Composition for suspension chain modified PSE elastomer, suspension chain modified PSE elastomer and preparation method of suspension chain modified PSE elastomer

Abstract

The invention relates to a composition for a suspension chain modified PSE elastomer, the suspension chain modified PSE elastomer and a preparation method of the suspension chain modified PSE elastomer, and belongs to the technical field of high polymer material science and engineering. The composition is prepared from 55 to 75 weight percent of PUSH resin, 14 to 25 weight percent of bisphenol A epoxy resin, 0.3 to 1 weight percent of accelerant and 10 to 25 weight percent of draping chain compound, the drape chain compound is selected from at least one of phenyl glycidyl ether, C12 to C14 glycidyl ether and cardanol glycidyl ether; wherein the PUSH resin is obtained by polymerizing isocyanate, a combination A and 2, 2 '-(1, 2-ethanedioxy) diethanethiol 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 overhanging chain modified 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 modifying a pendant chain modified PSE elastomer, a pendant chain modified 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, 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 and repair 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 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 impairment, sleep interruption, rapid heartbeat, listlessness, etc. In severe cases, symptoms such as a significant reduction or permanent loss of hearing, mental disorder, and endocrine disorders 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 of 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.

[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 pendant-chain modified PSE elastomer, and the pendant-chain modified PSE elastomer provided by the present invention has excellent comprehensive damping performance, especially a wider damping temperature range.

[0007] Another purpose of the present invention is to provide a preparation method of a pendant-chain modified PSE elastomer. The preparation process of this method is simple and suitable for large-scale production.

[0008] To achieve the above purposes, the first aspect of the present invention is to provide a composition for a pendant-chain modified PSE elastomer, which includes the following components by mass percentage: 55-75 wt% of PUSH resin, 14-25 wt% of bisphenol A epoxy resin, 0.3-1 wt% of accelerator, and 10-25 wt% of pendant-chain compound;

[0009] The pendant-chain compound is selected from at least one of phenyl glycidyl ether, C12-C14 alkyl glycidyl ether, and cardanol glycidyl ether;

[0010] Among them, the PUSH resin is obtained by polymerizing isocyanate, combination A, and 2,2'-(1,2-ethylenedioxy)bis(ethanethiol) with a molar ratio of 1:0.4-0.6:0.9-1.1;

[0011] The combination A is polypropylene glycol and polyether triol with a molar ratio of 1:0.3-4.

[0012] The present invention introduces difunctional polypropylene glycol and trifunctional polyether triol into the blended soft segment of the PUSH resin, and adjusts the branching degree of the polyurethane resin by regulating the dosage relationship between the two. An appropriate content of the branched structure helps to increase the resistance to molecular motion, and the system consumes more energy by increasing the molecular motion, thereby improving the damping performance of the material. However, too large a branching degree 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.

[0013] Furthermore, the present invention uses 2,2'-(1,2-ethylenedioxy)bis(ethanethiol) for chain extension and 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, bisphenol A epoxy resin, and an appropriate pendant chain compound are blended, and the ring-opening reaction between the mercapto groups and epoxy groups is used to form a blend crosslinked network of polyurethane and epoxy resin. By controlling the dosage relationship between the difunctional polypropylene glycol and trifunctional polyether triol in the blend 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 the molecular chains to move smoothly and an appropriate frictional resistance. Moreover, due to the presence of the branched structure, an appropriate amount of microphase separation structure will also be formed inside the matrix, which helps the material dissipate energy better during movement. Under the action of these microphase separation structures, the molecular chains are more tightly entangled, and the frictional resistance between the molecular chains and chain segments during movement will also be greater, thereby obtaining a pendant chain modified PSE elastomer with excellent damping performance, especially with a wide damping temperature range.

