Composition for PSE elastomer, PSE elastomer and preparation method of PSE elastomer

Abstract

The invention relates to a composition for a PSE elastomer, the PSE elastomer and a preparation method of the PSE elastomer, and belongs to the technical field of high polymer material science and engineering. The composition comprises the following components in percentage by mass: 72 to 80 weight percent of PUSH resin, 19 to 28 weight percent of bisphenol A epoxy resin and 0.3 to 1 weight percent of accelerant, wherein the PUSH resin is obtained by polymerizing isocyanate, a combination A and 2, 2 '-(1, 2-ethanedioxy) diethyl mercaptan according to a molar ratio of 1: (0.4-0.6): (0.9-1.1), and the combination A is prepared from polypropylene glycol and polyether triol according to a molar ratio of 1: (0.3-4). The PSE elastomer provided by the invention has excellent comprehensive damping performance and especially has a wider damping temperature range.

Description

Technical Field

[0001] The present invention relates to a composition for PSE elastomer, a PSE elastomer and a preparation method thereof, belonging to the technical field of polymer materials science and engineering. Background Art

[0002] With the continuous development of modern technologies and industries, the types of mechanical equipment used by people are increasing continuously. Subsequently, vibrations, impacts, and frictions, etc. will affect the normal operation of the equipment, exacerbate the fatigue wear of the equipment, shorten the service life of the equipment, and increase the maintenance investment of the equipment. In addition, vibrations will also cause some parts in the mechanical equipment to become loose, affecting the stability during the use of the instrument, and even endangering the personal safety of the user seriously in severe cases. Moreover, the noise generated during the operation of the equipment will not only affect people's daily work, but also cause harm to people's physical and mental health. Research shows that working in a noisy environment for a long time will cause varying degrees of harm to the human body, showing conditions such as hearing function damage, sleep interruption, rapid heartbeat, listlessness, etc. In severe cases, symptoms such as a significant decrease or permanent loss of hearing, mental disorder, and endocrine disorder will occur.

[0003] In order to reduce the hazards caused by vibrations and noises, damping materials are often used to reduce mechanical vibrations and absorb noises. A damping material is a vibration attenuation material that uses the damping energy dissipation mechanism to reduce or even eliminate vibrations during the transmission of vibrations. It can convert the mechanical vibration energy generated during the vibration process into other forms of energy such as heat energy and electrical energy and dissipate the energy, thereby reducing the impact brought by vibrations and noises. Polymer-based viscoelastic damping materials are widely used in the research and development and use of damping materials due to their unique viscoelasticity. Among them, polyurethane is widely used in various fields due to its diverse raw material types, flexible and easy-to-design molecular structure, stable damping performance, and controllable preparation, etc.

[0004] Generally speaking, the damping performance of polyurethane viscoelastic damping materials is mainly reflected in its glass transition region. However, the glass transition temperature region of a single-component polyurethane is relatively narrow, and the effective damping temperature range (tanδ≥0.3) is generally only 20 - 30°C, which cannot meet the actual application requirements.

[0005] Due to the generally poor damping performance of traditional polyurethane elastomers, there are problems such as a not-high peak value of the loss factor and a narrow effective damping temperature range, which limit their application in various fields. Therefore, it is necessary to modify polyurethane to improve its comprehensive damping performance to meet the application requirements of specific fields. Summary of the Invention

[0006] Aiming at the problems existing in the above-mentioned prior art, one of the purposes of the present invention is to provide a PSE elastomer. The PSE elastomer provided by the present invention has excellent comprehensive damping performance, especially a wider damping temperature range.

[0007] The second object of the present invention is to provide a preparation method of a PSE elastomer. The preparation process of this method is simple and suitable for large-scale production.

[0008] To achieve the above object, the first aspect of the present invention is to provide a composition for a PSE elastomer, comprising the following components by mass percentage: 72-80 wt% of PUSH resin, 19-28 wt% of bisphenol A epoxy resin, and 0.3-1 wt% of accelerator;

[0009] Among them, the PUSH resin is polymerized from isocyanate, combination A, and 2,2'-(1,2-ethylenedioxydioxy)bis(ethyl mercaptan) with a molar ratio of 1:0.4-0.6:0.9-1.1;

[0010] The combination A is polypropylene glycol and polyether triol with a molar ratio of 1:0.3-4.

[0011] In the present invention, by introducing difunctional polypropylene glycol and trifunctional polyether triol into the blended soft segment of the PUSH resin and adjusting the dosage relationship between the two to regulate the degree of branching of the polyurethane resin, an appropriate content of the branched structure helps to increase the resistance to molecular movement. By increasing the molecular movement, the system consumes more energy, thereby improving the damping performance of the material. However, too large a degree of branching and crosslinking density are not conducive to the movement of molecular chains, reducing the energy loss of the matrix and thus weakening the comprehensive damping performance of the material.

