Polyurethane elastomer for submarine cable bending limiter and preparation method thereof

Abstract

The invention belongs to the technical field of polyurethane elastomers, and particularly relates to a polyurethane elastomer for a submarine cable bending limiter and a preparation method of the polyurethane elastomer. The polyurethane elastomer for the submarine cable bending limiter is composed of a polymer component and a prepolymer component, and the polymer component comprises the following raw materials: micromolecular polyol, micromolecular polyol amine, polyether polyol 1, polyether polyol 2, polyether polyol 3, an aromatic diol chain extender, an organic metal catalyst and glass fiber powder. The prepolymer component is prepared from the following raw materials: polytetrahydrofuran ether glycol, special polyphenyl ether polyol, MDI type isocyanate and glass fiber powder. The polyurethane elastomer for the submarine cable bending limiter provided by the invention is excellent in product mechanical property, has good high temperature resistance and hydrolysis resistance, and meets the requirements of the market on high-performance submarine cable bending limiter materials; the invention further provides a preparation method, and the preparation process is simple.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane elastomers, and in particular relates to a polyurethane elastomer for a submarine cable bending limiter and a preparation method thereof. Background Art

[0002] Submarine cable bend limiter is a device used to protect submarine communication cables. It can prevent the cable from excessive bending due to excessive force during installation, transportation and operation, thereby extending the service life of the cable and ensuring the stability and security of information transmission. With the vigorous development of China's offshore oil and gas and offshore wind power resources, submarine cables are facing various complex marine environments, and the long-term safety and reliability of submarine cables is particularly critical.

[0003] At present, the main technical requirements for submarine cable bend limiter materials are as follows: submarine cable bend limiter materials need to have high tensile strength and toughness to meet the requirements of mechanical strength during installation and rigorous use; the selection of bend limiter materials should ensure that they can withstand the temperature near the submarine cable during their service life and maintain a high performance retention rate when the submarine cable is heated; the bend limiter is located below the water surface and must be in long-term contact with seawater and have excellent anti-hydrolysis and anti-fatigue properties.

[0004] CN110922556A discloses a polyurethane elastomer material resistant to seawater corrosion and a preparation method thereof, which is composed of two components A and B. Component A is glycerol polyether polyol, toughening polyether polyol, chain extender, catalyst and hydrophobic nano powder, and component B is polyisocyanate curing agent. The high specific surface area and low surface energy characteristics of the hydrophobic nano powder significantly improve the hydrophobicity, mechanical strength and seawater corrosion resistance of the polyurethane elastomer material, with a contact angle of 105-128°, a tensile strength of 28-48MPa, and a weight loss of only 1-6% due to seawater corrosion. At the same time, the wear resistance is enhanced and the wear loss is low. However, the mechanical properties after seawater corrosion are not further tested, and the hydrophobic nano powder with a porous structure is easy to absorb non-polar dirt (such as oil stains, etc.) in seawater, which is easy to accelerate the aging and decomposition of the product.

[0005] CN118562091A discloses a cast polyurethane elastomer and a preparation method thereof. Polytetramethylene glycol, polycaprolactone diol, liquefied MDI and hydrogenated MDI constitute material A; polytetramethylene glycol, 1,4-butanediol (BOD), 4,4'-methylenebis(2-chloroaniline) (MOCA) and antioxidants, light stabilizers, etc. are used as material B, and the two are mixed, cast and vulcanized to obtain a polyurethane elastomer; liquefied MDI replaces solid MDI, MOCA and BDO cooperate to extend the chain to regulate the curing time, and at the same time, polycaprolactone is introduced to improve the performance. The product has excellent mechanical properties, high resilience, small permanent deformation at break, and excellent seawater resistance. However, the ester bond in polycaprolactone is easily hydrolyzed in the marine environment, resulting in a rapid decrease in the mechanical properties of the product, and the life of the product cannot be guaranteed. Summary of the invention

[0006] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art and provide a polyurethane elastomer for a submarine cable bending limiter. The product has excellent mechanical properties, good high temperature resistance and hydrolysis resistance, and meets the market demand for high-performance submarine cable bending limiter materials; the present invention also provides a preparation method thereof, and the preparation process is simple.

