Ultrahigh damping type polyurethane elastomer shock insulation support and preparation method thereof
By using a polyurethane material combining closed isocyanate and hexahydroxy polyether with polyester polyol to form a tightly interpenetrating network structure, the problem of poor tensile strength and weather resistance of natural rubber bearings under high hardness is solved, achieving ultra-high damping performance and stability.
Patent Information
- Application Number
- CN202512024908.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-30
- Publication Date
- 2026-02-27
AI Technical Summary
Existing natural rubber seismic isolation bearings are difficult to simultaneously possess excellent tensile strength and elongation at break under high hardness conditions, and their poor weather resistance and aging resistance lead to unstable mechanical properties after long-term use.
Polyurethane materials combining closed isocyanate and hexahydroxy polyether with polyester polyol improve damping performance by forming a tight interpenetrating network structure and intermolecular hydrogen bonding, and ensure material homogeneity by controlling reaction conditions.
While maintaining excellent mechanical properties, polyurethane seismic isolation bearings have achieved ultra-high damping performance and improved weather resistance, solving the aging problem of natural rubber bearings and improving the stability and service life of the materials.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of polyurethane elastomer, in particular to a super high damping polyurethane elastomer isolation bearing and a preparation method thereof. BACKGROUND
[0002] The widely used isolation device is a laminated rubber isolation bearing, which uses the horizontal performance of the bearing to prolong the natural period of the structure, avoid the high energy frequency band of the seismic wave, and achieve the purpose of reducing the seismic energy input of the structure and reducing the seismic response of the structure. The structure of the laminated rubber isolation bearing is composed of multiple layers of steel plates and rubber alternately stacked. The stacking of rubber and steel plates can change the small vertical stiffness of the rubber body, so that it can not only reduce the horizontal seismic action, but also withstand a large vertical load. The commonly used laminated rubber bearing is a natural rubber bearing, a lead rubber bearing and a high damping rubber bearing. The main rubber used in the rubber part of the three bearings is natural rubber. Natural rubber has good elasticity, but due to the limitations of the internal molecular structure of natural rubber, it is difficult to achieve excellent tensile strength and elongation at break while achieving high hardness, and it also provides large damping performance. In addition, natural rubber has poor weather resistance and poor aging resistance, and after long-term use, cracks and unstable mechanical properties of the isolation bearing may occur due to material aging.
[0003] The polyurethane material itself has high hardness and excellent mechanical properties. SUMMARY
[0004] Therefore, the purpose of the present application is to provide a super high damping polyurethane elastomer isolation bearing, which comprises the following components by mole:
[0005] 100 parts of blocked isocyanate, 15-25 parts of hexahydroxy polyether, 15-25 parts of polyester, 10-20 parts of chain extender, 0.1-0.5 parts of catalyst and 0.5-5 parts of initiator.
[0006] Preferably, the blocked isocyanate is diethylamine siloxane-terminated toluene diisocyanate. The blocked isocyanate is stable at a lower temperature and does not react with hydroxyl or amino groups. When the temperature rises to the unblocking temperature, the free isocyanate is released and reacts with hydroxyl or amino groups to form urethane.
[0007] More preferably, the preparation method of the diethylamine siloxane-terminated toluene diisocyanate comprises the following steps:
[0008] Vacuumize toluene diisocyanate at 40-50℃ under nitrogen protection for 1-2h, add diethylamine siloxane drop by drop, stir for 2-4h until it becomes a light yellow paste, take out the paste and place it in a vacuum drying box at 40-45℃ for 24-48h of vacuum drying to obtain diethylamine siloxane-terminated isocyanate;
[0009] The molar ratio of the toluene diisocyanate to the diethylamine siloxane is 1:2-2.1.
