Polyurethane-epoxy hybrid microporous elastomer as well as preparation method and application thereof

Abstract

The invention provides a polyurethane-epoxy hybrid microporous elastomer as well as a preparation method and application thereof. The preparation method comprises the following steps: S1, by taking dicyclopentadiene, hydrogen peroxide and formic acid as raw materials, carrying out epoxidation reaction under the catalysis of solid acid resin in the presence of a butanone solvent to prepare dicyclopentadiene-based epoxy resin; s2, dissolving dicyclopentadiene epoxy resin in an epoxy cross-linking agent, uniformly mixing the dicyclopentadiene epoxy resin with first polymer dihydric alcohol subjected to vacuum dehydration, adding isocyanate, and reacting to obtain a component B containing epoxy groups and isocyanate groups at the same time; s3, uniformly mixing second polymer dihydric alcohol, a tertiary amine epoxy curing agent, a chain extender, water and silicone oil to obtain a component A; the tertiary amine epoxy curing agent is also used as a catalyst for a polyurethane curing reaction; and S4, mixing the component A and the component B, injecting the mixture into a mold, and carrying out a curing reaction to form the polyurethane-epoxy hybrid microporous elastomer.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer synthesis and polymer foaming materials, and particularly relates to a polyurethane-epoxy hybrid microporous elastomer, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, the Chinese elevator market has shown a steady growth trend, and the industrial scale has continued to expand. According to relevant data, the global elevator industry market scale is approximately 122.98 billion US dollars, and China is the largest market. The annual elevator sales volume in China is approximately 1 million units, and the average annual growth rate remains between 5% and 8%. This growth is not only due to the acceleration of the urbanization process, the renovation of old communities, the promotion of infrastructure construction, and the increasing demand for elevator updates, but also due to the continuous progress of various subdivision technologies related to elevators and the continuous reduction of costs.

[0003] Elevators are special safety equipment, and polymer buffers are safety components among them. In order to minimize the harm caused by elevator accidents to personnel, the new inspection regulation TSG T7007-2022 was officially released in July 2022, further clarifying and refining the test specifications and requirements for polyurethane buffer components in GB / T 7588-2020. The content includes: after the buffer completes 96-hour damp heat aging at 85°C / 85% RH, the testing agency conducts 10 heavy-load (car self-weight + rated load) and 10 light-load (car self-weight) impact tests on the buffer at a maximum speed not lower than 1.15 m / s. The buffer should have no permanent damage such as cracking. At the same time, it is required that the maximum deceleration of any impact test cannot exceed 6.0g, the rebound speed cannot exceed 1.0 m / s, the average deceleration cannot exceed 1.0g, and the time when the deceleration exceeds 2.5g cannot exceed 0.04s. At the same time, it is required to ensure a service life of more than 10 years.

[0004] The prior art improves the impact resistance and buffering performance of polyurethane buffers by adding mechanical devices to the buffer foam. For example, patent CN201711396082.6 makes the buffer meet the requirements of GB / T 7588-2003 by adding a compressive device to the polyurethane buffer foam. In order to meet the requirements of GB / T7588-2020, patent CN202110958173.4 adds a magnet device to the polyurethane buffer foam, relying on the repulsive force between the magnets to improve the impact resistance and buffering performance of the polyurethane buffer. The above methods are all due to the lack of theoretical support for the raw materials they select and the microstructure of the polyurethane polymer prepared based on the raw materials, resulting in the performance not meeting the relevant standards. Adding auxiliary tooling is a helpless move, which not only increases the product cost but also makes the prepared composite buffer containing auxiliary tooling deviate from the original intention of the country and the elevator industry to promote and apply polyurethane buffers.

[0005] Chinese Patent Publication No. CN110698625A discloses a method for preparing a viscoelastic microporous elastomer. It prepares a microporous elastomer with an IPN structure by hybridizing a polyurethane resin and an epoxy resin, forming a large number of polyurethane networks with excellent deformation recovery ability. It can rely on the special network structure inside the polymer to consume a large amount of external impact energy and has excellent deformation recovery ability. However, the mechanical properties of the technology disclosed in this patent are difficult to meet the requirements of polyurethane buffers for elevators.

