Low-temperature-resistant super-high-resilience polyurethane elastomer, and preparation method and application thereof

Abstract

The present application relates to the technical fields of polyurethane elastomer, in particular to a kind of low temperature resistant super high resilience polyurethane elastomer and its preparation method and application.The present application provides a kind of low temperature resistant super high resilience polyurethane elastomer, including A component and B component;By mass fraction, the A component includes 0-100 parts of polyurethane prepolymer and 0.1-1 parts of antioxidant;With the mass fraction of the polyurethane prepolymer as benchmark, the B component includes 5-9 parts of chain extender and 0.1-1 parts of catalyst;The raw material of the polyurethane prepolymer includes polytetrahydrofuran dihydric alcohol polyol and isocyanate;The number average molecular weight of the polytetrahydrofuran dihydric alcohol polyol is >1000.The low temperature resistant super high resilience polyurethane elastomer can satisfy the use of sealing product in northeast and other extremely cold regions for a long time.

Description

Technical Field

[0001] This invention relates to the field of polyurethane elastomer technology, and in particular to a low-temperature resistant, ultra-high resilience polyurethane elastomer, its preparation method, and its application. Background Technology

[0002] Polyurethane elastomers are copolymerized from soft and hard segments. The soft segments consist of polyethers or polyester polyols, while the hard segments consist of isocyanates and small-molecule chain extenders. The type and structure of the soft segments determine the material's elasticity, low-temperature performance, and hydrolysis resistance, while the type and structure of the hard segments determine the material's tear strength, hardness, and heat resistance. Due to their excellent wear resistance, elasticity, mechanical strength, wide hardness range, ease of processing, and environmental friendliness, they are widely used in sealing components in coal mines, engineering machinery, military, and chemical industries.

[0003] Currently, conventional polyurethane elastomer materials on the market typically have a rebound rate between 20% and 60%, and can only be used in environments as low as -40 degrees Celsius. If the temperature drops below -45 degrees Celsius, the material's mechanical properties deteriorate drastically, resulting in significant elasticity loss and even brittle fracture, leading to oil leaks and rendering it ineffective for sealing. This limits the use of sealing products in extremely cold regions. Therefore, developing a low-temperature resistant, ultra-high rebound polyurethane material is an effective way to overcome these shortcomings and expand the application range of sealing products. Summary of the Invention

[0004] The purpose of this invention is to provide a low-temperature resistant, ultra-high resilience polyurethane elastomer, its preparation method, and its application. This low-temperature resistant, ultra-high resilience polyurethane elastomer can meet the requirements of long-term use of sealing products in extremely cold regions such as Northeast China.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a low-temperature resistant, ultra-high resilience polyurethane elastomer, comprising component A and component B;

[0007] By weight, component A comprises 0 to 100 parts of polyurethane prepolymer and 0.1 to 1 part of antioxidant;

[0008] Based on the mass fraction of the polyurethane prepolymer, component B comprises 5 to 9 parts chain extender and 0.1 to 1 part catalyst;

[0009] The raw materials for preparing the polyurethane prepolymer include polytetrahydrofuran diols and isocyanates.

[0010] The polytetrahydrofuran diol has a number average molecular weight >1000.

[0011] Preferably, the method for preparing the polyurethane prepolymer includes the following steps:

[0012] Isocyanate is added to polytetrahydrofuran diol polyol and a prepolymerization reaction is carried out in a protective atmosphere to obtain the polyurethane prepolymer.

[0013] Preferably, the mass ratio of the isocyanate to the polytetrahydrofuran diol is (190-286):(400-600);

[0014] The prepolymerization reaction is carried out under stirring conditions; the stirring temperature is 60-80℃, the stirring speed is 200-400 r / min, and the stirring time is 3h.

[0015] Preferably, the polytetrahydrofuran diol includes one or two of conventional polytetrahydrofuran diol, tetrahydrofuran-propylene oxide coether diol, tetrahydrofuran-ethylene oxide coether diol, and side-methyl-tetrahydrofuran coether diol;

[0016] The isocyanate is diphenylmethane diisocyanate.

