was dewatered under-0.095 MPa at 120 ℃ for 1.5h with mechanical stirring at 90r/min, and this step removed water from the starting material.
(2) After the temperature of the system is reduced to 60 ℃, 18g of hexamethylene diisocyanate, 0.02g of dibutyltin dilaurate serving as a catalyst and 10mL of N, N-dimethylformamide serving as a solvent are added, the rotating speed is adjusted to 180r/min, the temperature is raised to be stable to 77 ℃, and then the reaction is carried out for 2h, so that the polyisocyanate-terminated polylactic acid-based polyurethane prepolymer is obtained.
(3) And adding 6g of chain extender 1, 4-butanediol under mechanical stirring at 250r/min to ensure that the molar ratio of-NCO: -OH in the system is 1:1, reacting for 4min at 90 ℃, taking out a product, placing the product in a 100 ℃ oven for 12h (in the step, the state of a sample needs to be observed, and vacuumizing the oven after curing to remove a small amount of N, N-dimethylformamide existing in the polyurethane), thus obtaining the polylactic acid-based thermoplastic polyurethane finished product.
(4) The material produced was tested to yield the following data: the number average molecular weight was 51561, PDI was 1.26, tensile strength was 14.82MPa, elongation at break was 525%, tan. delta. max was 0.97, and Tg was-4.2 ℃.
Example 6
Using polylactic acid dihydric alcohol (PLA) with Mn being 2000 as a soft segment, and Hexamethylene Diisocyanate (HDI) and 2-methyl-1, 3-propanediol (MPO) as hard segments, designing PLA: HDI: MPO being 1:2:1 (molar ratio), and preparing the thermoplastic polylactic acid-based polyurethane elastomer by a prepolymer method:
(1) 58g of polylactic acid diol (Mn 2000) was dewatered under-0.095 MPa at 120 ℃ for 1.5h with mechanical stirring at 90r/min, and this step removed water from the starting material.
(2) After the temperature of the system is reduced to 60 ℃, 9.5g of hexamethylene diisocyanate, 0.02g of dibutyltin dilaurate serving as a catalyst and 10mL of N, N-dimethylformamide serving as a solvent are added, the rotating speed is adjusted to 120r/min, the temperature is raised to 87 ℃ stably, and then the reaction is carried out for 4h, so that the polyisocyanate-terminated polylactic acid-based polyurethane prepolymer is obtained.
(3) 2.6g of chain extender 2-methyl-1.3 propylene glycol is added under the mechanical stirring of 400r/min, the molar ratio of-NCO to-OH in the system is ensured to be 1:1, the product is taken out after the reaction is carried out for 15min at the temperature of 90 ℃ and is placed in an oven at the temperature of 100 ℃ for 9h (the state of a sample is required to be observed in the step, and the oven is vacuumized after the solidification for removing a small amount of N, N-dimethylformamide existing in the polyurethane), so that the finished product of the polylactic acid-based thermoplastic polyurethane is obtained.
(4) The material produced was tested to yield the following data: the number average molecular weight was 52824, the PDI was 1.27, the tensile strength was 3.2MPa, the elongation at break was 316%, tan. delta. max was 0.75, and the Tg was-6.5 ℃.
Example 7
Using polylactic acid dihydric alcohol (PLA) with Mn being 2000 as a soft segment, using Hexamethylene Diisocyanate (HDI) and 1, 5-Pentanediol (PDO) as hard segments, designing PLA: HDI: PDO being 1:2:1 (molar ratio), and preparing the thermoplastic polylactic acid-based polyurethane elastomer by a prepolymer method:
(1) 57.6g of polylactic acid diol (Mn 2000) was dewatered under-0.095 MPa at 120 ℃ for 1.5h with mechanical stirring at 90r/min, and this step removed water from the starting material.
(2) After the temperature of the system is reduced to 60 ℃, 9.5g of hexamethylene diisocyanate, 0.02g of dibutyltin dilaurate serving as a catalyst and 10mL of N, N-dimethylformamide serving as a solvent are added, the rotating speed is adjusted to 120r/min, the temperature is raised to 80 ℃ stably, and then the reaction is carried out for 3h, so that the polyisocyanate-terminated polylactic acid-based polyurethane prepolymer is obtained.