[0006] Chinese Patent Application No. CN202310079293.6 discloses a material system with an interpenetrating network structure. However, during the mold curing process of this patent, a release agent needs to be coated to easily demold. The technology disclosed in this patent can meet the impact test of a heavy load of 700 kg, but it is difficult to meet the heavy load impact of 1300 kg.

[0007] In summary, there is still room for improvement in the technology of polymer buffers for elevators. Summary of the Invention

[0008] To overcome or improve the defect of poor performance of polymer buffers for elevators in the above-mentioned prior art and achieve the technical goal by applying pure polymer materials, the first object of the present invention is to provide a method for preparing a polyurethane-epoxy hybrid microporous elastomer; the second object of the present invention is to provide the polyurethane-epoxy hybrid microporous elastomer prepared by this preparation method; the third object of the present invention is to provide the application of this polyurethane-epoxy hybrid microporous elastomer as a buffer material in the preparation of elevator buffers. This material has good demolding processability, high mechanical strength, good buffering performance, and more excellent hydrolysis resistance. Through the double bond oxidation reaction of dicyclopentadiene, a polycyclic aliphatic epoxy compound is obtained, which is mixed and cured with a two-component polyurethane resin to obtain a polyurethane-epoxy hybrid microporous elastomer with an interpenetrating network structure.

[0009] The object of the present invention is achieved by the following technical means:

[0010] On the one hand, the present invention provides a method for preparing a polyurethane-epoxy hybrid microporous elastomer, including the following steps:

[0011] S1: Using dicyclopentadiene, hydrogen peroxide, and formic acid as raw materials, in the presence of a methyl ethyl ketone solvent, an epoxidation reaction is catalyzed by a solid acid resin to prepare dicyclopentadienyl epoxy resin;

[0012] S2: Dissolve the dicyclopentadienyl epoxy resin obtained in S1 in an epoxy crosslinking agent, mix it evenly with the first polymer diol that has been vacuum dehydrated, add isocyanate, and after reaction, obtain a B component containing both epoxy groups and isocyanate groups, and the NCO% in the B component is between 4.96% and 16.57%;

[0013] By weight parts, the raw material proportion of the B component is as follows:

[0014]

[0015] S3: Mix the second polymer diol, tertiary amine epoxy curing agent, chain extender, water and silicone oil evenly to obtain the A component; the tertiary amine epoxy curing agent also serves as a catalyst for the polyurethane curing reaction;

[0016] By weight parts, the raw material proportion of the A component is as follows:

[0017]

[0018] S4: Mix the A component and the B component at a weight ratio of (30 - 120):100, inject them into a mold, and form a polyurethane-epoxy hybrid microporous elastomer through a curing reaction.

[0019] Preferably, in step S1, the molar ratio of dicyclopentadiene, hydrogen peroxide and formic acid is 1:2:1.

[0020] Preferably, in step S2, the reaction temperature for adding the isocyanate is 80°C, and the reaction time is 2 h.

[0021] Among them, in step S1, the molar ratio of dicyclopentadiene, hydrogen peroxide and formic acid is 1:2:1.

[0022] Preferably, in step S4, the mold does not need to be coated with a release agent, and debonding from the mold substrate can be achieved by relying on the low surface energy formed by the dicyclopentadienyl structure introduced by the polyurethane-epoxy hybrid microporous elastomer.

[0023] Preferably, the solid acid resin catalyst is a strongly acidic cation exchange resin, and its weight is 5% of the weight of dicyclopentadiene. According to the specific embodiments of the present invention, the strongly acidic cation exchange resin is selected from one of D001 type, D072 type of Elast (Shanghai) New Materials Co., Ltd. or LXP-160 type of Shandong Shoucheng Chemical Co., Ltd.