[0014] Furthermore, one end of the pendant chain compound intersects with the crosslinked network of the polyurethane elastomer, and the other end moves freely in the system. As the number of pendant chains introduced into the main chain increases, the number of branches on the main chain increases, and the complexity of the polymer long chain increases. The probability of mutual friction when the molecular chains and chain segments move also increases. When the pendant chain compound provided by the present invention is introduced into the main chain, corresponding changes occur in the internal structure of the material, such as an increase in the intermolecular distance and an increase in free volume. The chain segments have a larger movement space and a higher collision probability, and these changes are more conducive to energy dissipation. When the molecular chain segments are subjected to an external force, the pendant structure on the main chain will also friction and even entangle with the crosslinked network of the polymer, which will all result in higher energy loss, thereby achieving the purpose of broadening the damping temperature range and increasing the loss factor.

[0015] As a preferred embodiment, the combination A is polypropylene glycol and polyether triol with a molar ratio of 1:0.3 - 3. The inventors have found that in this preferred case, the PSE elastomer provided by the present invention has excellent comprehensive damping performance, especially with a wider damping temperature range.

[0016] As a preferred embodiment, the composition comprises the following components in mass percentage: 55 - 68 wt% of PUSH resin, 14 - 20 wt% of bisphenol A epoxy resin, 0.3 - 1 wt% of accelerator, and 17 - 25 wt% of pendant chain compound.

[0017] As a preferred embodiment, the pendant chain compound is dodecyl to tetradecyl glycidyl ether and / or cardanol glycidyl ether. The inventors have found that the pendant chain modified PSE elastomer prepared under this preferred condition not only has excellent comprehensive damping performance and a wider damping temperature range, but also has excellent comprehensive mechanical properties.

[0018] As a preferred embodiment, the PUSH resin is prepared by a method comprising the following steps:

[0019] (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;

[0020] (2) In the presence of catalyst II, the polyurethane prepolymer and 2,2'-(1,2-ethylenedioxy)bis(ethanethiol) are subjected to a second reaction to obtain the PUSH resin.

[0021] As a preferred embodiment, the protective atmosphere is a nitrogen atmosphere and / or an argon atmosphere.

[0022] As a preferred embodiment, the catalyst I is selected from at least one of dibutyltin dilaurate, organic zinc catalyst and organic bismuth catalyst.

[0023] As a preferred embodiment, the catalyst II is an organic base catalyst.

[0024] 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.

[0025] As a preferred embodiment, the conditions of the first reaction include: temperature is 70-90 °C, and time is 2.5-3.5 h.

[0026] As a preferred embodiment, the conditions of the second reaction include: temperature is 70-90 °C, and time is 3.5-6 h.

[0027] As a preferred embodiment, the isocyanate is isophorone diisocyanate and / or dicyclohexylmethane diisocyanate.

[0028] As a preferred embodiment, the number average molecular weight of the polypropylene glycol is 500-2000 g / mol.

[0029] As a more preferred embodiment, the polypropylene glycol is PPG-2000.

[0030] As a preferred embodiment, the number-average molecular weight of the polyether triol is 2000 to 5000 g / mol.

[0031] As a more preferred embodiment, the polyether triol is polyether triol C3050A.

[0032] As a preferred embodiment, the accelerator is 2,4,6-tris(dimethylaminomethyl)phenol.

[0033] As a preferred embodiment, the bisphenol A epoxy resin is bisphenol A epoxy resin E-51.

[0034] The second aspect of the present invention provides a method for preparing a pendant-chain modified PSE elastomer, which is carried out using the components in the composition for pendant-chain modified PSE elastomer described in the first aspect above, and includes:

[0035] Debubbling and mixing PUSH resin, bisphenol A epoxy resin, accelerator and pendant-chain compound under vacuum, and then curing the obtained mixture to obtain the pendant-chain modified PSE elastomer.

[0036] As a preferred embodiment, the conditions for debubbling 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.

[0037] As a preferred embodiment, the conditions for curing treatment include: temperature of 75 - 85 °C and time of 4.5 - 5.5 h.