[0007] The polyurethane elastomer for the submarine cable bending limiter of the present invention is composed of a polymer component and a prepolymer component in a mass ratio of 100:(83-107), and the polymer component includes the following raw materials in mass fractions: Small molecule polyol: 5-8 parts; Small molecule polyol amine: 6-8 parts; Polyether polyol 1: 10-25 parts; Polyether polyol 2: 30-37 parts; Polyether polyol 3: 10-24 parts; Aromatic diol chain extender: 10-31 parts; Organic metal catalyst: 0.01-0.03 parts; Glass fiber powder: 10-20 parts; The prepolymer component includes the following raw materials in parts by weight: Polytetramethylene glycol: 6.1-18.7 parts; Special polyphenylene ether polyol: 2.8-4.9 parts; MDI isocyanate: 76.6-90.8 parts; Glass fiber powder: 10-20 parts.

[0008] The polyether polyol 1 is a polyether polyol with a functionality of ≥3 and a number average molecular weight of ≤700, and the polyether polyol 1 is one or two of DV-125, MN-500, and MN-700.

[0009] The polyether polyol 2 is a polyether polyol with a functionality of ≥3 and a number average molecular weight of ≥8000, and the polyether polyol 2 is one or two of 10LD8001, 10LD8005, and 10LD8007.

[0010] The polyether polyol 3 is a polyether polyol with a functionality of 2 and a number average molecular weight of ≤2000. The polyether polyol 3 is one or two of INOVOL C204, INOVOL C210 and INOVOL C220.

[0011] The mesh number of the glass fiber powder is 1000-1250 mesh, and preferably one of the alkali-free glass fiber powders with mesh numbers of 1000 mesh and 1250 mesh commercially available from Shenzhen Yataida Technology Co., Ltd., or a mixture of the two mesh numbers in any proportion.

[0012] The small molecule polyol is one or two of 1,4-butanediol, diethylene glycol and methyl propylene glycol.

[0013] The small molecule polyol amine is one or two of diisopropanolamine, triisopropanolamine and triethanolamine.

[0014] The aromatic diol chain extender is one or both of XYlink HQEE-L and XYlink HER-L.

[0015] The organic metal catalyst is one or two of bismuth isooctanoate and dibutyltin di(isooctylmaleate).

[0016] The polytetramethylene ether glycol is one or two of PTMEG250, PTMEG650 and PTMEG1000.

[0017] The special polyphenylene ether polyol is one or both of NORYL AP2001G and NORYL N190.

[0018] The MDI type isocyanate is a mixture of carbodiimide modified diphenylmethane diisocyanate (liquefied MDI) and MDI-100 in a mass ratio of 1: (0.4-4).

[0019] The method for preparing the polyurethane elastomer for the submarine cable bending limiter comprises the following steps: (1) Polymer component: small molecule polyol, small molecule polyol amine, polyether polyol 1, polyether polyol 2, polyether polyol 3, aromatic diol chain extender, organic metal catalyst and glass fiber powder are put into a reaction kettle and mixed uniformly under vacuum to obtain a polymer component; (2) Prepolymer component: Heat polytetramethylene glycol to 110-130°C, then add special polyphenylene ether polyol and stir until melted, cool to 55-60°C, then add MDI type isocyanate to the reactor in batches, keep stirring at 75-85°C for 1-2 hours to obtain a prepolymer with an -NCO content of 23.0-27.0wt.%, finally add glass fiber powder, continue to stir evenly, and obtain a prepolymer component; (3) The polymer component and the prepolymer component are heated to 30-40°C, mixed evenly according to the mass ratio, poured into a mold at 50-70°C, and post-vulcanized at 70-90°C for 10-16h after the mold is opened to obtain a polyurethane elastomer for a submarine cable bending limiter.

[0020] Compared with the prior art, the present invention has the following beneficial effects: (1) The polyurethane elastomer for the submarine cable bending limiter of the present invention has a liquid aromatic diol chain extender containing benzene rings added to the polymer component, and a special polyphenylene ether polyol containing multiple benzene rings added to the prepolymer component. The effect of the benzene rings of the two makes the product have excellent high temperature resistance and low water absorption rate, and at the same time increases the hydrolysis resistance of the product.

[0021] (2) The polyurethane elastomer for the submarine cable bend limiter of the present invention introduces polyether polyols of different functionalities and different number average molecular weights under the synergistic effect of small molecule polyols and small molecule polyol amines, so that the product has both high temperature hardness and excellent toughness, and solves the problem of excessive brittleness of the product caused by the introduction of aromatic diol chain extenders and special polyphenylene ether polyols, so that it can meet the requirements of transportation, installation and laying of submarine cable bend limiters.

[0022] (3) The polyurethane elastomer for the submarine cable bending limiter of the present invention further increases the tensile strength and high temperature resistance of the product by introducing glass fiber powder of a certain mesh size, thereby reducing internal stress and increasing support.