[0024] In the above preparation method, the main function of the epoxy crosslinking agent is to play a bridging role between molecules during the ring-opening curing of dicyclopentadienyl epoxy, avoiding curing defects caused by the large steric hindrance effect of dicyclopentadienyl epoxy itself. Preferably, the epoxy crosslinking agent is a small molecule epoxy compound with an epoxy group functionality of 1 to 3 or a mixture thereof. As an example, the epoxy crosslinking agent is one or more of butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, glycerol triglycidyl ether, and trimethylolpropane triglycidyl ether.

[0025] Preferably, the first polymer diol is one of polypropylene oxide ether diol, polytetrahydrofuran ether diol, polycaprolactone diol, polytetrahydrofuran ether-polycaprolactone block diol, polyethylene adipate diol, polybutylene adipate diol, polyneopentyl adipate diol, and polyhexylene adipate diol, and the molecular weight of the first polymer diol is 2000 g / mol.

[0026] Preferably, the isocyanate is one of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI).

[0027] Preferably, the second polymer diol is one of polypropylene oxide ether diol, polytetrahydrofuran ether diol, polycaprolactone diol, polytetrahydrofuran ether-polycaprolactone block diol, polyethylene adipate diol, polybutylene adipate diol, polyneopentyl adipate diol, and polyhexylene adipate diol, and the molecular weight of the second polymer diol is 2000 g / mol.

[0028] In the above preparation method, the tertiary amine epoxy curing agent catalyzes the curing and foaming reactions of the polyurethane. Preferably, the tertiary amine epoxy curing agent is selected from one of triethylamine, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0029] Preferably, the chain extender is a small molecule diol selected from one of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and hexylene glycol.

[0030] Preferably, the silicone oil is selected from one of DC193 of Momentive Performance Materials Inc. in the United States and S-9547 of Shanghai Maihao Co., Ltd.

[0031] On the other hand, the present invention also provides a polyurethane-epoxy hybrid microporous elastomer prepared by the preparation method described above. Preferably, the density of the polyurethane-epoxy hybrid microporous elastomer is 450-750 kg / cm 3 .

[0032] On the other hand, the present invention also provides a hybrid polymer microporous elastomer containing dicyclopentadiene, which is applied to the manufacture of pit buffers for low-speed elevators (≤1.0 m / s) to provide maximum protection for internal property when the elevator car undergoes free fall.

[0033] In the present invention, since the dicyclopentadiene structure is an aliphatic polycyclic structure, it naturally has excellent hydrophobicity, which can endow the material surface with low polarity and surface energy, prevent water vapor molecules from adhering, and thus greatly reduce the permeability of small molecules to the material, reducing the occurrence of aging reactions such as hydrolysis that reduce the service life. Therefore, in the selection of the soft segment polyol in the polyurethane reaction, there is more variety. Besides polypropylene oxide ether diol, polytetrahydrofuran ether diol, and polycaprolactone diol with good hydrophobicity, adipic acid-based polyester diol with wide sources can also be selected.

[0034] Dicyclopentadiene is a by-product in the petroleum refining process, with wide sources and low cost. Through the oxidation system of hydrogen peroxide and formic acid, the double bond in its structure can be oxidized to an epoxy group, thus obtaining an epoxide with an aliphatic polycyclic structure. When the B component composed of the epoxide and the polyurethane prepolymer is mixed with the A component composed of the polyol and the tertiary amine curing agent, the thermosetting cross-linking reaction of the epoxide and the thermoplastic chain growth reaction of the isocyanate catalyzed by a large amount of tertiary amine can occur simultaneously. The two curing reactions occur simultaneously, and two different polymer networks of epoxy and polyurethane can be formed in the cured product, thus forming an interpenetrating network structure (IPN). This structure has the following advantages: (1) When the polymer with the IPN structure undergoes compression and recovery due to impact, not only the friction caused by the relative slippage of the molecular chains within and between the same cross-linked network during deformation will occur, but also the friction of the molecular chains between different networks will occur, thus consuming most of the impact energy and converting it into heat energy; (2) The large number of cyclic structures brought by dicyclopentadiene to the cured product network endow the buffer with great rigidity, so that the load upper limit of products of the same model is significantly improved; (3) The large number of aliphatic polycyclic structures in the epoxy cross-linked network provide excellent self-lubricating properties for the buffer material. In the demolding process, even external demolding agents do not need to be coated, protecting the environment and operators. In addition, microscopically, it greatly improves the roughness of the molecular chains in the cross-linked network, increases the friction force when the relative slippage occurs within and between the molecular chains, and significantly improves the mechanical properties and hydrolysis resistance of the buffer material.