[0017] Preferably, the antioxidant includes antioxidant 1010 and / or antioxidant 168.

[0018] Preferably, it also includes wear-resistant agents;

[0019] Based on the mass fraction of the polyurethane prepolymer, the mass fraction of the wear-resistant agent is 0.3 to 2 parts.

[0020] Preferably, the chain extender includes one or two of 1,4-butanediol, hydroquinone dihydroxyethyl ether, and ethylene glycol.

[0021] Preferably, the catalyst comprises an organotin catalyst and / or an organobismuth catalyst;

[0022] The organotin catalyst contains 28% tin by mass.

[0023] The bismuth content in the organic bismuth catalyst is 28% by mass.

[0024] This invention also provides a method for preparing the low-temperature resistant, ultra-high resilience polyurethane elastomer described in the above technical solution, comprising the following steps:

[0025] After melting the polyurethane prepolymer, an antioxidant is added to obtain component A;

[0026] The chain extender and catalyst are mixed to obtain component B;

[0027] After mixing components A and B, the mixture is cured in a mold to obtain the low-temperature resistant ultra-high resilience polyurethane elastomer.

[0028] The present invention also provides the application of the low-temperature resistant ultra-high resilience polyurethane elastomer described in the above technical solution or the low-temperature resistant ultra-high resilience polyurethane elastomer prepared by the preparation method described in the above technical solution in sealing products.

[0029] This invention provides a low-temperature resistant, ultra-high resilience polyurethane elastomer, comprising component A and component B. Component A, by mass parts, comprises 0-100 parts of polyurethane prepolymer and 0.1-1 parts of antioxidant. Based on the mass parts of the polyurethane prepolymer, component B comprises 5-9 parts of chain extender and 0.1-1 parts of catalyst. The raw materials for preparing the polyurethane prepolymer include polytetrahydrofuran diol polyols and isocyanates. The number average molecular weight of the polytetrahydrofuran diol polyol is >1000. The polytetrahydrofuran diol polyol used in the low-temperature resistant, ultra-high resilience polyurethane elastomer of this invention has excellent low-temperature resistance, solving the problem that conventional polyurethane elastomer materials (whose molecular chains gradually lose flexibility at low temperatures, transitioning from a highly elastic state to a glassy state, resulting in loss of original elasticity and strength, brittleness, and even brittle fracture) cannot be used in low-temperature environments below -45°C. This significantly improves the low-temperature resistance and resilience of the material. The added wear-resistant agent can greatly improve the wear resistance of the material and extend the service life of the polyurethane elastomer. Detailed Implementation

[0030] This invention provides a low-temperature resistant, ultra-high resilience polyurethane elastomer, comprising component A and component B;

[0031] By weight, component A comprises 0 to 100 parts of polyurethane prepolymer and 0.1 to 1 part of antioxidant;

[0032] Based on the mass fraction of the polyurethane prepolymer, component B comprises 5 to 9 parts chain extender and 0.1 to 1 part catalyst;

[0033] The raw materials for preparing the polyurethane prepolymer include polytetrahydrofuran diols and isocyanates.

[0034] The polytetrahydrofuran diol has a number average molecular weight >1000.

[0035] In this invention, unless otherwise specified, all raw materials used in the preparation are commercially available products well known to those skilled in the art.

[0036] Based on mass parts, component A of the low-temperature resistant ultra-high resilience polyurethane elastomer of the present invention comprises 0 to 100 parts of polyurethane prepolymer, preferably 10 to 80 parts, and more preferably 30 to 60 parts.

[0037] In this invention, the method for preparing the polyurethane prepolymer preferably includes the following steps:

[0038] Isocyanate is added to polytetrahydrofuran diol polyol and a prepolymerization reaction is carried out in a protective atmosphere to obtain the polyurethane prepolymer.

