CN118027342A - High heat-resistant thermoplastic polyurethane elastomer composite material and preparation method thereof - Google Patents
High heat-resistant thermoplastic polyurethane elastomer composite material and preparation method thereof Download PDFInfo
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- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- BUUSNVSJZVGMFY-UHFFFAOYSA-N 4-ethylheptane-3,3-diol Chemical compound CCCC(CC)C(O)(O)CC BUUSNVSJZVGMFY-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
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- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
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- 239000001257 hydrogen Substances 0.000 description 10
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a high heat-resistant thermoplastic polyurethane elastomer composite material and a preparation method thereof. The invention adopts the aromatic isocyanate with symmetrical structure as a hard segment to prepare the synthetic high heat-resistant thermoplastic polyurethane elastomer, adopts the polycarbonate compound as a soft segment to improve the wet skid resistance of the thermoplastic polyurethane elastomer, finally obtains the high heat-resistant thermoplastic polyurethane elastomer composite material which has photo-thermal self-repairing performance and can solve the problem of magic triangle, and provides a new thought for preparing self-repairing polyurethane tires.
Description
Technical Field
The invention belongs to the field of polyurethane materials, in particular relates to a polyurethane elastomer composite material capable of realizing photo-thermal self-repairing, and especially relates to a thermoplastic polyurethane elastomer composite material with high heat resistance and capable of solving the problem of magic triangle, and a preparation method thereof, and the thermoplastic polyurethane elastomer composite material can be applied to the field of synthetic rubber, in particular self-repairing tires.
Background
During running of the automobile, the tire may be leaked due to the puncture of the tire by the foreign matter, so that the running state of the automobile is unstable, which requires the tire to be replaced immediately or repaired temporarily. In order to quickly restore the running function of the vehicle, some self-repairing tires have been developed. Chinese patent CN114058293a discloses a self-repairing tire sealant based on butyl rubber and conjugated diene rubber. Chinese patent CN114106475A discloses a rubber composition for a sealing material based on butyl rubber and a pneumatic tire. However, the rolling resistance of the existing self-repairing tire is generally high, so that the vehicle oil consumption is high, and the self-repairing tire is based on synthetic rubber and has the problems of high energy consumption, high material consumption, high pollution and irrecoverability. In addition, the conventional radial tire has a fatal disadvantage in that it is easy to burst the tire, which causes damage to driving safety. The non-pneumatic tire is generated with the situation, the problems of air leakage, tire burst and the like are avoided, the comfort is also greatly improved, the non-pneumatic tire becomes a popular research object in the tire industry, most of the existing non-pneumatic tire is composed of a spoke of thermoplastic polyurethane and a rubber tread, the polarity difference between the rubber tread and a non-pneumatic hub is large, the adhesion is difficult, and the problem of adhesion with the hub can be solved by the polyurethane non-pneumatic tire tread which can meet the 'magic triangle' problem.
The use of thermoplastic polyurethane elastomers (TPU) instead of conventional synthetic rubber tires is one of the important approaches to solve the above problems, and TPU has become a research hotspot for non-pneumatic tires. TPU is generally a polymeric elastomeric material prepared by prepolymerizing a polyester polyol or polyether polyol with a sub-stoichiometric amount of a diisocyanate and then reacting with a diamine or glycol chain extender. TPU is soluble and fusible, has strong structural designability, and can obtain TPU materials with different physical properties by selecting different soft and hard segment structures or changing the content of soft and hard segments. The hydrogen bond of TPU is reversible, so a non-covalent bond (hydrogen bond) self-healing TPU elastomer can be developed through molecular structural design. Nano particles such as Nano-Fe 3O4, MXene, graphene and the like are widely absorbed at 400-900 nm, and can generate a large amount of heat under the irradiation of near infrared light (NIR), so that the TPU/Nano particle composite material can be designed to carry out self-repairing through hydrogen bond assembly under the irradiation of NIR. At present, hydrogen bond self-repairing polyurethane realized by adopting photo-heat is not available. The self-repairing polyurethane and the composite material thereof are mainly used in the fields of coating, strain sensors, flexible electronics and the like, such as China patent CN113512173A, CN113980302A, but are not used for self-repairing tires.