[0035] Advantages of the present invention:

[0036] The polyurethane-epoxy hybrid microcellular elastomer material prepared by the present invention has the advantages of hydrolysis resistance, good buffering performance, excellent impact resistance, and good demolding processability. When it is used for the preparation of elevator pit buffers, it can improve the service life of elevator pit buffers and their ability to absorb and dissipate impact energy, and ultimately enhance the protection of property inside the car by the buffer product.

[0037] The hybrid microcellular elastomer prepared by the present invention belongs to a polyurethane-epoxy interpenetrating network structure. The unique dicyclopentadiene structure endows the product with very strong rigidity and energy loss generated by friction between chain segments during deformation, making it very suitable for the performance requirements of buffers used in low-speed elevators (≤1.0 m / s). In addition to meeting the requirements for polyurethane buffers in GB / T 7588-2020, TSG T7007, EN 81-20 / 50, ASME A17.1 and the industry standard T / CEA 0055-2024 in China, it further improves the service life of existing buffers and their ability to absorb and dissipate external impact energy, and ultimately enhances the protection ability of polyurethane buffer products for people and objects inside the car.

[0038] Compared with CN202310079293.6, the aliphatic polycyclic structure of a large amount of dicyclopentadiene in the present invention endows better hydrophobicity than the technology of CN202310079293.6, and its performance retention rate after aging under the "double 85" conditions is higher. In addition, it endows the surface of the product with excellent self-lubricating characteristics, and the mold can be easily demolded without applying a release agent. Description of the Drawings

[0039] Figure 1 It is the test curve of the 5th test in Example 3 under the maximum mass condition;

[0040] Figure 2 It is the test curve of the 4th test in Example 3 under the minimum mass condition;

[0041] Figure 3 It is the aging compression curve of the sample in Example 3. Detailed Description of the Invention

[0042] In order to have a clearer understanding of the technical features, objectives, and beneficial effects of the present invention, the technical solutions of the present invention are described in detail below, but it should not be construed as a limitation on the scope of implementation of the present invention; unless otherwise specified, the raw materials used in the following examples are all obtained through regular commercial channels in the art; unless otherwise specified, the methods used are all conventional preparation methods in the art.

[0043] Example 1

[0044] A preparation method of a polyurethane-epoxy hybrid microcellular elastomer, comprising the following steps:

[0045] S1: Prepare the corresponding raw materials of dicyclopentadiene, hydrogen peroxide and formic acid according to a molar ratio of 1:2:1, which are 20 mol, 40 mol and 20 mol respectively. Use the D001 type solid acid resin of Yilaite Company (weight is 5 wt% of dicyclopentadiene) as the catalyst, and use methyl ethyl ketone with the same weight as the total weight of the liquid reactants (i.e., the total weight of dicyclopentadiene, hydrogen peroxide and formic acid) as the solvent. Put dicyclopentadiene, formic acid, the catalyst and the solvent into a four-necked round-bottom flask. Place the flask in a water bath, and equip it with a stirrer, a thermometer sleeve, a condenser and a dropping funnel for dropping hydrogen peroxide. Under continuous stirring and at a temperature of 50 °C, hydrogen peroxide is added dropwise to the reaction mixture. After the dropping is completed, the temperature is raised to 65 °C and the reaction continues for 5 hours. After the reaction is completed, filter to remove the solid acid resin catalyst, and use a rotary vacuum evaporator to remove the solvent and small molecule substances from the reaction solution at 70 °C, and a total of 2900 g of dicyclopentadienyl epoxy resin is obtained. S2: Take the dicyclopentadienyl epoxy resin obtained in S1 and dissolve it in the epoxy cross-linking agent benzyl glycidyl ether with a functionality of 1, and mix it evenly with the poly(tetrahydrofuran) ether diol that has been vacuum dehydrated. Raise the temperature to 80 °C, add molten p-phenylene diisocyanate and react for 2 h to obtain component B containing both epoxy groups and isocyanate groups, and the NCO% of component B = 16.57%;