[0039] In this invention, the molecular weight of the polytetrahydrofuran diol polyol is >1000, preferably 2000-3000. The polytetrahydrofuran diol polyol includes one or two of conventional polytetrahydrofuran diol, tetrahydrofuran-propylene oxide coether diol, tetrahydrofuran-ethylene oxide coether diol, and side-methyl-tetrahydrofuran coether diol. When the polytetrahydrofuran diol polyol is two of the above-mentioned specific selections, this invention does not impose any special limitation on the ratio of the two substances; they can be mixed in any ratio. In this invention, the polytetrahydrofuran diol polyol is preferably pretreated. The pretreatment preferably includes: sequentially melting and dehydrating the polytetrahydrofuran diol polyol to obtain the molten polytetrahydrofuran diol polyol. In this invention, the melting temperature is preferably 60–90°C, more preferably 65–85°C, and most preferably 70–80°C; the melting method is preferably water bath heating. In this invention, the dehydration temperature is preferably 100–120°C, more preferably 105–115°C, and most preferably 108–112°C; the dehydration is preferably carried out under vacuum conditions, and the vacuum degree is preferably -0.097 MPa; the dehydration time is preferably 1–2 hours. After dehydration, this invention also preferably includes cooling. This invention does not impose any special limitations on the cooling process; a process well-known to those skilled in the art can be used, ensuring that the temperature is reduced to 40–60°C.

[0040] In this invention, the isocyanate is preferably diphenylmethane diisocyanate. In this invention, the isocyanate is preferably pretreated, and the pretreatment preferably includes melting the isocyanate to obtain the molten isocyanate. In this invention, the melting temperature is preferably 50–70°C, more preferably 55–65°C, and most preferably 58–62°C. In this invention, the melting method is preferably water bath heating.

[0041] In this invention, the mass ratio of the isocyanate to the polytetrahydrofuran diol is preferably (190-286):(400-600), more preferably (200-260):(450-550), and most preferably (210-230):(480-520).

[0042] In this invention, the protective atmosphere is preferably a nitrogen atmosphere. In this invention, the prepolymerization reaction is preferably carried out under stirring conditions, and the stirring speed is preferably 200–400 r / min, more preferably 250–350 r / min, and most preferably 280–320 r / min. In this invention, the temperature of the prepolymerization reaction is preferably 60–80°C, more preferably 65–75°C, and most preferably 68–72°C; the duration of the prepolymerization reaction is preferably 3 hours.

[0043] After the prepolymerization reaction is completed, the present invention preferably includes vacuum degassing, and the vacuum degassing time is preferably 1 hour; the present invention does not impose any special limitations on other conditions for vacuum degassing, and can use processes well known to those skilled in the art.

[0044] In this invention, the polyurethane prepolymer is preferably a polyurethane prepolymer with an NCO content of 6% to 10%.

[0045] Based on the mass fraction of the polyurethane prepolymer, component A of the low-temperature resistant ultra-high resilience polyurethane elastomer of the present invention includes 0.1 to 1 part of antioxidant, preferably 0.3 to 0.8 parts, and more preferably 0.4 to 0.6 parts. In the present invention, the antioxidant preferably includes antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) and / or antioxidant 168 (tris(2,4-di-tert-butylphenyl) phosphite). When the antioxidant includes antioxidant 1010 and antioxidant 168, the present invention does not impose any special limitation on the ratio of antioxidant 1010 and antioxidant 168; they can be mixed in any ratio. In a specific embodiment of the present invention, the antioxidant includes antioxidant 1010 and antioxidant 168 in a mass ratio of 1:3.

[0046] In this invention, the antioxidant is used to prevent the material from undergoing oxidative degradation during processing and subsequent use.

[0047] Based on the mass fraction of the polyurethane prepolymer, component A of the low-temperature resistant ultra-high resilience polyurethane elastomer of the present invention preferably includes 0.3 to 2 parts of abrasion-resistant agent, more preferably 0.5 to 1.5 parts, and most preferably 0.8 to 1.2 parts. In the present invention, the abrasion-resistant agent preferably includes an organosilicon abrasion-resistant agent; the organosilicon abrasion-resistant agent is preferably purchased from Guangzhou Yourun Synthetic Materials Co., Ltd., model CUBD-NML; when the organosilicon abrasion-resistant agent is two or more of the above-mentioned specific selections, the present invention does not have any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0048] In this invention, the wear-resistant agent serves to improve the wear resistance of the material.