[0010] Preferably, the molecular weight of the hexahydroxyl polyether is 9000-12000. The functionality of the hexahydroxyl polyether is 6, which is obtained by ring-opening polymerization of double pentaerythritol-initiated propylene oxide and ethylene oxide, has six molecular chains, and each molecular chain has a molecular weight of 1500-2000. The hexahydroxyl polyether can react with isocyanate to generate a cross-linked interpenetrating network structure of polyurethane. Due to the six molecular chains, the generated cross-linked interpenetrating network structure is more compact, the mechanical properties of the polyurethane can be improved, the load-bearing capacity of the polyurethane can be increased, and the movement resistance between the molecular chains of the polyurethane elastomer can be greatly increased, so that the polyurethane elastomer has super-high damping performance.
[0011] More preferably, the preparation method of the hexahydroxyl polyether comprises the following steps:
[0012] Potassium hydroxide and metallic potassium are mixed in a molar ratio of 2:1 to obtain an activated catalyst, and then 20-30 molar ratios of double pentaerythritol and 35-45 molar ratios of alkylene oxide are added to generate an anionic polymerization reaction to obtain the hexahydroxyl polyether. The alkylene oxide is a mixture of propylene oxide and ethylene oxide in a molar ratio of 1:1.5.
[0013] Preferably, the polyester is polycaprolactone diol.
[0014] Preferably, the chain extender is 3,3'-dichloro-4,4'diphenyl methane diamine (MOCA). The MOCA can enhance the tensile strength and other mechanical properties of the polyurethane elastomer, balance the toughness technical indexes of tear strength and elongation at break, deformation and impact absorption energy, and shorten the post-curing time in the process.
[0015] Preferably, the catalyst is at least one of dibutyltin dilaurate and stannous octoate. The catalyst can accelerate the reaction and post-curing time of the polyurethane elastomer.
[0016] Preferably, the initiator is benzoyl peroxide (BPO). The initiator can polymerize the double bond in the molecular chain.
[0017] Another object of the present application is to provide a preparation method of the super-high-damping polyurethane elastomer seismic isolation bearing.
[0018] (1) Preparation of the polyurethane elastomer material
[0019] The hexahydroxyl polyether, the polyester, the blocked isocyanate, the chain extender and the catalyst are mixed and stirred at a rotating speed of 3000-5000 r / min for 20-40 min to obtain the polyurethane elastomer material.
[0020] (2) Preparation of polyurethane elastomer shock-absorbing support
[0021] The polyurethane elastomer shock-absorbing support is obtained by pouring the polyurethane elastomer material into a mold, demolding after reaction at 150-170 DEG C for 60-90 min, and then curing at 70-90 DEG C for 24-48 h.
[0022] In the present application, the soft segment part of the polyurethane is mixed with hexahydroxy polyether polyol and polyester polyol. The polyether polyol is good in water resistance and molecular chain flexibility, but low in tensile strength. The polyester polyol is good in heat resistance and high in tensile strength, but not resistant to water. The combination of the two can solve the problem of water resistance of the polyester polyol and the problem of poor mechanical properties of the polyether polyol. In addition, the hexahydroxy polyether polyol gives the material a multi-arm structure. The existence of the multi-arm structure enables the formation of an interpenetrating network structure in the polyurethane structure, increases the intermolecular entanglement, and the hydrogen bonding between the polyester polyol molecules can increase the intermolecular force. The combination of the two increases the viscoelasticity of the material, and gives the support excellent damping performance under the premise of excellent mechanical properties.
[0023] Compared with the prior art, the present application has the following beneficial effects:
[0024] (1) The soft segment of the polyurethane in the present application is mixed with hexahydroxy polyether polyol and polyester polyol. The multi-arm structure enables the formation of a more compact and complex interpenetrating network structure in the polyurethane structure, greatly increases the intermolecular entanglement, and the hydrogen bonding between the polyester polyol molecules can increase the intermolecular force. The combination of the two increases the viscoelasticity of the material and gives the material excellent damping performance.
[0025] (2) The hard segment of the polyurethane in the present application uses a blocked isocyanate, which is low in sensitivity to humidity. The isocyanate and hydroxyl groups do not react at room temperature. The blocking of the isocyanate needs to be removed at high temperature for the reaction to proceed. The use of this material makes the reaction controllable, the polymer viscosity and molecular chain can grow smoothly, prevents the formation of gels during the reaction process, and improves the uniformity of the product. DETAILED DESCRIPTION
[0026] The present application will be further described below in conjunction with examples.