TPU has poor heat resistance, and the long-term use temperature is generally not higher than 80 ℃, which becomes an important problem for preventing the TPU from being used for tire products, and self-repairing at high temperature cannot be realized. Chinese patent CN112574385A discloses a wet-skid-resistant low-rolling-resistance thermoplastic polyurethane elastomer and a preparation method, and the prepared polyurethane has good heat resistance and wet-skid-resistant low-rolling-resistance performance, but the system has higher isocyanate proportion (the molar ratio of dihydric alcohol, diisocyanate and chain extender is preferably 1:1.5-4:0.5-3), which is not beneficial to environmental protection, and meanwhile, the self-repairing performance is not considered.
Disclosure of Invention
In the prior art, self-repairing polyurethane is prepared by adopting a cross-linking structure and a dynamic covalent bond, wherein the former is difficult to repeatedly process, and the latter needs to introduce various groups, so that the structure is complex. The polyurethane synthesized in this way has low or no degree of microphase separation, or poor dynamic properties, or high heat generation and low heat resistance, which affect its use in more complex situations, in particular sealing at high temperatures and as a tire. According to the invention, nano particles such as nano-Fe 3O4 are blended with thermoplastic polyurethane elastomer (TPU), so that the composite material can generate high heat under near infrared light (NIR) and realize self-repairing through the reversibility of hydrogen bonds. Meanwhile, special aromatic isocyanates with symmetrical structures such as paraphenylene diisocyanate (PPDI), 1, 5-Naphthalene Diisocyanate (NDI) and the like are used as hard segments to prepare the synthetic TPU, and the synthetic TPU has high heat resistance under the condition of low hard segment content. The polycarbonate compound is used as a soft segment to improve the wet skid resistance of the TPU, so that the high heat-resistant thermoplastic polyurethane elastomer composite material with photo-thermal self-repairing performance and capable of solving the problem of magic triangle is finally obtained, and a new idea is provided for preparing the self-repairing polyurethane tire.
The invention aims to provide a high heat-resistant thermoplastic polyurethane elastomer composite material, which comprises a thermoplastic polyurethane elastomer matrix and nanoparticle filler, wherein the thermoplastic polyurethane elastomer comprises a soft segment structure formed by polycarbonate compound chain segments and a hard segment structure derived from aromatic isocyanate and chain extender chain segments, and the nanoparticle filler is nanoparticle with a photo-thermal effect.
In the high heat-resistant thermoplastic polyurethane elastomer composite material, the nanoparticle filler comprises, but is not limited to, nano-particles with photo-thermal effects such as nano-Fe 3O4, MXene, graphene and the like; the particle size of the nanoparticle filler is 50-1000 nm, preferably 100-500 nm. The nanoparticle filler is used in an amount of 0 to 15 parts by weight, but not 0, preferably 3 to 10 parts by weight, based on 100 parts by weight of the thermoplastic polyurethane elastomer.
The thermoplastic polyurethane elastomer comprises the following components: the polycarbonate compound with the end group of the polycarbonate compound being hydroxyl is, for example, common polycarbonate diol (PCDL); the aromatic isocyanate is aromatic diisocyanate with a symmetrical structure, and is preferably at least one of paraphenylene diisocyanate (PPDI) and 1, 5-Naphthalene Diisocyanate (NDI); the chain extender is saturated micromolecular dihydric alcohol, including but not limited to at least one of ethylene glycol, diethylene glycol, triethylene glycol, 1, 3-propylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-Butanediol (BDO), 1, 3-butanediol, 2, 3-butanediol, neopentyl glycol, 1, 5-pentanediol, 1, 2-pentanediol, diethyl pentanediol, 1, 6-Hexanediol (HDO) and 2-ethyl-1, 3-hexanediol.
The thermoplastic polyurethane elastomer comprises a soft segment and a hard segment, wherein the soft segment is a polycarbonate compound chain segment, the hard segment is an aromatic isocyanate and chain extender chain segment, and the content of the soft segment is 70-95%, preferably 80-90%; the hard segment content is 5 to 30%, preferably 10 to 20%.
The second object of the present invention is to provide a method for preparing the high heat-resistant thermoplastic polyurethane elastomer composite material, comprising: and blending the thermoplastic polyurethane elastomer and the nanoparticle filler to obtain the composite material.
The preparation method specifically comprises the following steps: and melting the thermoplastic polyurethane elastomer, adding the nanoparticle filler, and blending to obtain the composite material. Wherein the temperature of melting and blending is 100-200 ℃, preferably 120-180 ℃.