[0049] Based on the mass fraction of the polyurethane prepolymer, the low-temperature resistant ultra-high resilience polyurethane elastomer of the present invention further includes component B, which comprises 5 to 9 parts of chain extender, preferably 6 to 8 parts, and more preferably 6.6 to 7.5 parts. In the present invention, the chain extender preferably includes one or two of 1,4-butanediol, hydroquinone dihydroxyethyl ether, and ethylene glycol. When the chain extender is two of the above-mentioned specific selections, the present invention does not impose any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0050] Based on the mass fraction of the polyurethane prepolymer, component B in the low-temperature resistant ultra-high resilience polyurethane elastomer of the present invention comprises 0.1 to 1 part of catalyst, preferably 0.2 to 0.8 parts, and more preferably 0.4 to 0.6 parts. In the present invention, the catalyst preferably comprises an organotin catalyst and / or an organobismuth catalyst; the mass percentage of tin in the organotin catalyst is preferably 28%, and the mass percentage of bismuth in the organobismuth catalyst is preferably 28%. In the present invention, the organotin catalyst preferably comprises stannous octoate; the organobismuth catalyst preferably comprises bismuth isooctanoate.

[0051] In this invention, the catalyst is used to promote the reaction between the prepolymer and the chain extender, thereby improving product performance.

[0052] This invention also provides a method for preparing the low-temperature resistant, ultra-high resilience polyurethane elastomer described in the above technical solution, comprising the following steps:

[0053] After melting the polyurethane prepolymer, an antioxidant is added to obtain component A;

[0054] The chain extender and catalyst are mixed to obtain component B;

[0055] After mixing components A and B, the mixture is cured in a mold to obtain the low-temperature resistant ultra-high resilience polyurethane elastomer.

[0056] In this invention, an antioxidant is added after the polyurethane prepolymer is melted to obtain component A.

[0057] In this invention, when component A includes a wear-resistant agent, the preferred method for preparing component A is to melt the polyurethane prepolymer and then add an antioxidant and a wear-resistant agent.

[0058] In this invention, the melting temperature is preferably 60-80°C, more preferably 65-75°C, and most preferably 68-72°C; the melting is preferably carried out in an oven.

[0059] In this invention, after adding the antioxidant or after adding both the antioxidant and the wear-resistant agent, stirring is preferred. This invention does not impose any special limitations on the stirring process; any process well-known to those skilled in the art can be used. After stirring, this invention also preferably includes vacuum degassing, the vacuum degassing time of which is preferably 30–60 min, more preferably 35–55 min, and most preferably 40–50 min.

[0060] The preparation method of the present invention preferably includes mixing a chain extender and a catalyst to obtain component B.

[0061] In this invention, the mixing is preferably performed by heating the chain extender before adding the catalyst. The heating temperature is preferably 60–80°C, more preferably 65–75°C, and most preferably 68–72°C. This invention does not impose any particular limitation on the heating time; the chain extender can be completely melted at the aforementioned heating temperature. The heating is preferably performed in an oven. This invention does not impose any particular limitation on the method of adding the catalyst; any method well-known to those skilled in the art can be used.

[0062] After the mixing is completed, the present invention preferably includes vacuum degassing. The present invention does not have any special limitations on the vacuum degassing process, and a process well known to those skilled in the art can be used to fully degas the mixture.

[0063] After obtaining component A and component B, the present invention mixes component A and component B and cures them in a mold to obtain the low-temperature resistant ultra-high resilience polyurethane elastomer.

[0064] In this invention, the mixing is preferably carried out under vacuum and stirring conditions. The present invention does not impose any special limitations on the vacuum conditions; conditions well known to those skilled in the art can be used. In this invention, the stirring speed is preferably 1000–1500 r / min, more preferably 1100–1400 r / min, and most preferably 1200–1300 r / min; the stirring time is preferably 1 min.