[0012] Furthermore, the present invention uses 2,2'-(1,2-ethylenedioxydioxy)bis(ethyl mercaptan) for chain extension and end capping to synthesize a branched polyurethane resin (PUSH resin) with isophorone diisocyanate (IPDI) as the hard segment and mercapto groups at the ends. Then, the PUSH resin and bisphenol A epoxy resin are blended, and the ring-opening reaction between mercapto groups and epoxy groups is used to form a blend crosslinked network of polyurethane and epoxy resin. By controlling the dosage relationship between difunctional polypropylene glycol and trifunctional polyether triol in the blended soft segment, a polymer with an appropriate degree of crosslinking can be obtained. The polymer with an appropriate degree of crosslinking has a space that allows molecular chains to move smoothly and an appropriate frictional resistance. Moreover, due to the existence of the branched structure, an appropriate amount of microphase separation structure will also be formed inside the matrix, which helps the material to better dissipate energy during movement. The molecular chains are more tightly entangled under the action of these microphase separation structures, and the frictional resistance between molecular chains and chain segments during movement will also be greater, thereby obtaining a PSE elastomer with excellent damping performance, especially with a wide damping temperature range.

[0013] As a preferred embodiment, the combination A is polypropylene glycol and polyether triol with a molar ratio of 1:0.3 to 3. The inventors have found that in this preferred case, the PSE elastomer provided by the present invention has excellent comprehensive damping performance, especially a wider damping temperature range.

[0014] As a preferred embodiment, the composition comprises the following components in mass percentage: 73-78 wt% of PUSH resin, 21-27 wt% of bisphenol A epoxy resin, and 0.3-0.8 wt% of accelerator.

[0015] As a preferred embodiment, the PUSH resin is prepared by a method comprising the following steps:

[0016] (1) In the presence of a protective atmosphere and catalyst I, polypropylene glycol, polyether triol and isocyanate are subjected to a first reaction to obtain a polyurethane prepolymer;

[0017] (2) In the presence of catalyst II, the polyurethane prepolymer is subjected to a second reaction with 2,2'-(1,2-ethylenedioxy)bis(ethanethiol) to obtain the PUSH resin.

[0018] As a preferred embodiment, the protective atmosphere is a nitrogen atmosphere and / or an argon atmosphere.

[0019] As a preferred embodiment, the catalyst I is selected from at least one of dibutyltin dilaurate, organic zinc catalyst and organic bismuth catalyst.

[0020] As a preferred embodiment, the catalyst II is an organic base catalyst.

[0021] As a more preferred embodiment, the catalyst II is a diazabicyclic compound. As a most preferred embodiment, the catalyst II is 1,5-diazabicyclo[4.3.0]non-5-ene and / or 1,8-diazabicyclo[5,4,0]undec-7-ene.

[0022] As a preferred embodiment, the conditions of the first reaction include: temperature of 70-90 °C and time of 2.5-3.5 h.

[0023] As a preferred embodiment, the conditions of the second reaction include: temperature of 70-90 °C and time of 3.5-6 h.

[0024] As a preferred embodiment, the isocyanate is isophorone diisocyanate and / or dicyclohexylmethane diisocyanate.

[0025] As a preferred embodiment, the number average molecular weight of the polypropylene glycol is 500-2000 g / mol.

[0026] As a more preferred embodiment, the polypropylene glycol is PPG-2000.

[0027] As a preferred embodiment, the number-average molecular weight of the polyether triol is 2000-5000 g / mol.

[0028] As a more preferred embodiment, the polyether triol is polyether triol C3050A.

[0029] As a preferred embodiment, the accelerator is 2,4,6-tris(dimethylaminomethyl)phenol.

[0030] As a preferred embodiment, the bisphenol A epoxy resin is bisphenol A epoxy resin E-51.

[0031] The present invention also provides a method for preparing a PSE elastomer, which is carried out using the components in the PSE elastomer composition described in the first aspect above, including:

[0032] Defoaming and mixing the PUSH resin, bisphenol A epoxy resin and accelerator under vacuum, and then curing the obtained mixture to obtain the PSE elastomer.

[0033] As a preferred embodiment, the dosage of the PUSH resin is 72-80 wt%, the dosage of the bisphenol A epoxy resin is 19-28 wt%, and the dosage of the accelerator is 0.3-1 wt%.

[0034] As a preferred embodiment, the conditions for defoaming and mixing include: first running at 900-1100 r / min for 8-12 s, then increasing the rotation speed to 1400-1600 r / min and running for 90-110 s, and finally reducing the rotation speed to 900-1100 r / min and running for 8-12 s.

[0035] As a preferred embodiment, the conditions for the curing treatment include: temperature of 75-85 °C and time of 4.5-5.5 h.