[0038] The present invention also provides a pendant-chain modified PSE elastomer prepared by the method for preparing a pendant-chain modified PSE elastomer described in the second aspect above.

[0039] Compared with the prior art, the present invention has at least the following advantages:

[0040] The preparation method provided by the present invention is simple, and the pendant-chain modified PSE elastomer provided by the present invention has excellent comprehensive damping performance, especially a wider damping temperature range. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 It is the synthesis route diagram of PUSH resin prepared in Preparation Example 1 of the present invention;

[0042] Figure 2 It is the synthesis route diagram of the pendant-chain modified PSE elastomer of the present invention;

[0043] Figure 3It is the infrared spectrum diagram of PUSH-31 resin;

[0044] Figure 4 In (a) of , it is the peak value of the average loss factor and the average effective damping temperature range diagram of the pendant chain modified PSE elastomer at multiple frequencies, Figure 4 In (b) of , it is the tanδ-T diagram of the pendant chain modified PSE elastomer at 20 Hz. Specific embodiments

[0045] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and 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.

[0046] The following further illustrates the present invention 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 of ordinary skill in the art without creative efforts still fall within the protection scope of the present invention.

[0047] The present invention will be described in detail below through examples. In the following examples, without special instructions, various raw materials and instruments used are commercially available products, and the specific sources of the raw materials are shown in Table 1.

[0048] Table 1

[0049] Drug Name Specification Manufacturer Polypropylene glycol (PPG-2000) Industrial grade Shanghai Titan Scientific Co., Ltd. Polyether polyol (C3050A) Industrial grade Zhuolian Zhichuang High Polymer Materials Technology Co., Ltd. Isophorone diisocyanate (IPDI) 99％ Shanghai Titan Scientific Co., Ltd. 2,2’-(1,2-Ethylenedioxy)bis(ethanethiol) 98％ Shanghai Titan Scientific Co., Ltd. Dibutyltin dilaurate (DBTDL) 95％+ Shanghai Titan Scientific Co., Ltd. 1,5-Diazabicyclo[4.3.0]non-5-ene (DBN) 98％+ Shanghai Titan Scientific Co., Ltd. Bisphenol A epoxy resin (E-51) Industrial grade Nan Ya Electronic Materials (Kunshan) Co., Ltd. Phenyl glycidyl ether (690) Industrial grade Guangzhou Yuanda New Materials Co., Ltd. C12-14 alkyl glycidyl ether (AGE) Industrial grade Guangzhou Yuanda New Materials Co., Ltd. Cardanol glycidyl ether (513) Industrial grade Cardolite Chemical (Zhuhai) Co., Ltd. 2,4,6-Tris(dimethylaminomethyl)phenol (DMP-30) 80％+ Shanghai Titan Scientific Co., Ltd.

[0050] 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.

[0051] The preparation examples of the present invention are used to prepare PUSH resin.

[0052] Preparation Example 1

[0053] (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) are reacted at 80 °C for 3 h to obtain a polyurethane prepolymer;

[0054] (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.

[0055] Figure 1 This is the synthetic route diagram for preparing the PUSH resin in this preparation example.

[0056] The amounts of substances involved in this preparation example are listed in Table 2.

[0057] Table 2

[0058]

[0059] The preparation example of the present invention is used to prepare pendant chain modified PSE elastomers.

[0060] Example 1

[0061] The PUSH resin (PUSH-31), bisphenol A epoxy resin, accelerator (2,4,6-tris(dimethylaminomethyl)phenol, DMP-30) and pendant chain compound 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 operated at 1000 r / min for 10 s, then the rotation speed was increased to 1500 r / min and operated for 100 s, and finally the rotation speed was reduced to 1000 r / min and operated 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 pendant chain modified PSE elastomer of the present invention.