[0065] In this invention, the curing process preferably involves pouring the mixture obtained from the mixing process into a preheated mold for curing. In this invention, the preheating temperature of the mold is preferably 110–130°C, more preferably 115–125°C, and most preferably 118–122°C. In this invention, the curing temperature is preferably 120°C, and the curing time is preferably 16–20 hours, more preferably 18–19 hours.

[0066] The present invention also provides the application of the low-temperature resistant ultra-high resilience polyurethane elastomer described in the above technical solution or the low-temperature resistant ultra-high resilience polyurethane elastomer prepared by the preparation method described in the above technical solution in sealing products.

[0067] The following detailed description, in conjunction with embodiments, illustrates the low-temperature resistant ultra-high resilience polyurethane elastomer, its preparation method, and its applications provided by the present invention. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0068] Example 1

[0069] Preparation of polyurethane prepolymer:

[0070] 500g of conventional polytetrahydrofuran diol (molecular weight 2000) was melted in a water bath at 70°C and then added to a reactor. The mixture was heated to 120°C and dehydrated under a vacuum of -0.097MPa for 1 hour. The mixture was then cooled to 50°C and set aside for later use.

[0071] Diphenylmethane diisocyanate was melted in a water bath at 60°C and then cooled to 50°C for later use.

[0072] 238g of pretreated diphenylmethane diisocyanate and 500g of pretreated conventional polytetrahydrofuran diol were added to a reactor. Under nitrogen purging, the mixture was stirred at 300r / min at 65°C for 3h, followed by vacuum degassing at 80°C for 30min to obtain a polyurethane prepolymer with an NCO content of 8.0±0.2%.

[0073] Preparation of component A:

[0074] After heating 500g of the polyurethane prepolymer to 110°C and melting it, add 0.5g of antioxidant 1010 and 1.5g of antioxidant 168, and stir until completely dissolved to obtain component A.

[0075] Preparation of component B:

[0076] 42g of 1,4-butanediol (BDO) and 0.5g of an organic bismuth catalyst (specifically bismuth isooctanoate, with a bismuth mass percentage of 28%) were mixed evenly, heated to 80°C and vacuum dehydrated for 30min, and then cooled to 30°C to obtain component B.

[0077] Preparation of low-temperature resistant, ultra-high resilience polyurethane elastomer materials:

[0078] 502g of component A at 80℃ and 42.5g of component B at 30℃ were mixed and stirred in a container under vacuum (stirring speed of 1200r / min for 1min). The resulting mixture was poured into a tube mold preheated at 120℃ and placed in an oven at 120℃ for 20h to obtain the low-temperature resistant ultra-high resilience polyurethane elastomer material.

[0079] Example 2

[0080] Preparation of polyurethane prepolymer:

[0081] 500g of tetrahydrofuran-propylene oxide copolyether diol (molecular weight 2000) was melted in a water bath at 70°C and then added to a reactor. The mixture was heated to 120°C and dehydrated under a vacuum of -0.097MPa for 1 hour. The mixture was then cooled to 50°C and set aside for later use.

[0082] Diphenylmethane diisocyanate was melted in a water bath at 60°C and then cooled to 50°C for later use.

[0083] 238g of the pretreated diphenylmethane diisocyanate and 500g of the pretreated tetrahydrofuran-propylene oxide copolyether diol were added to a reactor. Under nitrogen purging, the mixture was stirred at 300r / min at 65°C for 3h, followed by vacuum degassing at 80°C for 30min to obtain a polyurethane prepolymer with an NCO content of 8.0±0.2%.

[0084] Preparation of component A:

[0085] After heating 500g of the polyurethane prepolymer to 110°C and melting it, add 0.5g of antioxidant 1010 and 1.5g of antioxidant 168, and stir until completely dissolved to obtain component A.

[0086] Preparation of component B:

[0087] 42g of 1,4-butanediol (BDO) and 0.5g of an organic bismuth catalyst (specifically bismuth isooctanoate, with a bismuth mass percentage of 28%) were mixed evenly, heated to 80°C and vacuum dehydrated for 30min, and then cooled to 30°C to obtain component B.