[0046] The raw material ratio of the said component B is as follows:

[0047]

[0048] S3: Mix the poly(tetrahydrofuran)-polycaprolactone block diol (Type 7201A of British Paster Company), 2,4,6-tris(dimethylaminomethyl)phenol, water and DC193 evenly according to the following ratio to obtain component A:

[0049]

[0050] According to the molar numbers of the active hydrogen and isocyanate groups of the two components, component A: component B = 120:100 (weight ratio);

[0051] S4: Use a low-pressure two-component foaming machine with a high-speed rotating stirring function to stir and pour the above-mentioned component A and component B according to the ratio of component A: component B = 120:100 (weight ratio) into an iron metal mold without applying a release agent, and rely on the heat released by the dual curing of polyurethane and epoxy to achieve rapid curing and demoulding to obtain a polyurethane-epoxy hybrid microporous elastomer with a density of 750 kg / cm 3 ³.

[0052] Example 2

[0053] A preparation method of a polyurethane-epoxy hybrid microporous elastomer, comprising the following steps:

[0054] S1: The same as in Example 1.

[0055] S2: Take the dicyclopentadienyl epoxy obtained in S1 and dissolve it in the epoxy crosslinking agent trimethylolpropane triglycidyl ether with a functionality of 3, and mix it evenly with the poly(hexamethylene adipate) diol that has been vacuum dehydrated. Heat it up to 80 °C, add the molten 4,4'-diphenylmethane diisocyanate (MDI) and react for 2 h to obtain the B component containing both epoxy groups and isocyanate groups, and the NCO% of the B component = 4.96%.

[0056] The raw material ratio of the said B component is as follows:

[0057]

[0058] S3: Mix the poly(propylene oxide) ether diol, N,N-dimethylbenzylamine, 1,4-butanediol, water, and S-9547 evenly according to the following ratio to obtain the A component:

[0059]

[0060] According to the molar numbers of the active hydrogen and isocyanate groups in the two components, A component: B component = 30:100 (weight ratio);

[0061] S4: Use a low-pressure two-component foaming machine with a high-speed rotating stirring function to stir and pour the above A component and B component according to the ratio of A component: B component = 30:100 (weight ratio) into an iron metal mold without applying a mold release agent, and rely on the heat released by the dual curing of polyurethane and epoxy to achieve rapid curing and demolding to obtain a polyurethane-epoxy hybrid microporous elastomer with a density of 450 kg / cm 3 ³.

[0062] Example 3

[0063] A preparation method of a polyurethane-epoxy hybrid microporous elastomer, comprising the following steps:

[0064] S1 Prepare the corresponding raw materials of dicyclopentadiene, hydrogen peroxide and formic acid in a molar ratio of 1:2:1, with weights of 20 mol, 40 mol, and 20 mol respectively. Use the LXP-160 type solid acid resin of Shoucheng Chemical Co., Ltd. (weight: 5 wt% of dicyclopentadiene) as the catalyst, and use methyl ethyl ketone with the same weight as the total weight of the liquid reactants (i.e., the total weight of dicyclopentadiene, hydrogen peroxide and formic acid) as the solvent. Put dicyclopentadiene, formic acid, the catalyst and the solvent into a four-necked round-bottom flask. The flask is placed in a water bath and equipped with a stirrer, a thermometer sleeve, a condenser and a dropping funnel for dropping hydrogen peroxide. Under continuous stirring and at a temperature of 50 °C, hydrogen peroxide is added dropwise to the reaction mixture. After the addition is complete, the temperature is raised to 65 °C and the reaction continues for 5 hours. After the reaction is completed, filter to remove the solid acid resin catalyst, and use a rotary vacuum evaporator to remove the solvent and small molecule substances from the reaction solution at 70 °C, and a total of 2900 g of dicyclopentadienyl epoxy resin is obtained.