The thermoplastic polyurethane elastomer is prepared by the following method: and (3) after the pre-polymerization reaction of the polycarbonate compound and the aromatic isocyanate, adding a chain extender to perform chain extension reaction, and curing to obtain the thermoplastic polyurethane elastomer. Wherein the molar ratio of the polycarbonate compound to the aromatic isocyanate to the chain extender is 1: (1.25-2.5): (0.25 to 1.5), preferably 1: (1.5-2.25): (0.5-2.25); the molecular weight of the polycarbonate compound is 500-3000, preferably 1000-2000. .
In the preparation method of the thermoplastic polyurethane elastomer, the pre-polymerization reaction conditions are as follows: reacting for 0.5-3 h at 70-95 ℃; the chain extension reaction conditions are as follows: reacting for 10-60 min at 80-95 ℃; the curing reaction conditions are as follows: reacting for 16-24 h at 100-120 ℃; the reaction is carried out under a protective gas atmosphere, which may be nitrogen as is commonly used.
According to the invention, the thermoplastic polyurethane elastomer provided by the invention is a polyurethane elastomer based on polycarbonate compounds and aromatic isocyanate with symmetrical structures, and is preferably a polyurethane elastomer based on PCDL-PPDI or a polyurethane elastomer based on PCDL-NDI.
Wherein, the specific preparation process of the polyurethane elastomer based on PCDL-PPDI can adopt the following steps: firstly, carrying out vacuum dehydration on PCDL for 1.5-2 h, then adding PPDI to carry out prepolymerization for 0.5-1 h at 70-90 ℃, then adding a chain extender to carry out chain extension for 10-30 min at 80-90 ℃, and then carrying out 16-24 h curing on the obtained product to finally obtain the polyurethane elastomer based on PCDL-PPDI;
The specific preparation process of the polyurethane elastomer based on PCDL-NDI can adopt the following steps: firstly, carrying out vacuum dehydration on PCDL for 1.5-2 h, then adding NDI to carry out prepolymerization for 2-3 h at 80-95 ℃, then adding a chain extender to carry out chain extension for 0.5-1 h at 90-95 ℃, and then carrying out 16-24 h curing on the obtained product to finally obtain the polyurethane elastomer based on PCDL-NDI.
The polyurethane synthesized by adopting the aromatic isocyanate in the invention has good heat resistance, and the higher the symmetry of the isocyanate is, the better the heat resistance of the synthesized polyurethane is. The polyurethane synthesized by adopting special aromatic isocyanate with symmetrical structures such as paraphenylene diisocyanate (PPDI) and Naphthalene Diisocyanate (NDI) and the like as hard segments has high heat resistance. While the TPU/nanoparticle composite material is self-repaired through hydrogen bond assembly under NIR irradiation, the excellent performance of the material is not damaged.
In addition, the invention uses polycarbonate or modified polycarbonate diol (PCDL) as a soft segment to improve the wet skid resistance of the TPU material, because PCDL has high ester group content, under the condition that the length of the hard segment is the same as the molecular weight of the soft segment, the hard segment and the soft segment can form strong hydrogen bond action, and the crystallization of the soft segment can be inhibited to a certain extent, so that the wet skid resistance is improved.
Compared with the prior art, the invention has the following advantages:
1. The polycarbonate compound adopted by the invention has high ester group content, the soft segment of the synthesized TPU material is not crystallized, the product has better elasticity at low temperature, the loss factor at 0 ℃ is high, namely, the wet skid resistance is good, and meanwhile, the loss factor at 60 ℃ is very low, which indicates that the material has lower rolling resistance at the same time, and the TPU material capable of well balancing the magic triangle problem is obtained by combining the excellent wear resistance of polyurethane;
2. the PPDI or NDI adopted by the invention is a hard segment, the structure is symmetrical, the regularity is good, and the obtained TPU material still has good high temperature resistance under the condition of lower hard segment content;
3. The nanoparticle filler adopted by the invention has excellent photo-thermal effect, and can well generate high heat under near infrared light, so that the hydrogen bond self-repairing of the TPU composite material is realized, meanwhile, the addition of the nanoparticles does not influence the 60 ℃ loss factor of the material, and the problem that the rolling resistance of the existing self-repairing tire is generally higher is solved;
4. The preparation method adopted by the TPU is water removal-prepolymerization-chain extension-post curing, the blending of the TPU and the nano particles is completed through simple banburying, the process is simple, the repeatability is good, and meanwhile, the TPU and the composite material thereof can be circularly processed for multiple times, so that the TPU is environment-friendly.