[0088] Preparation of low-temperature resistant, ultra-high resilience polyurethane elastomer materials:

[0089] 502g of component A at 80℃ and 42.5g of component B at 30℃ were mixed and stirred in a container under vacuum (stirring speed of 1200r / min for 1min). The resulting mixture was poured into a tube mold preheated at 120℃ and placed in an oven at 120℃ for 20h to obtain the low-temperature resistant ultra-high resilience polyurethane elastomer material.

[0090] Example 3

[0091] Preparation of polyurethane prepolymer:

[0092] 500g of side-methyl-tetrahydrofuran copolyether diol (molecular weight 2000) was melted in a water bath at 70°C and then added to a reactor. The mixture was heated to 120°C and dehydrated under a vacuum of -0.097MPa for 1 hour. The mixture was then cooled to 50°C and set aside for later use.

[0093] Diphenylmethane diisocyanate was melted in a water bath at 60°C and then cooled to 50°C for later use.

[0094] 238g of the pretreated diphenylmethane diisocyanate and 500g of the pretreated side-methyl-tetrahydrofuran copolyether diol were added to a reactor. Under nitrogen purging, the mixture was stirred at 300r / min at 65°C for 3h, followed by vacuum degassing at 80°C for 30min to obtain a polyurethane prepolymer with an NCO content of 8.0±0.2%.

[0095] Preparation of component A:

[0096] After heating 500g of the polyurethane prepolymer to 110°C and melting it, add 0.5g of antioxidant 1010 and 1.5g of antioxidant 168, and stir until completely dissolved to obtain component A.

[0097] Preparation of component B:

[0098] After mixing 42g of 1,4-butanediol (BDO) and 0.5g of an organic bismuth catalyst (specifically bismuth isooctanoate with a bismuth content of 28%) evenly, the mixture was heated to 80°C and vacuum dehydrated for 30 minutes, then cooled to 30°C to obtain component B.

[0099] Preparation of low-temperature resistant, ultra-high resilience polyurethane elastomer materials:

[0100] 502g of component A at 80℃ and 42.5g of component B at 30℃ were mixed and stirred in a container under vacuum (stirring speed of 1200r / min for 1min). The resulting mixture was poured into a tube mold preheated at 120℃ and placed in an oven at 120℃ for 20h to obtain the low-temperature resistant ultra-high resilience polyurethane elastomer material.

[0101] Example 4

[0102] Preparation of polyurethane prepolymer:

[0103] 500g of conventional polytetrahydrofuran diol (molecular weight 3000) was melted in a water bath at 70°C and then added to a reactor. The mixture was heated to 120°C and dehydrated under a vacuum of -0.097MPa for 1 hour. The mixture was then cooled to 50°C and set aside for later use.

[0104] Diphenylmethane diisocyanate was melted in a water bath at 60°C and then cooled to 50°C for later use.

[0105] 210.9 g of pretreated diphenylmethane diisocyanate and 500 g of pretreated conventional polytetrahydrofuran diol were added to a reactor. Under nitrogen purging, the mixture was stirred at 300 r / min at 65°C for 3 h, followed by vacuum degassing at 80°C for 30 min to obtain a polyurethane prepolymer with an NCO content of 8.0 ± 0.2%.

[0106] Preparation of component A:

[0107] After heating 500g of the polyurethane prepolymer to 110°C and melting it, add 0.5g of antioxidant 1010, 1.5g of antioxidant 168 and 2.5g of wear-resistant agent (purchased from Guangzhou Yourun Synthetic Materials Co., Ltd., model CUBD-NML), and stir until completely dissolved to obtain component A.

[0108] Preparation of component B:

[0109] After mixing 42g of 1,4-butanediol (BDO) and 0.5g of an organic bismuth catalyst (specifically bismuth isooctanoate with a bismuth content of 28%) evenly, the mixture was heated to 80°C and vacuum dehydrated for 30 minutes, then cooled to 30°C to obtain component B.