[0065] S2: Take the dicyclopentadienyl epoxy resin obtained in S1 and dissolve it in 1,4-butanediol diglycidyl ether with a functionality of 2, and mix it evenly with the polycaprolactone diol that has been vacuum dehydrated. Raise the temperature to 80 °C, add hexamethylene diisocyanate and react for 2 h to obtain component B containing both epoxy groups and isocyanate groups, and the NCO% of component B = 13.86%;

[0066] The raw material ratio of the said component B is as follows:

[0067]

[0068] S3: Mix polyneopentyl glycol adipate diol, triethylamine, 1,6-hexanediol, water, and S-9547 evenly in the following ratio to obtain component A:

[0069]

[0070] According to the molar numbers of active hydrogen and isocyanate groups in the two components, component A: component B = 100:100 (weight ratio);

[0071] S4: Use a low-pressure two-component foaming machine with a high-speed rotation stirring function to stir and pour the above component A and component B in the ratio of component A: component B = 100:100 (weight ratio) into a metal iron mold without applying a release agent, and rely on the heat released by the dual curing of polyurethane and epoxy to achieve rapid curing and demolding to obtain a polyurethane-epoxy hybrid microporous elastomer with a density of 550 kg / cm 3 ³.

[0072] Example 4

[0073] The present invention provides a method for preparing a polyurethane-epoxy hybrid microporous elastomer, comprising the following steps:

[0074] S1: The same as in Example 3.

[0075] S2: Take the dicyclopentadienyl epoxy obtained in S1 and dissolve it in the epoxy crosslinking agent diglycol diglycidyl ether with a functionality of 2, and mix it evenly with the poly(propylene oxide) ether diol that has been vacuum dehydrated. Heat it to 80 °C, add isophorone diisocyanate and react for 2 h to obtain Component B containing both epoxy groups and isocyanate groups, and the NCO% of Component B = 7.56%.

[0076] The raw material ratio of the said Component B is as follows:

[0077]

[0078] S3: Mix the polytetrahydrofuran ether diol, N,N-dimethylcyclohexylamine, ethylene glycol, water, and DC-193 evenly according to the following ratio to obtain Component A:

[0079]

[0080] According to the molar numbers of the active hydrogen and isocyanate groups in the two components, Component A: Component B = 50:100 (weight ratio);

[0081] S4: Use a low-pressure two-component foaming machine with a high-speed rotating stirring function to stir and pour the above-mentioned Component A and Component B according to the ratio of Component A: Component B = 50:100 (weight ratio) into an uncoated metal iron mold, and rely on the heat released by the dual curing of polyurethane and epoxy to achieve rapid curing and demolding to obtain a polyurethane-epoxy hybrid microporous elastomer with a density of 650 kg / cm 3 of.

[0082] Test experiment:

[0083] Test items: Gauge impact test, 10-week durability aging test

[0084] Gauge impact test: Use the polyurethane-epoxy hybrid microporous elastomers prepared in Examples 1 to 4 above as buffers, age them at 85 °C / 85% RH humidity for 96 h, and perform the test after standing at room temperature for 24 h. Among them, the sample of Example 1 is numbered 1, the sample of Example 2 is numbered 2, the sample of Example 3 is numbered 3, and the sample of Example 4 is numbered 4. Due to the presence of a large number of aliphatic cyclic structures, the rigidity and impact resistance of the buffer prepared by the present invention are significantly improved. Therefore, during the test, under the condition of unchanged light load, the heavy load is increased from the original 700 kg to 1350 kg.