Drawings
FIG. 1 is an infrared spectrum of a thermoplastic polyurethane elastomer of examples 1 to 3. The infrared spectra of the three thermoplastic polyurethane elastomers are substantially similar. Characteristic peaks of carbonyl groups (v (c=o)) and hydrogen bonding NH stretching vibration peaks (v (NH)) were observed at about 1700 and 3300cm -1, respectively, and stretching vibration of isocyanate groups (NCO) belonging to PPDI was not observed at 2270cm -1, indicating that all isocyanate groups reacted during polymerization, successfully synthesizing the TPU material.
FIG. 2 shows the results of DMA test of the thermoplastic polyurethane elastomers of examples 1 to 3. Examples 1 to 3 have values of Tan delta at 0℃of 0.434, 0.440 and 0.411, respectively, and Tan delta at 60℃of 0.056, 0.053 and 0.052, respectively.
FIG. 3 shows TMA test results of the thermoplastic polyurethane elastomers of examples 1 to 3. TMA results show that the softening point temperatures T (ε＝5％) of the three samples of examples 1-3 are 142.8 ℃, 165.2 ℃ and 195.3 ℃ respectively, which shows that the TPU material has good heat resistance, and the heat resistance of the TPU material is obviously improved along with the increase of the average hard segment length.
FIG. 4 is a schematic view of the self-healing effect of the thermoplastic polyurethane elastomer composite of example 5. Example 5 was prepared to give a1 cm. Times.1 cm. Times.0.1 cm sample (a); cutting the sample from the middle, and destroying the sample; splicing the cut sample pieces together (c); and (d) irradiating for 1min under near infrared light, and healing the separated sample pieces to restore the original state.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The test instruments and test conditions used in the examples are as follows:
Infrared testing: using ATR mode, the wave number is 4000-600 cm -1, and the resolution is 4cm -1;
DSC analysis: the temperature of the sample is reduced from 25 ℃ to 100 ℃ under the nitrogen atmosphere, the temperature is kept for 5min, and then the temperature is increased from 100 ℃ to 200 ℃ at the temperature increasing and decreasing speed of 10 ℃/min;
DMA analysis: strain 0.1%, frequency 10Hz, heating rate 3 ℃/min, test temperature range-90 ℃ to 110 ℃ stretching mode;
TMA analysis: the test probe is cylindrical, a constant external force of 1N is applied, and the temperature is from room temperature to 260 ℃ at 5 ℃/min;
Mechanical property test: the stretching rate is 500mm/min, and the sample size is 25mm by 4mm by 1mm;
Shore a hardness: GB/T531.1-2008.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
Example 1: preparation of thermoplastic polyurethane elastomer
A TPU-1 having a hard segment content of 10.0% was synthesized from a commercially available polycarbonate diol PCDL having a molecular weight of 2000 as soft segment, p-phenylene diisocyanate PPDI and 1, 4-butanediol BDO as hard segment, as example 1.
The preparation process comprises the following steps:
① 50g of PCDL is added into a reaction vessel, and water is removed for 1.5 hours under the conditions of 110 ℃ and-0.097 MPa and 100rpm, so that the water in the raw materials is removed;
② Copolymerizing the dehydrated PCDL with 5g of PPDI, and copolymerizing for 0.5h under the conditions of 75 ℃ and the rotating speed of 150rpm and normal pressure to obtain an isocyanate terminated prepolymer;
③ Adding 0.56g BDO for chain extension, and carrying out chain extension for 10min at 90 ℃ and 300rpm under normal pressure to obtain polyurethane product;
④ And heating the polyurethane in an oven at 100 ℃ for 24 hours to obtain the final polyurethane elastomer.
Example 2: preparation of thermoplastic polyurethane elastomer
Example 2 was a TPU-2 having a hard segment content of 12.5% and having a commercially available polycarbonate diol PCDL of molecular weight 2000 as soft segments and PPDI and BDO as hard segments.