[0027] Example 1
[0028] A preparation method of a super-high-damping polyurethane elastomer shock-absorbing support is as follows:
[0029] (1) Preparation of blocked isocyanate
[0030] 100 moles of toluene diisocyanate were vacuumed at 50°C for 1 hour under nitrogen protection, 205 moles of diethylamine siloxane were added dropwise under nitrogen protection, and the reaction was stirred for 2 hours until it became a light yellow paste. The paste was taken out and placed in a vacuum drying oven at 40°C for 48 hours to obtain diethylamine siloxane-terminated isocyanate, which was sealed for later use;
[0031] (2) Preparation of hexahydroxyl polyether
[0032] Under the action of 2 moles of potassium hydroxide and metal potassium bimetallic catalyst and 1 mole of activated catalyst, anionic polymerization reaction occurred between 20 moles of dipentaerythritol and 35 moles of propylene oxide and ethylene oxide to prepare about 20 moles of hexahydroxyl polyether;
[0033] (3) Preparation of polyurethane elastomer material
[0034] 20 moles of hexahydroxyl polyether, 20 moles of polyester (polycaprolactone diol), 100 moles of blocked isocyanate, 20 moles of chain extender (3,3'-dichloro-4,4'-diphenyl methane diamine), 0.2 moles of catalyst (stannous octoate), and 0.3 moles of initiator (BPO) were mixed and stirred at a speed of 3000 r / min for 20 min to obtain polyurethane elastomer material;
[0035] (4) Molding of polyurethane elastomer seismic isolation bearing
[0036] The polyurethane elastomer material was quickly poured into a mold, reacted at 150°C for 90 min, demolded, and then aged at 70°C for 48 h to obtain the finished product.
[0037] Example 2
[0038] A preparation method of an ultrahigh damping type polyurethane elastomer seismic isolation bearing, the steps are as follows:
[0039] (1) Preparation of blocked isocyanate
[0040] 100 moles of toluene diisocyanate were vacuumed at 50°C for 1 hour under nitrogen protection, 205 moles of diethylamine siloxane were added dropwise under nitrogen protection, and the reaction was stirred for 3 hours until it became a light yellow paste. The paste was taken out and placed in a vacuum drying oven at 40°C for 48 hours to obtain diethylamine siloxane-terminated isocyanate, which was sealed for later use;
[0041] (2) Preparation of hexahydroxyl polyether
[0042] Under the action of 2 moles of potassium hydroxide and metal potassium bimetallic catalyst and 1 mole of activated catalyst, anionic polymerization reaction occurred between 20 moles of dipentaerythritol and 35 moles of propylene oxide and ethylene oxide to prepare about 20 moles of hexahydroxyl polyether;
[0043] (3) Preparation of polyurethane elastomer materials
[0044] 25 moles of hexahydroxy polyether, 15 moles of polyester, 100 moles of blocked isocyanate, 10 moles of chain extender, 0.4 moles of catalyst (stannous octoate), and 0.1 moles of initiator were mixed and stirred at 4000 r / min for 30 min to obtain a polyurethane elastomer material.
[0045] (4) Molding of polyurethane elastomer seismic isolation bearings
[0046] The polyurethane elastomer material is quickly poured into a mold, reacted at 160°C for 60 minutes, demolded, and then cured at 80°C for 36 hours to obtain the finished product.
[0047] Example 3
[0048] A method for preparing an ultra-high damping polyurethane elastomer seismic isolation bearing, comprising the following steps:
[0049] (1) Preparation of blocked isocyanates
[0050] 100 moles of toluene diisocyanate were vacuumed at 50°C under nitrogen protection for 1 hour. 205 moles of diethylamine siloxane were added dropwise under nitrogen protection and stirred for 4 hours until a pale yellow slurry was formed. The slurry was then removed and placed in a vacuum drying oven at 40°C for 48 hours to obtain diethylamine siloxane-terminated isocyanate, which was then sealed for later use.