[0085] The free-fall impact test was carried out on the same sample (H80mm*D80mm) with a heavy load (1350kg) weight and a light load (200kg) weight for 10 times (20 times for each sample). A velocity sensor, an acceleration sensor, and a displacement sensor were fixed on the weight to record the relevant data changes during this process. The test was conducted at the National Elevator Testing Center (NETEC) of CABR Machinery Inspection and Testing (Beijing) Co., Ltd., and a special equipment type test report and certificate were obtained. This product is the first product in the world to obtain certifications of GB / T 7588-2020, TSG T-7007, and EN81-20 / 50 simultaneously.

[0086] 10-week durability aging performance test: Inject the A and B components of Example 3 into a square mold to obtain a sample of 30mm*10mm*105mm. Before entering the 85°C / 85%RH aging chamber, conduct a 50% compression test on it to obtain the initial compression curve. Then, take it out for compression tests respectively in the 1st to 9th weeks from the start of aging, and calculate the attenuation ratio of the force at a deformation of 15mm to characterize the anti-aging performance of the sample under the double 85 humidity and heat conditions for 1500h. And conduct 1 heavy-load gauge impact test on the sample of Example 3 that was put into the aging chamber and aged for 9 weeks (1500h) at the same time.

[0087] Test data:

[0088] Table 1. Heavy-load and light-load impact test data

[0089]

[0090]

[0091]

[0092] Note: a ave —Average deceleration, unit g n ;

[0093] a max —Maximum deceleration, unit g n ;

[0094] t 2.5 —Time when the deceleration peak exceeds 2.5g n Time, unit s;

[0095] v 反 —Rebound velocity, unit m / s;

[0096] L max —Maximum buffer stroke, unit mm;

[0097] a 50— Deceleration value at 50% of the actual height of the buffer, unit: g n ;

[0098] Table 1 shows the test results of the impact tests of the maximum load (1350 kg) and light load (200 kg) for 4 samples in Examples 1, 2, 3 and 4. It can be seen that when the polyurethane-epoxy hybrid microporous elastomer material provided by the present invention is used for the elevator pit buffer, the average deceleration is less than 1.0 g n , the maximum deceleration is less than 6.0 g n , the deceleration time above 2.5 g n is less than 40 ms, the car rebound speed is less than 1.0 m / s, and there is no permanent deformation of the sample after the test. The typical impact test curves under the maximum mass condition and the minimum mass condition are respectively as Figure 1 and Figure 2 shown.

[0099] The aging compression curve of the sample in Example 3 is as Figure 3 shown, and part of the data is shown in Table 2. It can be seen that there is an obvious decrease in the sample in the first week. This is because under the high humidity and high temperature environment, water vapor molecules may still penetrate into the sample and adhere to the polymer network skeleton, acting as a plasticizer. At this time, although the mechanical data decreases, it is not caused by material degradation. The data in the subsequent 2-9 weeks basically has no obvious change, which also verifies this point. The pressure of the sample at 15 mm deformation in the ninth week is 32897 N. Compared with 34715 N in the initial state, the performance retention rate is 94.76%. It fully shows that the hybrid polymer buffer containing dicyclopentadiene structure developed by this technology has basically no performance attenuation under the extreme aging conditions of up to 9 weeks for a total of 1500 h, which is more than 15 times the requirements of the current inspection regulations standard.

[0100] Table 2. Part of the data of the 10-week durability aging performance test

[0101]

[0102]

[0103]

[0104] The sample of Example 3 that was aged synchronously for 9 weeks was subjected to 1 heavy load impact test, and the data is shown in Table 3.

[0105] Table 3. Impact test data of aging for 1500 h at 85°C / 85%RH

[0106] Test item Test result Action speed (m / s) 1.19 Average deceleration (g) 0.88 Maximum deceleration (g) 5.24 Duration of over 2.5g (ms) 32 Rebound speed (m / s) 0.33

[0107] It can be seen from the experimental results in Table 3 that all data well meet the requirements for the buffer at the bottom of the elevator pit specified in GB / T 7588-2020 and EN81-20 / 50. Currently, no commercially available buffer using the same type of technology has been found to meet the above standards.

[0108] It should be particularly noted that the above embodiments are only examples for clear illustration and not limitations on the implementation manners. For those skilled in the art, many variations can be derived based on the above description. Here, it is not necessary and impossible to list all the variations. However, those variations that are obviously derived therefrom are still within the protection scope of the present invention.