[0023] (4) The preparation method of the polyurethane elastomer for the submarine cable bending limiter of the present invention has a simple preparation process. The prepared product has a Shore hardness of 80-85D, a tensile strength of up to 56MPa, an elongation at break ≥11%, and a DIN abrasion ≤210mm. 3 , high temperature hardness ≥ Shore 45D at 80°C, tensile strength ≥ 17MPa, and it also has the characteristics of low water absorption and hydrolysis resistance, meeting the market demand for high-performance submarine cable bending limiter materials. DETAILED DESCRIPTION

[0024] The present invention is further described below in conjunction with the following examples and comparative examples. The raw materials used in the examples and comparative examples are all conventional commercially available raw materials unless otherwise specified, and the process methods used in the examples and comparative examples are all conventional methods in the art unless otherwise specified.

[0025] The raw materials used in the embodiments and comparative examples are described as follows: DV-125: number average molecular weight 375, functionality 3, Shandong Bluestar Dongda Co., Ltd.; MN-500: number average molecular weight 500, functionality 3, Shandong Bluestar Dongda Co., Ltd.; MN-700: number average molecular weight 700, functionality 3, Shandong Bluestar Dongda Co., Ltd.; MN-3050D: number average molecular weight 3000, functionality 3, Shandong Bluestar Dongda Co., Ltd.; 10LD8001: number average molecular weight 8000, functionality 4.6, Shandong Bluestar Dongda Co., Ltd.; 10LD8005: number average molecular weight 9000, functionality 4.5, Shandong Bluestar Dongda Co., Ltd.; 10LD8007: number average molecular weight 8000, functionality 4.3, Shandong Bluestar Dongda Co., Ltd.; INOVOL C204: number average molecular weight 400, functionality 2, Shandong INOVOL New Materials Co., Ltd. INOVOL C210: number average molecular weight 1000, functionality 2, Shandong INOVOL New Materials Co., Ltd. INOVOL C220: number average molecular weight 2000, functionality 2, Shandong INOVOL New Materials Co., Ltd. INOVOL C240: number average molecular weight 4000, functionality 2, Shandong INOVOL New Materials Co., Ltd. XYlink HQEE-L: 4-hydroxyethyloxyethyl-1-hydroxyethylphenylene diether, Suzhou Xiangyuan New Materials Co., Ltd. XYlink HER-L: 3-hydroxyethyloxyethyl-1-hydroxyethylphenylene diether, Suzhou Xiangyuan New Materials Co., Ltd. PTMEG 250: number average molecular weight 250, functionality 2, Hyosung Chemical (Jiaxing) Co., Ltd. PTMEG 650: number average molecular weight 650, functionality 2, Hyosung Chemical (Jiaxing) Co., Ltd. PTMEG 1000: number average molecular weight 1000, functionality 2, Hyosung Chemical (Jiaxing) Co., Ltd. NORYL AP2001G: industrial grade, Saudi Basic Industries Corporation; NORYL N190: Industrial grade, Saudi Basic Industries Corporation; Glass fiber powder: 1000 mesh, alkali-free, Shenzhen Yataida Technology Co., Ltd.; Glass fiber powder: 1250 mesh, alkali-free, Shenzhen Yataida Technology Co., Ltd.; Calcined talc: 1250 mesh, Hebei Leijiang New Material Technology Co., Ltd.

[0026] Example 1 The polyurethane elastomer for the submarine cable bending limiter is composed of a polymer component and a prepolymer component in a mass ratio of 100:100, and the polymer component includes the following raw materials in mass fractions: Methylpropanediol: 5 parts; Diisopropanolamine: 2 parts; Triisopropanolamine: 5 parts; MN-500: 15 parts; 10LD8001: 30 parts; INOVOL C210: 23 parts; XYlink HQEE-L: 20 pieces; Bismuth isooctanoate: 0.02 parts; 1250 mesh glass fiber powder: 10 parts; 1000 mesh glass fiber powder: 5 parts; The prepolymer component includes the following raw materials in parts by weight: PTMEG1000: 18.7 parts; Special polyphenylene ether polyol NORYL AP2001G: 4 parts; Special polyphenylene ether polyol NORYL N190: 0.7 parts; MDI type isocyanate MDI-100: 61.3 parts; MDI type isocyanate liquefied MDI: 15.3 parts; 1250 mesh glass fiber powder: 15 parts.