[0036] The present invention also provides a PSE elastomer prepared by the method for preparing a PSE elastomer described in the second aspect above.

[0037] Compared with the prior art, the present invention has at least the following advantages:

[0038] The preparation method provided by the present invention is simple, and the PSE elastomer provided by the present invention has excellent comprehensive damping performance, especially a wider damping temperature range. Description of the Drawings

[0039] Figure 1 It is a synthetic route diagram for preparing the PUSH resin in Preparation Example 1 of the present invention;

[0040] Figure 2 This is the synthetic route diagram of the PSE elastomer of the present invention;

[0041] Figure 3 This is the infrared spectrum diagram of the PUSH resin;

[0042] Figure 4 In (a) of [], it is the peak value of the average loss factor of the PSE elastomer at multiple frequencies and the average effective damping temperature range diagram, Figure 4 In (b) of [], it is the tanδ-T diagram of the PSE elastomer at 10 Hz. Detailed implementation manners

[0043] The endpoints and any values within the ranges disclosed herein are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0044] The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the following specific embodiments. Obviously, the embodiments described below are only a part of the embodiments, and all other embodiments obtained by those skilled in the art without creative efforts still fall within the protection scope of the present invention.

[0045] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, various raw materials and instruments used are commercially available products, and the specific sources of the raw materials are shown in Table 1.

[0046] Table 1

[0047]

[0048]

[0049] Note: The number-average molecular weight of PPG-2000 in Table 1 is 2000 g / mol, the number-average molecular weight of C3050A is 3000 g / mol, and PPG-2000, C3050A and DBTDL are used after drying to remove water.

[0050] The preparation examples of the present invention are used to prepare the PUSH resin.

[0051] Preparation Example 1

[0052] (1) In the presence of a nitrogen atmosphere and dibutyltin dilaurate (0.15 g), polypropylene glycol (PPG-2000), polyether triol (C3050A) and isophorone diisocyanate (IPDI) were reacted at 80 °C for 3 h to obtain a polyurethane prepolymer;

[0053] (2) In the presence of 0.30 g of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), the above polyurethane prepolymer was reacted with 2,2'-(1,2-ethanediyl dioxy)bis(ethanethiol) at 80 °C for 4 h to obtain the PUSH resin.

[0054] Figure 1 This is the synthetic route diagram for preparing the PUSH resin in this preparation example.

[0055] The amounts of substances involved in this preparation example are listed in Table 2.

[0056] Unless otherwise specified, the remaining preparation examples were carried out according to the method of Preparation Example 1. The difference is that the amounts of raw materials used in each preparation example are not the same. For specific details, see the cases listed in Table 2.

[0057] Table 2

[0058]

[0059] The preparation examples of the present invention are used to prepare PSE elastomers.

[0060] Example 1

[0061] The PUSH resin, bisphenol A epoxy resin (E-51) and accelerator (2,4,6-tris(dimethylaminomethyl)phenol, DMP-30) were degassed and mixed in a vacuum degassing and dispersing machine. The conditions for the degassing treatment were as follows: The system was evacuated. First, it was run at 1000 r / min for 10 s, then the rotation speed was increased to 1500 r / min and run for 100 s, and finally the rotation speed was reduced to 1000 r / min and run for 10 s. After the instrument stopped rotating, the vacuum state of the system was released to obtain a mixture; then the obtained mixture was spread in a polytetrafluoroethylene mold with a groove depth of 2 mm and placed in a constant temperature air blast drying oven. The temperature of the oven was adjusted to 80 °C for curing treatment and the time was set to 5 h.

[0062] Figure 2 This is the synthetic route diagram for the PSE elastomer of the present invention.

[0063] The types and amounts of substances involved in this example are listed in Table 3.

[0064] Unless otherwise specified, the remaining examples are carried out according to the method of Example 1. The difference is that the types and amounts of raw materials used in each example are not the same. For specific details, refer to the situations listed in Table 3.

[0065] Table 3

[0066] Naming PUSH resin type PUSH resin (dosage / g) E51 resin (dosage / g) DMP-30 (dosage / g) Comparative Example 1 PSE-40 PUSH-40 74.625 24.875 0.5 Example 1 PSE-31 PUSH-31 74.625 24.875 0.5 Example 2 PSE-22 PUSH-22 74.625 24.875 0.5 Example 3 PSE-13 PUSH-13 74.625 24.875 0.5 Comparative Example 2 PSE-04 PUSH-04 74.625 24.875 0.5

[0067] Since the sample after mixing PUSH-40 resin and E-51 resin cannot be cured into a film, PSE-40 elastomer does not participate in the subsequent characterization and testing.