[0051] (2) Preparation of hexahydroxy polyether
[0052] Approximately 15 moles of hexahydroxy polyether were prepared by anionic polymerization of 15 moles of dipentaerythritol and 45 moles of propylene oxide and ethylene oxide under the action of 2 moles of potassium hydroxide and 1 mole of potassium bimetallic catalysis and activation catalyst.
[0053] (3) Preparation of polyurethane elastomer materials
[0054] 15 moles of hexahydroxy polyether, 25 moles of polyester, 100 moles of blocked isocyanate, 30 moles of chain extender, 0.5 moles of catalyst (stannous octoate), and 0.5 moles of initiator were mixed and stirred at 5000 r / min for 40 min to obtain a polyurethane elastomer material.
[0055] (4) Molding of polyurethane elastomer seismic isolation bearings
[0056] The polyurethane elastomer material is quickly poured into a mold, reacted at 170°C for 60 minutes, demolded, and then cured at 70°C for 48 hours to obtain the finished product.
[0057] Comparative Example 1
[0058] A preparation method of a super-high damping polyurethane elastomer seismic isolation support, steps as follows:
[0059] In comparison with Example 1, the blocked isocyanate is replaced by TDI, and the preparation process of Comparative Example 1 comprises the following steps:
[0060] (1) Preparation of hexahydroxy polyether
[0061] Under the action of 2 moles of potassium hydroxide and 1 mole of activated catalyst of metal potassium bimetallic catalyst, 20 moles of dipentaerythritol and 35 moles of propylene oxide and ethylene oxide undergo anionic polymerization to prepare about 20 moles of hexahydroxy polyether;
[0062] (2) Preparation of polyurethane elastomer material
[0063] 20 moles of hexahydroxy polyether, 20 moles of polyester (polycaprolactone diol), 100 moles of TDI, 20 moles of chain extender (3,3'-dichloro-4,4'diphenyl methane diamine), 0.2 moles of catalyst (stannous octoate), and 0.3 moles of initiator (BPO) are mixed and stirred at a speed of 3000 r / min for 20 min to obtain a polyurethane elastomer material;
[0064] (3) Molding of polyurethane elastomer seismic isolation support
[0065] The polyurethane elastomer material is quickly poured into a mold, and after reaction at 80°C for 60 min, the mold is removed, and then the product is obtained after curing at 70°C for 48 h.
[0066] Comparative Example 2
[0067] A preparation method of a super-high damping polyurethane elastomer seismic isolation support, steps as follows:
[0068] In comparison with Example 2, the hexahydroxy polyether is replaced by polyether diol, and the preparation steps are the same as those of Example 2.
[0069] Comparative Example 3
[0070] A preparation method of a super-high damping polyurethane elastomer seismic isolation support, steps as follows:
[0071] In comparison with Example 3, the hexahydroxy polyether is replaced by polyether diol, and the blocked isocyanate is replaced by TDI, and the preparation process of Comparative Example 3 comprises the following steps:
[0072] (1) Preparation of polyurethane elastomer material
[0073] The 15 moles of polyether diol, 25 moles of polyester, 100 moles of blocked isocyanate, 30 moles of chain extender, 0.5 moles of catalyst (stannous octoate), and 0.5 moles of initiator (BPO) are mixed and stirred at a rotation speed of 5000 r / min for 40 min to obtain a polyurethane elastomer material.
[0074] (2) Molding of the polyurethane elastomer shock insulation bearing
[0075] The polyurethane elastomer material is quickly poured into a mold, and after reaction at 80℃ for 60 min, the mold is demolded, and then the product is obtained after curing at 70℃ for 48 h.
[0076] Comparative Example 4
[0077] A preparation method of a super-high-damping polyurethane elastomer shock insulation bearing, compared with Example 1, in which the blocked isocyanate is replaced by TDI, and the preparation steps are the same as those of Example 1.