[0110] Preparation of low-temperature resistant, ultra-high resilience polyurethane elastomer materials:

[0111] 504.5g of component A at 80℃ and 42.5g of component B at 30℃ were mixed and stirred in a container under vacuum (stirring speed of 1200r / min for 1min). The resulting mixture was poured into a tube mold preheated at 120℃ and placed in an oven at 120℃ for 20h to obtain the low-temperature resistant ultra-high resilience polyurethane elastomer material.

[0112] Example 5

[0113] Preparation of polyurethane prepolymer:

[0114] 500g of tetrahydrofuran-propylene oxide copolyether diol (molecular weight 3000) was melted in a water bath at 70°C and then added to a reactor. The mixture was heated to 120°C and dehydrated under a vacuum of -0.097MPa for 1 hour. The mixture was then cooled to 50°C and set aside for later use.

[0115] Diphenylmethane diisocyanate was melted in a water bath at 60°C and then cooled to 50°C for later use.

[0116] 210.9 g of the pretreated diphenylmethane diisocyanate and 500 g of the pretreated tetrahydrofuran-propylene oxide copolyether diol were added to a reactor. Under nitrogen purging, the mixture was stirred at 300 r / min at 65°C for 3 h, followed by vacuum degassing at 80°C for 30 min to obtain a polyurethane prepolymer with an NCO content of 8.0 ± 0.2%.

[0117] Preparation of component A:

[0118] After heating 500g of the polyurethane prepolymer to 110°C and melting it, add 0.5g of antioxidant 1010, 1.5g of antioxidant 168 and 2.5g of wear-resistant agent (purchased from Guangzhou Yourun Synthetic Materials Co., Ltd., model CUBD-NML), and stir until completely dissolved to obtain component A.

[0119] Preparation of component B:

[0120] After mixing 42g of 1,4-butanediol (BDO) and 0.5g of an organic bismuth catalyst (specifically bismuth isooctanoate with a bismuth content of 28%) evenly, the mixture was heated to 80°C and vacuum dehydrated for 30 minutes, then cooled to 30°C to obtain component B.

[0121] Preparation of low-temperature resistant, ultra-high resilience polyurethane elastomer materials:

[0122] 504.5g of component A at 80℃ and 42.5g of component B at 30℃ were mixed and stirred in a container under vacuum (stirring speed of 1200r / min for 1min). The resulting mixture was poured into a tube mold preheated at 120℃ and placed in an oven at 120℃ for 20h to obtain the low-temperature resistant ultra-high resilience polyurethane elastomer material.

[0123] Example 6

[0124] Preparation of polyurethane prepolymer:

[0125] 500g of side-methyl-tetrahydrofuran copolyether diol (molecular weight 3000) was melted in a water bath at 70°C and then added to a reactor. The mixture was heated to 120°C and dehydrated under a vacuum of -0.097MPa for 1 hour. The mixture was then cooled to 50°C and set aside for later use.

[0126] Diphenylmethane diisocyanate was melted in a water bath at 60°C and then cooled to 50°C for later use.

[0127] 210.9 g of the pretreated diphenylmethane diisocyanate and 500 g of the pretreated side-methyl-tetrahydrofuran copolyether diol were added to a reactor. Under nitrogen purging, the mixture was stirred at 300 r / min at 65°C for 3 h, followed by vacuum degassing at 80°C for 30 min to obtain a polyurethane prepolymer with an NCO content of 8.0 ± 0.2%.

[0128] Preparation of component A:

[0129] After heating 500g of the polyurethane prepolymer to 110°C and melting it, add 0.5g of antioxidant 1010, 1.5g of antioxidant 168 and 2.5g of wear-resistant agent (purchased from Guangzhou Yourun Synthetic Materials Co., Ltd., model CUBD-NML), and stir until completely dissolved to obtain component A.

[0130] Preparation of component B:

[0131] After mixing 42g of 1,4-butanediol (BDO) and 0.5g of an organic bismuth catalyst (specifically bismuth isooctanoate with a bismuth content of 28%) evenly, the mixture was heated to 80°C and vacuum dehydrated for 30 minutes, then cooled to 30°C to obtain component B.