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

[0064] Table 3

[0065]

[0066] Test Example

[0067] Fourier transform infrared spectroscopy characterization: The PUSH resin prepared in the preparation example was subjected to infrared spectroscopy testing using an ALPHA II type Fourier transform infrared spectrometer (produced by Bruker, Germany). Using the test conditions with a resolution of 4 cm -1 in 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 See specifically Figure 3 .

[0068] From Figure 3 it can be seen that the -NCO infrared characteristic peak of PUSH-31 resin 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 in the infrared spectrum -1 , indicating that the PUSH resin has been successfully synthesized.

[0069] Mechanical property test: The mechanical properties of the pendant-chain modified PSE elastomer were characterized by performing uniaxial tensile tests. The pendant-chain modified PSE elastomer prepared in the above examples was sampled according to the GB / T 528-2009 standard, and a TH-8203A tensile testing machine (Suzhou Tuobo Machinery Equipment Co., Ltd.) equipped with a 500N tensile sensor was used to perform uniaxial tensile tests on the cured elastomer samples. At room temperature (25±2°C, 50±10%RH), the dumbbell-shaped specimens were tested at a constant rate of 100 mm / min. The specific results are shown in Table 4.

[0070] Table 4

[0071] Sample Name Tensile strength (MPa) Elongation at break (%) PSE-31 0.120 602.4 PSE-31-AGE 0.201 1687.8 PSE-31-513 0.287 644.7

[0072] Dynamic thermomechanical analysis: The pendant-chain modified PSE elastomer was characterized by a DMA Q800 dynamic thermomechanical analyzer from TA Instruments, 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 1°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 5.

[0073] Table 5

[0074] Sample Average loss factor peak Average effective damping temperature range (°C) PSE-31 0.79 92.5 PSE-31-690 1.32 107.6 PSE-31-AGE 0.87 105.9 PSE-31-513 1.02 112.8

[0075] Figure 4 In (a) of Figure 4Among them, (b) is the tanδ-T graph of the pendant chain modified PSE elastomer at 20 Hz. From the peak value of the average loss factor and the average effective damping temperature range under multi-frequency conditions, combined with the chart information, it can be seen that the damping performance of the pendant chain modified elastomer has been effectively improved compared with the unmodified PSE-31 elastomer. Among them, after being modified with the pendant chain 690 containing a benzene ring, the peak value of the average loss factor of the material has been significantly improved, increasing from 0.79 to 1.32. After being modified with the pendant chain AGE containing a long carbon chain, the average effective damping temperature range of the material has increased from 92.5 °C of the unmodified one to 105.9 °C of the modified one. The average effective damping temperature range of the elastomer modified with the pendant chain 513 having both a benzene ring and a long carbon chain structure in its structure is the largest, being 112.8 °C. Compared with the unmodified elastomer, the increase amplitude of its effective damping temperature range is the largest.

[0076] 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 solution 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 a pendant chain modified PSE elastomer, characterized in that: The invention comprises the following components in percentage by weight: 55-75 wt% of PUSH resin, 14-25 wt% of bisphenol A epoxy resin, 0.3-1 wt% of accelerator and 10-25 wt% of pendant chain compound; The pendant chain compound is selected from at least one of phenyl glycidyl ether, carbon twelve to tetradecyl glycidyl ether and cardanol glycidyl ether; 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. The composition for pendant chain modified PSE elastomer 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. The composition for pendant chain modified PSE elastomer 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 pendant chain modified 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 pendant chain modified 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 pendant chain modified 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 pendant chain modified PSE elastomer, characterized in that: The method is carried out using the components in the pendant chain modified PSE elastomer composition according to any one of claims 1 to 6, comprising: The PUSH resin, bisphenol A epoxy resin, accelerator and pendant chain compound are degassed and mixed under vacuum, and then the obtained mixture is cured to obtain the pendant chain modified PSE elastomer.

8. The method for preparing a pendant chain modified 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 pendant chain modified 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 pendant chain modified PSE elastomer prepared by the method for preparing a pendant chain modified PSE elastomer according to any one of claims 7 to 9.

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