The preparation process comprises the following steps:
① 50g of PCDL is added into a reaction vessel, and water is removed for 1.5 hours under the conditions of 110 ℃ and-0.097 MPa and 100rpm, so that the water in the raw materials is removed;
② Copolymerizing the dehydrated PCDL with 6g of PPDI, and copolymerizing for 0.5h under the conditions of 75 ℃ and the rotating speed of 150rpm and normal pressure to obtain an isocyanate terminated prepolymer;
③ Adding 1.13g BDO to carry out chain extension, and carrying out chain extension for 10min at 90 ℃ and 300rpm under normal pressure to obtain polyurethane product;
④ And heating the polyurethane in an oven at 100 ℃ for 24 hours to obtain the final polyurethane elastomer.
Example 3: preparation of thermoplastic polyurethane elastomer
A commercially available polycarbonate diol PCDL with a molecular weight of 2000 was used as soft segment, PPDI and BDO as hard segment, and TPU-3 with a hard segment content of 15.0% was synthesized as example 3.
The preparation process comprises the following steps:
① 50g of PCDL is added into a reaction vessel, and water is removed for 1.5 hours under the conditions of 110 ℃ and-0.097 MPa and 100rpm, so that the water in the raw materials is removed;
② Copolymerizing the dehydrated PCDL with 6.72g of PPDI, and copolymerizing for 0.5h at 75 ℃ and a rotating speed of 150rpm under normal pressure to obtain an isocyanate terminated prepolymer;
③ Adding 1.62g BDO to carry out chain extension, and carrying out chain extension for 10min at 90 ℃ and 400rpm under normal pressure to obtain polyurethane product;
④ And heating the polyurethane in an oven at 100 ℃ for 24 hours to obtain the final polyurethane elastomer.
Example 4: preparation of thermoplastic polyurethane elastomer
TPU-4, having a hard segment content of 15.3%, was synthesized as example 4 using a commercially available polycarbonate diol PCDL of molecular weight 2000 as the soft segment and NDI and BDO as the hard segments.
The preparation process comprises the following steps:
① 50g of PCDL is added into a reaction vessel, and water is removed for 1.5 hours under the conditions of 110 ℃ and-0.097 MPa and 100rpm, so that the water in the raw materials is removed;
② Copolymerizing the dehydrated PCDL with 7.88g NDI, and copolymerizing for 2.5 hours at 90 ℃ and a rotating speed of 150rpm under normal pressure to obtain an isocyanate-terminated prepolymer;
③ Adding 1.13g BDO to carry out chain extension, and carrying out chain extension for 0.5h at the temperature of 95 ℃ and the rotating speed of 400rpm under the normal pressure condition to obtain the product polyurethane;
④ And heating the polyurethane in an oven at 100 ℃ for 24 hours to obtain the final polyurethane elastomer.
Example 5: preparation of thermoplastic polyurethane elastomer composite
Based on 100phr of thermoplastic polyurethane elastomer TPU-3 prepared in example 3, 3phr of nano-Fe 3O4 (particle size 150 to 250 nm) are added as in example 5. Firstly, TPU-3 is added into a Hash internal mixer, banburying is carried out for 3min at 150 ℃ and 60rpm, then nano-Fe 3O4 with metered parts is added, banburying is carried out for 5min at 60rpm, and then the process is finished.
Example 6: preparation of thermoplastic polyurethane elastomer composite
Based on 100phr of thermoplastic polyurethane elastomer TPU-3 prepared in example 3, 6phr of nano-Fe 3O4 are added as in example 6. Firstly, TPU-3 is added into a Hash internal mixer, banburying is carried out for 3min at 160 ℃ and 60rpm, then nano-Fe 3O4 with metered parts is added, banburying is carried out for 5min at 60rpm, and then the process is finished.
Example 7: preparation of thermoplastic polyurethane elastomer composite
9Phr of nano-Fe 3O4 were added to give example 7 based on 100phr of thermoplastic polyurethane elastomer TPU-3 prepared in example 3. Firstly, TPU-3 is added into a Hash internal mixer, banburying is carried out for 3min at 170 ℃ and 60rpm, then nano-Fe 3O4 with metered parts is added, banburying is carried out for 5min at 60rpm, and then the process is finished.
Comparative example 1
The test was carried out using a commercially available TPU product (Korschuang 8785A), hot-pressed at 180℃for 10min, and hot-pressed to form.