[0132] Preparation of low-temperature resistant, ultra-high resilience polyurethane elastomer materials:

[0133] 504.5g of component A at 80℃ and 42.5g of component B at 30℃ were mixed and stirred in a container under vacuum (stirring speed of 1200r / min for 1min). The resulting mixture was poured into a tube mold preheated at 120℃ and placed in an oven at 120℃ for 20h to obtain the low-temperature resistant ultra-high resilience polyurethane elastomer material.

[0134] Test case

[0135] The low-temperature resistant, ultra-high resilience polyurethane elastomer materials described in Examples 1-6 were subjected to performance tests, and the test results are shown in Table 1.

[0136] Table 1. Performance parameters of the low-temperature resistant, ultra-high resilience polyurethane elastomer materials described in Examples 1-6.

[0137]

[0138] As shown in Table 1, the low-temperature resistant ultra-high resilience polyurethane elastomer material of the present invention has good low-temperature resistance, and tetrahydrofuran-propylene oxide copolyether diol, as the soft segment, has even better low-temperature resistance. The larger the molecular weight of the polyol, the greater the flexibility, the more complete the microphase separation, the better the low-temperature resistance, and the better the resilience. At the same time, when a wear-resistant agent is added, the low-temperature resistant ultra-high resilience polyurethane elastomer material has even better wear resistance.

[0139] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A low-temperature resistant, ultra-high resilience polyurethane elastomer, characterized in that, Includes component A and component B; Preparation of Component A: 500g of polyurethane prepolymer was heated to 110℃ and melted. Then, 0.5g of antioxidant 1010, 1.5g of antioxidant 168 and 2.5g of wear-resistant agent of type CUBD-NML were added and stirred until completely dissolved to obtain Component A. Preparation of component B: 42g of 1,4-butanediol and 0.5g of bismuth isooctanoate with a bismuth content of 28% were mixed evenly, heated to 80℃ and vacuum dehydrated for 30min, and then cooled to 30℃ to obtain component B; The NCO content in the polyurethane prepolymer is 8.0 ± 0.2%, and the preparation process is as follows: 500g of tetrahydrofuran-propylene oxide copolyether diol was melted in a water bath at 70°C and then added to a reactor. The mixture was heated to 120°C and dehydrated under a vacuum of -0.097MPa for 1 hour. The mixture was then cooled to 50°C and set aside for later use. The molecular weight of the tetrahydrofuran-propylene oxide copolyether diol was 3000. Diphenylmethane diisocyanate was melted in a water bath at 60°C and then cooled to 50°C for later use. 210.9g of the pretreated diphenylmethane diisocyanate and 500g of the pretreated tetrahydrofuran-propylene oxide copolyether diol were added to a reactor. Under nitrogen purging, the mixture was stirred at 300r / min at 65°C for 3h, followed by vacuum degassing at 80°C for 30min to obtain the polyurethane prepolymer. The preparation method of the low-temperature resistant ultra-high resilience polyurethane elastomer is as follows: 504.5g of component A at 80℃ and 42.5g of component B at 30℃ were mixed and stirred in a container under vacuum at a speed of 1200r / min for 1min. The resulting mixture was poured into a tube mold preheated at 120℃ and placed in an oven at 120℃ for 20h to obtain the low-temperature resistant ultra-high resilience polyurethane elastomer.

2. The method for preparing the low-temperature resistant ultra-high resilience polyurethane elastomer according to claim 1, characterized in that, The preparation process is as follows: 504.5g of component A at 80℃ and 42.5g of component B at 30℃ were mixed and stirred in a container under vacuum at a speed of 1200r / min for 1min. The resulting mixture was poured into a tube mold preheated at 120℃ and placed in an oven at 120℃ for 20h to obtain the low-temperature resistant ultra-high resilience polyurethane elastomer.

3. The application of the low-temperature resistant ultra-high resilience polyurethane elastomer of claim 1 or the low-temperature resistant ultra-high resilience polyurethane elastomer prepared by the preparation method of claim 2 in sealing products.

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