Claims

1. A preparation method of a polyurethane-epoxy hybrid microporous elastomer, characterized in that, It includes the following steps: S1: Using dicyclopentadiene, hydrogen peroxide and formic acid as raw materials, in the presence of methyl ethyl ketone solvent, through the catalysis of solid acid resin, an epoxidation reaction occurs to prepare dicyclopentadienyl epoxy resin; S2: Dissolving the dicyclopentadienyl epoxy resin obtained in S1 in an epoxy crosslinking agent, and mixing it evenly with the first polymer diol that has been vacuum dehydrated, adding isocyanate, and after reaction, obtaining component B containing both epoxy groups and isocyanate groups, and the NCO% in component B is between 4.96% and 16.57%; By weight, the raw material ratio of component B is as follows: S3: Mixing the second polymer diol, tertiary amine epoxy curing agent, chain extender, water and silicone oil evenly to obtain component A; the tertiary amine epoxy curing agent also serves as a catalyst for the polyurethane curing reaction; By weight, the raw material ratio of component A is as follows: S4: Mixing component A and component B in a weight ratio of (30 - 120):100, injecting them into a mold, and after curing reaction, forming a polyurethane-epoxy hybrid microporous elastomer.

2. The preparation method according to claim 1, wherein The solid acid resin catalyst is a strongly acidic cation exchange resin, and its weight is 5% of the weight of dicyclopentadiene.

3. The preparation method according to claim 1, wherein The epoxy crosslinking agent is a small molecule epoxy compound with an epoxy group functionality of 1 - 3 or a mixture thereof.

4. The preparation method according to claim 3, wherein The epoxy crosslinking agent is one or more of butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether.

5. The preparation method according to claim 1, characterized in that, The first polymer diol is one of polypropylene oxide ether diol, polytetrahydrofuran ether diol, polycaprolactone diol, polytetrahydrofuran ether-polycaprolactone block diol, polyethylene adipate diol, polybutylene adipate diol, polyneopentyl adipate diol, polyhexylene adipate diol, and the molecular weight of the first polymer diol is 2000 g / mol.

6. The preparation method according to claim 1, characterized in that, The isocyanate is one of diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate.

7. The preparation method according to claim 1, characterized in that, The second polymer diol is one of polypropylene oxide ether diol, polytetrahydrofuran ether diol, polycaprolactone diol, polytetrahydrofuran ether-polycaprolactone block diol, polyethylene adipate diol, polybutylene adipate diol, polyneopentyl adipate diol, polyhexylene adipate diol, and the molecular weight of the second polymer diol is 2000 g / mol.

8. The preparation method according to claim 1, characterized in that The tertiary amine epoxy curing agent is selected from one of triethylamine, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, 2,4,6-tris(dimethylaminomethyl)phenol.

9. The preparation method according to claim 1, wherein The chain extender is a small molecule diol, selected from one of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol.

10. The preparation method according to claim 1, characterized in that, The silicone oil is selected from one of DC193 of Momentive Performance Materials Inc. of the United States and S-9547 of Shanghai Maihao Co., Ltd.

11. The preparation method according to claim 1, characterized in that, In the step S1, the molar ratio of dicyclopentadiene, hydrogen peroxide and formic acid is 1:2:

1.

12. The preparation method according to claim 1, characterized in that, In the step S2, the reaction temperature for adding isocyanate is 80°C and the reaction time is 2 h.

13. A polyurethane-epoxy hybrid microporous elastomer, characterized in that, It is prepared by using the preparation method described in any one of claims 1 to 12.

14. The polyurethane-epoxy hybrid microporous elastomer according to claim 13, wherein The density of the polyurethane-epoxy hybrid microporous elastomer is 450 to 750 kg / cm 3 .

15. Application of the polyurethane-epoxy hybrid microporous elastomer described in claim 13 or 14 in manufacturing a pit buffer for low-speed elevators with a speed ≤ 1.0 m / s.

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