[0068] Test Example

[0069] Fourier transform infrared spectroscopy characterization: The PUSH resin prepared in the preparation example was tested by an ALPHA II type Fourier transform infrared spectrometer (produced by Bruker Corporation, Germany) for infrared spectroscopy. Using the test conditions with a resolution of 4 cm -1 under the total reflection mode, the sample was scanned 64 times, and the scanning range of the spectrum was: 4000 cm -1 to 500 cm -1 .

[0070] Figure 3 is the infrared spectrum of the PUSH resin. It can be seen from the figure that in the PUSH resin, the -NCO infrared characteristic peak at 2260 cm -1 has completely disappeared, indicating that IPDI has been fully reacted. The most significant stretching vibration peak of the mercapto group (-SH) in the resin appears at 2560 cm -1 in the infrared spectrum, indicating that the PUSH resin has been successfully synthesized.

[0071] Dynamic thermomechanical analysis: The PSE elastomer was characterized by a DMA Q800 dynamic thermomechanical analyzer from TA Instrument Company, USA. The material was tested in the tensile mode, using the dynamic frequency-varying temperature scanning mode, with a scanning temperature range of -80 to 100 °C, a heating rate of 3 °C / min, and the frequencies used were 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 Hz. The specific results are shown in Table 4.

[0072] Table 4

[0073] Sample Average loss factor peak Average effective damping temperature range (°C) PSE-31 0.79 92.5 PSE-22 0.83 87.5 PSE-13 0.87 80.3 PSE-04 0.79 56.7

[0074] Figure 4 (a) in is the peak value of the average loss factor and the average effective damping temperature range diagram of the PSE elastomer at multiple frequencies, Figure 4 (b) in is the tanδ-T diagram of the PSE elastomer at 10 Hz. From Figure 4As can be seen from (a) in the figure, the PSE elastomer material provided by the present invention has a larger peak value of the average loss factor at multiple frequencies and a wider average effective damping temperature range.

[0075] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A composition for PSE elastomer, characterized in that: The invention comprises the following components in percentage by weight: 72-80 wt % of PUSH resin, 19-28 wt % of bisphenol A epoxy resin and 0.3-1 wt % of accelerator; The PUSH resin is obtained by polymerizing isocyanate, combination A and 2,2'-(1,2-ethylenedioxy)bis(ethylenethiol) in a molar ratio of 1:0.4-0.6:0.9-1.1; The combination A is polypropylene glycol and polyether triol in a molar ratio of 1:0.3-4.

2. A PSE elastomer composition according to claim 1, characterized in that: The PUSH resin is prepared by a method comprising the following steps: (1) in the presence of a protective atmosphere and a catalyst I, subjecting polypropylene glycol, a polyether triol and an isocyanate to a first reaction to obtain a polyurethane prepolymer; (2) In the presence of catalyst II, the polyurethane prepolymer is subjected to a second reaction with 2,2'-(1,2-ethylenedioxy)bis(ethylenethiol) to obtain the PUSH resin.

3. A PSE elastomer composition according to claim 2, characterized in that: The catalyst I is selected from at least one of dibutyltin dilaurate, an organic zinc catalyst and an organic bismuth catalyst; And / or, the catalyst II is an organic base catalyst.

4. A PSE elastomer composition according to claim 2, characterized in that: The conditions of the first reaction include: temperature of 70-90°C and time of 2.5-3.5h; And / or, the conditions of the second reaction include: temperature of 70-90° C. and time of 3.5-6 h.

5. A PSE elastomer composition according to any one of claims 1 to 4, characterized in that: The isocyanate is isophorone diisocyanate and / or dicyclohexylmethane diisocyanate; And / or, the number average molecular weight of the polypropylene glycol is 500 to 2000 g / mol; And / or, the number average molecular weight of the polyether triol is 2000-5000 g / mol.

6. A PSE elastomer composition according to any one of claims 1 to 4, characterized in that: The accelerator is 2,4,6-tris(dimethylaminomethyl)phenol; And / or, the bisphenol A epoxy resin is bisphenol A epoxy resin E-51.

7. A method for preparing a PSE elastomer, characterized in that: The method is carried out using the components in the PSE elastomer composition according to any one of claims 1 to 6, and comprises: The PUSH resin, bisphenol A epoxy resin and accelerator are degassed and mixed under vacuum, and then the obtained mixture is cured to obtain the PSE elastomer.

8. The method for preparing a PSE elastomer according to claim 7, characterized in that: The degassing mixing conditions include: First run at 900-1100r / min for 8-12s, then increase the speed to 1400-1600r / min and run for 90-110s, and finally reduce the speed to 900-1100r / min and run for 8-12s.

9. The method for preparing a PSE elastomer according to claim 7 or 8, characterized in that: The curing treatment conditions include: a temperature of 75 to 85° C. and a time of 4.5 to 5.5 hours.

10. A PSE elastomer prepared by the method for preparing a PSE elastomer according to any one of claims 7 to 9.

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