Comparative example 2
The test was carried out using a commercially available TPU product (Langsheng PR 860), hot-pressed at 180℃for 10min, and hot-pressed to shape.
Tables 1 to 3 show the results of performance tests on the thermoplastic polyurethane elastomer composites prepared in examples 1 to 7 and the commercially available TPUs used in comparative examples 1 to 2.
TABLE 1 mechanical test results for examples 1 to 7 and comparative examples 1 to 2
TABLE 2 DMA test results of examples 1-6 and comparative examples
| Tg,SD/℃ | Tanδmax | 0℃Tanδ | 60℃Tanδ | |
| Example 1 | -8.6 | 0.676 | 0.434 | 0.056 |
| Example 2 | -9.3 | 0.690 | 0.440 | 0.053 |
| Example 3 | -9.9 | 0.637 | 0.411 | 0.052 |
| Example 4 | -9.3 | 0.599 | 0.421 | 0.042 |
| Example 5 | -9.9 | 0.638 | 0.417 | 0.051 |
| Example 6 | -9.9 | 0.637 | 0.416 | 0.052 |
| Example 7 | -10.0 | 0.632 | 0.409 | 0.050 |
| Comparative example 1 | -14.4 | 0.404 | 0.229 | 0.054 |
| Comparative example 2 | -12.3 | 0.587 | 0.344 | 0.049 |
TABLE 3 TMA test results for examples 1-6 and comparative example
| T(ε＝5％)/℃ | T(ε＝10％)/℃ | T(ε＝20％)/℃ | |
| Example 1 | 142.8 | 146.8 | 151.8 |
| Example 2 | 165.2 | 171.0 | 179.8 |
| Example 3 | 195.3 | 199.8 | 204.3 |
| Example 4 | 204.2 | 209.0 | 214.1 |
| Example 5 | 192.3 | 198.4 | 203.1 |
| Example 6 | 194.5 | 199.3 | 203.9 |
| Example 7 | 193.6 | 198.9 | 203.6 |
| Comparative example 1 | 185.6 | 189.0 | 190.6 |
| Comparative example 2 | 187.3 | 189.1 | 193.6 |
As can be seen from the mechanical test results in Table 1, the 100% elongation and 300% elongation of the three samples of examples 1 to 3 are both enhanced with the increase of the hard segment content, and the breaking strength and the breaking elongation of the samples are both higher values. As can be seen from the DMA test results in Table 2, the three samples of examples 1 to 7 have high loss factors at 0℃and show that the samples have good wet skid resistance, and also have very low loss factors at 60℃and lower rolling resistance. In addition, TMA results in table 3 indicate that the samples have high heat resistance; the softening point temperature value shows that the heat resistance of the sample is well enhanced along with the increase of the content of the hard segment, and the heat resistance of the NDI group TPU is better than that of the PPDI group under the same content of the hard segment.
The result shows that the PPDI-based and NDI-based thermoplastic polyurethane elastomer synthesized by the invention has high heat resistance under the condition of lower hard segment content, can solve the restriction of the devil triangle of the tire, can be used as tire materials, can be recycled, and is beneficial to environmental protection. The mechanical properties and wet skid resistance of the polyurethane elastomers synthesized in accordance with the invention are better than those of the two commercial TPUs of comparative examples 1 and 2, and the heat resistance of examples 3 and 4 is also better than that of comparative examples 1 and 2. Example 5 is based on example 3 with the addition of 3phr of nano-Fe 3O4. The Tan delta value of the composite material obtained in the example 5 at 0 ℃ and 60 ℃ has no obvious change, which shows that the addition of nano-Fe 3O4 does not influence the wet skid resistance and the rolling resistance of the material.
The thermoplastic polyurethane elastomer prepared in example 5 was prepared into 1cm×1cm×0.1cm specimens, which were cut off from the middle, irradiated with near infrared light for 1min (the temperature can reach 150 ℃), the separated specimens were healed, the original state was recovered, and each performance test was performed on the recovered specimens (recovered specimens), and the test results are shown in tables 4 to 6.