[0078] Comparative Example 5
[0079] A preparation method of a super-high-damping polyurethane elastomer shock insulation bearing, compared with Example 3, in which the hexahydroxy polyether is replaced by polyether diol, and the blocked isocyanate is replaced by TDI, and the preparation steps are the same as those of Example 3.
[0080] The polyurethane elastomer materials and shock insulation bearings of Examples 1-3 and Comparative Examples 1-3 will be tested:
[0081] (1) The tensile property test is performed according to the standard “Determination of Tensile Stress-Strain Properties of Vulcanized or Thermoplastic Rubber” (GB / T 528-2008);
[0082] (2) The equivalent damping ratio test method is performed according to the standard “Rubber Bearings Part 1: Test Methods for Shock Insulation Rubber Bearings” (GB / T 20688.1-2007).
[0083] The specific performance test results are shown in Table 1.
[0084] Table 1
[0085]
[0086] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered within the scope of protection of the present application.
Claims
1. A high-damping polyurethane elastomer seismic isolation bearing, characterized in that, The components include the following moles: 100 parts blocked isocyanate, 20-30 parts hexahydroxy polyether, 15-25 parts polyester, 10-20 parts chain extender, 0.1-0.5 parts catalyst, and 0.5-5 parts initiator.
2. The ultra-high damping polyurethane elastomer seismic isolation bearing according to claim 1, characterized in that, The blocked isocyanate is diethylamine siloxane-terminated toluene diisocyanate.
3. The ultra-high damping polyurethane elastomer seismic isolation bearing according to claim 2, characterized in that, The preparation method of the diethylamine siloxane-terminated toluene diisocyanate includes the following steps: Toluene diisocyanate was evacuated under nitrogen protection at 40-50℃ for 1-2 hours, and diethylamine siloxane was added dropwise. The mixture was stirred for 2-4 hours until it became a pale yellow slurry. The slurry was then removed and placed in a vacuum drying oven at 40-45℃ for 24-48 hours to obtain diethylamine siloxane-terminated isocyanate. The molar ratio of toluene diisocyanate to diethylamine siloxane is 1:2-2.
1.
4. The ultra-high damping polyurethane elastomer seismic isolation bearing according to claim 1, characterized in that, The molecular weight of the hexahydroxy polyether is 9000~12000.
5. The ultra-high damping polyurethane elastomer seismic isolation bearing according to claim 4, characterized in that, The preparation method of the hexahydroxy polyether includes the following steps: An activation catalyst is obtained by mixing potassium hydroxide and metallic potassium in a molar ratio of 2:
1. Then, 10-15 molar ratio of dipentaerythritol and 35-45 molar ratio of epoxy alkane are added to undergo an anionic polymerization reaction to obtain hexahydroxy polyether. The epoxy alkane is a mixture of propylene oxide and ethylene oxide in a molar ratio of 1:1.
5.
6. The ultra-high damping polyurethane elastomer seismic isolation bearing according to claim 1, characterized in that, The polyester is polycaprolactone diol.
7. The ultra-high damping polyurethane elastomer seismic isolation bearing according to claim 1, characterized in that, The chain extender is 3,3'-dichloro-4,4'-diphenylmethanediamine.
8. The ultra-high damping polyurethane elastomer seismic isolation bearing according to claim 1, characterized in that, The catalyst is at least one of dibutyltin dilaurate and stannous octoate.
9. The ultra-high damping polyurethane elastomer seismic isolation bearing according to claim 1, characterized in that, The initiator is benzoyl peroxide.
10. The method for preparing the ultra-high damping polyurethane elastomer seismic isolation bearing according to claim 1, characterized in that, Includes the following steps: (1) Preparation of polyurethane elastomer materials Hexahydroxy polyether, polyester, blocked isocyanate, chain extender and catalyst are mixed and stirred at 3000-5000 r / min for 20-40 min to obtain polyurethane elastomer material; (2) Preparation of polyurethane elastomer seismic isolation bearings The polyurethane elastomer material is poured into a mold, reacted at 150-170℃ for 60-90 minutes, demolded, and then cured at 70-90℃ for 24-48 hours to obtain the polyurethane elastomer seismic isolation bearing.