(3) Adding 2.9g of chain extender 1, 5-pentanediol under the mechanical stirring of 400r/min, ensuring that the molar ratio of-NCO: -OH in a system is 1:1, reacting for 9min at 90 ℃, taking out a product, placing the product in an oven at 100 ℃ for 9h (the state of a sample needs to be observed in the step, and vacuumizing the oven after curing to remove a small amount of N, N-dimethylformamide existing in polyurethane), thus obtaining the polylactic acid-based thermoplastic polyurethane finished product.
(4) The material produced was tested to yield the following data: the number average molecular weight was 43523, PDI was 1.33, tensile strength was 3.5MPa, elongation at break was 305%, tan. delta. max was 0.75, and Tg was-8.3 ℃.
Example 8
Using polylactic acid dihydric alcohol (PLA) with Mn being 3000 as a soft segment, using 4,4' -diphenylmethane diisocyanate (MDI) and 1, 4-butanediol as a hard segment, designing PLA: MDI: BDO being 1:1.5:0.5 (molar ratio), and preparing the thermoplastic polylactic acid-based polyurethane elastomer by a prepolymer method:
(1) 61.5g of polylactic acid diol (Mn. RTM.3000) was dewatered under-0.095 MPa at 120 ℃ for 1.5h with mechanical stirring at 90r/min, and this step removed water from the starting material.
(2) After the temperature of the system is reduced to 60 ℃, 7.6g of 4,4' -diphenylmethane diisocyanate, 0.02g of dibutyltin dilaurate serving as a catalyst and 10mL of N, N-dimethylformamide serving as a solvent are added, the rotating speed is adjusted to 120r/min, the temperature is raised to be stable to 80 ℃, and then the reaction is carried out for 3h, so that the polyisocyanate-terminated polylactic acid-based polyurethane prepolymer is obtained.
(3) Adding 0.91g of chain extender 1, 4-butanediol under mechanical stirring at 400r/min to ensure that the molar ratio of-NCO to-OH in the system is 1:1, reacting for 9min at 90 ℃, taking out a product, and placing for 9h in an oven at 100 ℃ to obtain a finished product of the polylactic acid-based thermoplastic polyurethane.
(4) The material produced was tested to yield the following data: the number average molecular weight was 32515, PDI was 1.23, tensile strength was 6.2MPa, elongation at break was 421%, tan. delta. max was 0.52, and Tg was 3.6 ℃.
In embodiments 1 to 8 of the invention, a series of polylactic acid-based thermoplastic polyurethane elastomers are synthesized by designing the use amounts of PLA, HDI and BDO. The Tg of the polylactic acid-based thermoplastic polyurethane elastomer synthesized by the prior art is 30-60 ℃, the elongation at break is lower than 250%, while the molecular weight distribution of the thermoplastic polylactic acid polyurethane elastomer synthesized by the invention is narrow, only 1.2-1.5, the glass transition temperature (Tg) is lower (-9-4 ℃), the loss factor tan delta max is 0.45-1.1, the damping temperature range (tan delta >0.3) is 17-27 ℃, the elongation at break is more than 300%, even close to 900%, which indicates that the polyurethane material has good mechanical properties and higher damping performance, and can be used as a green room temperature damping material.
Claims (10)
1. A polylactic acid-based thermoplastic polyurethane elastomer characterized by: the soft segment of the polyurethane elastomer is polylactic acid dihydric alcohol, and the hard segment of the polyurethane elastomer comprises diisocyanate compounds and micromolecular dihydric alcohol.
2. The polyurethane elastomer according to claim 1, characterized in that:
in the hard segment, the molar ratio of the diisocyanate compound to the micromolecular dihydric alcohol is 1.5: 1-3: 1.