TABLE 4 mechanical test results of example 5 and recovery samples
TABLE 5 DMA test results for example 5 and recovery samples
| Tg,SD/℃ | Tanδmax | 0℃Tanδ | 60℃Tanδ | |
| Example 5 | -9.9 | 0.638 | 0.417 | 0.051 |
| Restoring the sample | -9.9 | 0.633 | 0.418 | 0.050 |
TABLE 6 TMA test results for example 5 and recovery samples
| T(ε＝5％)/℃ | T(ε＝10％)/℃ | T(ε＝20％)/℃ | |
| Example 5 | 192.3 | 198.4 | 203.1 |
| Restoring the sample | 192.3 | 198.3 | 203.2 |
As can be seen from the test results of fig. 4 and tables 4 to 6, the composite material prepared by the embodiment of the invention can realize photo-thermal self-repair by breaking and recombining hydrogen bonds under NIR irradiation, and meanwhile, the original performances of heat resistance, magic triangle and the like of the material can not be damaged.
Claims (10)
1. A high heat-resistant thermoplastic polyurethane elastomer composite material comprises a thermoplastic polyurethane elastomer matrix and a nanoparticle filler, wherein the thermoplastic polyurethane elastomer comprises a soft segment structure formed by polycarbonate compound chain segments and a hard segment structure derived from aromatic isocyanate and chain extender chain segments, and the nanoparticle filler is a nanoparticle with a photo-thermal effect.
2. The composite material of claim 1, wherein the composite material comprises,
The nanoparticle filler is at least one selected from nano-Fe 3O4, MXene and graphene with a photo-thermal effect; and/or the number of the groups of groups,
The particle size of the nanoparticle filler is 50-1000 nm, preferably 100-500 nm.
3. The composite material of claim 1, wherein the thermoplastic polyurethane elastomer comprises:
The polycarbonate compound is a polycarbonate compound with a hydroxyl end group; and/or the number of the groups of groups,
The aromatic isocyanate is aromatic diisocyanate with a symmetrical structure, and is preferably at least one of p-phenylene diisocyanate and 1, 5-naphthalene diisocyanate; and/or the number of the groups of groups,
The chain extender is saturated micromolecular dihydric alcohol, preferably at least one of ethylene glycol, diethylene glycol, triethylene glycol, 1, 3-propylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-butanediol, 1, 3-butanediol, 2, 3-butanediol, neopentyl glycol, 1, 5-pentanediol, 1, 2-pentanediol, diethyl pentanediol, 1, 6-hexanediol and 2-ethyl-1, 3-hexanediol.
4. The composite material of claim 1, wherein the composite material comprises,
The nanoparticle filler is used in an amount of 0 to 15 parts by weight, but not 0, preferably 3 to 10 parts by weight, based on 100 parts by weight of the thermoplastic polyurethane elastomer; and/or the number of the groups of groups,
In the thermoplastic polyurethane elastomer, the content of the soft segment is 70-95%, preferably 80-90%; the hard segment content is 5 to 30%, preferably 10 to 20%.
5. A method of preparing the high heat resistant thermoplastic polyurethane elastomer composite of any one of claims 1 to 4, comprising: and blending the thermoplastic polyurethane elastomer and the nanoparticle filler to obtain the composite material.
6. The preparation method according to claim 5, wherein the method specifically comprises: and melting the thermoplastic polyurethane elastomer, adding the nanoparticle filler, and blending to obtain the composite material.
7. The process according to claim 6, wherein the temperature of melting and blending is 100 to 200 ℃, preferably 120 to 180 ℃.
8. The preparation method according to claim 5, wherein the thermoplastic polyurethane elastomer is prepared by the following method: and (3) after the pre-polymerization reaction of the polycarbonate compound and the aromatic isocyanate, adding a chain extender to perform chain extension reaction, and curing to obtain the thermoplastic polyurethane elastomer.
9. The method according to claim 8, wherein,
The molar ratio of the polycarbonate compound to the aromatic isocyanate to the chain extender is 1: (1.25-2.5): (0.25 to 1.5), preferably 1: (1.5-2.25): (0.5-2.25); and/or the number of the groups of groups,
The molecular weight of the polycarbonate compound is 500-3000, preferably 1000-2000.
10. The method according to claim 8, wherein,
The prepolymerization reaction conditions are as follows: reacting for 0.5-3 h at 70-95 ℃; and/or the number of the groups of groups,
The chain extension reaction conditions are as follows: reacting for 10-60 min at 80-95 ℃; and/or the number of the groups of groups,
The curing reaction conditions are as follows: reacting for 16-24 h at 100-120 ℃; and/or the number of the groups of groups,
The reaction is carried out under a protective gas atmosphere.
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