3. The polyurethane elastomer according to claim 1, characterized in that:
the diisocyanate compound is at least one selected from toluene diisocyanate, 4 '-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dimethyl biphenyl diisocyanate, 1, 5-naphthalene diisocyanate, p-phenylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate; and/or the presence of a gas in the gas,
the micromolecular dihydric alcohol is at least one selected from 1, 4-butanediol, ethylene glycol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 2, 3-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-1, 3-hexanediol and N-methyldiethanolamine.
4. A method for preparing the polyurethane elastomer according to claim 1, comprising the steps of:
mixing and copolymerizing polylactic acid dihydric alcohol and diisocyanate compounds to obtain a diisocyanate-terminated polylactic acid-based polyurethane prepolymer; then adding micromolecular dihydric alcohol for chain extension to obtain the polylactic acid-based thermoplastic polyurethane elastomer.
5. The preparation method according to claim 4, characterized in that the preparation method specifically comprises the following steps:
step one, adding polylactic acid dihydric alcohol and diisocyanate compounds into a reaction container, adding a catalyst A and a solvent B, and reacting and copolymerizing to obtain a diisocyanate-terminated polylactic acid-based polyurethane prepolymer;
wherein the catalyst A is an organic tin catalyst, preferably at least one of stannous octoate, dibutyltin diacetate, dibutyltin dilaurate and dibutyltin didodecyl sulfide;
the solvent B is selected from organic solvents, preferably at least one of tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide;
adding micromolecular dihydric alcohol under the stirring condition, and carrying out chain extension reaction to obtain a polylactic acid-based polyurethane precursor;
and step three, heating and curing the polyurethane precursor obtained in the step two to obtain the polylactic acid-based thermoplastic polyurethane elastomer.
6. The method of claim 5, wherein:
the number average molecular weight of the polylactic acid dihydric alcohol in the step one is 500-1000, preferably 1000-3000; and/or the presence of a gas in the gas,
the molar ratio of the polylactic acid dihydric alcohol to the diisocyanate compound is 1: 1.5-1: 3, preferably 1: 1.5-1: 2.5; and/or the presence of a gas in the gas,
the dosage of the catalyst A is 0.01-0.2 wt% of the total mass of the polylactic acid dihydric alcohol, the diisocyanate compound and the micromolecular dihydric alcohol, and preferably 0.02-0.05 wt%; and/or the presence of a gas in the gas,
the volume of the solvent B is 0-0.4 mL/g, preferably 0.1-0.2 mL/g of the total mass of the polylactic acid dihydric alcohol, the diisocyanate compound and the micromolecular dihydric alcohol; and/or the presence of a gas in the gas,
the copolymerization reaction is carried out at the normal pressure of 60-90 ℃.
7. The method of claim 5, wherein:
the small molecular diol in the step two is selected from at least one of 1, 4-butanediol, ethylene glycol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 2, 3-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-1, 3-hexanediol and N-methyldiethanolamine; and/or the presence of a gas in the gas,
the micromolecular dihydric alcohol is added according to the molar ratio of the polylactic acid dihydric alcohol to the micromolecular dihydric alcohol of 1: 0.5-1: 2, preferably 1: 0.5-1: 1.5; and/or the presence of a gas in the gas,
the chain extension reaction is carried out at the normal pressure of 75-90 ℃.
8. The method of claim 5, wherein:
the curing condition in the third step is that the curing is complete at 100-140 ℃; and/or
Step polyurethane precursor after curing, the small amount of solvent B present in the polyurethane precursor is removed in vacuo.
9. The method of claim 5, wherein:
dehydrating the polylactic acid dihydric alcohol in the step one before the copolymerization reaction;
and stirring and dehydrating at the temperature of 100-130 ℃ in a vacuum state.
10. A polylactic acid-based thermoplastic polyurethane elastomer obtained by the production method according to any one of claims 1 to 9, wherein:
the number average molecular weight of the polyurethane elastomer is 30000-100000, the molecular weight distribution is 1.2-1.9, the glass transition temperature Tg is-15-2 ℃, and the loss factor tan delta max is 0.45-1.1.
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