[0027] The method for preparing the polyurethane elastomer for the submarine cable bending limiter comprises the following steps: (1) Polymer component: methyl propylene glycol, diisopropanolamine, triisopropanolamine, MN-500, 10LD8001, INOVOL C210, XYlink HQEE-L, bismuth isooctanoate, and 1000 mesh and 1250 mesh glass fiber powders are put into a reactor and mixed uniformly under vacuum to obtain a polymer component; (2) Prepolymer component: Heat PTMEG1000 to 120°C, then add special polyphenylene ether polyol NORYLAP2001G and NORYL N190 and stir until melted, cool to 60°C, then add MDI type isocyanate into the reactor in batches, keep stirring at 80°C for 1.5 hours to obtain a prepolymer with an -NCO content of 23.0 wt.%, finally add 1250 mesh glass fiber powder, continue to stir evenly, and obtain a prepolymer component; (3) The polymer component and the prepolymer component were heated to 30°C, mixed evenly in a mass ratio of 100:100, poured into a mold at 50°C, and post-vulcanized at 90°C for 12 hours after the mold was opened to obtain a polyurethane elastomer for a submarine cable bending limiter.

[0028] Example 2 The polyurethane elastomer for the submarine cable bending limiter is composed of a polymer component and a prepolymer component in a mass ratio of 100:107, and the polymer component includes the following raw materials in mass fractions: 1,4-Butanediol: 5 parts; Triethanolamine: 7 parts; DV-125: 10 parts; 10LD8001: 20 parts; 10LD8005: 17 parts; INOVOL C220: 10 parts; XYlink HQEE-L: 25 pieces; XYlink HER-L: 6 pieces; Dibutyltin di(isooctylmaleate): 0.01 parts; 1250 mesh glass fiber powder: 10 parts; The prepolymer component includes the following raw materials in parts by weight: PTMEG250: 1.8 parts; PTMEG650: 5.5 parts; Special polyphenylene ether polyol NORYL AP2001G: 4.9 parts; MDI type isocyanate MDI-100: 26.8 parts; MDI type isocyanate liquefied MDI: 62.5 parts; 1250 mesh glass fiber powder: 10 parts.

[0029] The method for preparing the polyurethane elastomer for the submarine cable bending limiter comprises the following steps: (1) Polymer component: 1,4-butanediol, triethanolamine, DV-125, 10LD8001, 10LD8005, INOVOLC220, XYlink HQEE-L, XYlink HER-L, dibutyltin di(isooctylmaleate), and 1250 mesh glass fiber powder are put into a reaction kettle and mixed evenly under vacuum to obtain a polymer component; (2) Prepolymer component: Heat PTMEG250 and PTMEG650 to 110°C, then add special polyphenylene ether polyol NORYL AP2001G and stir until melted, cool to 55°C, then add MDI type isocyanate into the reactor in batches, keep stirring at 78°C for 2 hours to obtain a prepolymer with an -NCO content of 25.0wt.%, finally add 1250 mesh glass fiber powder, continue to stir evenly, and obtain a prepolymer component; (3) The polymer component and the prepolymer component were heated to 35°C, mixed evenly in a mass ratio of 100:107, poured into a mold at 55°C, and post-vulcanized at 80°C for 16 hours after the mold was opened to obtain a polyurethane elastomer for a submarine cable bending limiter.

[0030] Example 3 The polyurethane elastomer for the submarine cable bending limiter is composed of a polymer component and a prepolymer component in a mass ratio of 100:96, and the polymer component includes the following raw materials in mass fractions: Diethylene glycol: 6 parts; 1,4-Butanediol: 2 parts; Triisopropanolamine: 8 parts; MN-500: 6 parts; MN-700: 6 parts; 10LD8005: 30 parts; INOVOL C204: 18 parts; INOVOL C210: 6 parts; XYlink HQEE-L: 18 copies; Dibutyltin di(isooctylmaleate): 0.02 parts; Bismuth isooctanoate: 0.01 part; 1000 mesh glass fiber powder: 20 parts; The prepolymer component includes the following raw materials in parts by weight: PTMEG650: 6.1 parts; Special polyphenylene ether polyol NORYL AP2001G: 4.1 parts; MDI type isocyanate MDI-100: 44.9 parts; MDI type isocyanate liquefied MDI: 44.9 parts; 1000 mesh glass fiber powder: 20 parts.

[0031] The method for preparing the polyurethane elastomer for the submarine cable bending limiter comprises the following steps: (1) Polymer component: Diethylene glycol, 1,4-butanediol, triisopropanolamine, 10LD8005, MN-500, MN-700, INOVOL C204, INOVOL C210, XYlink HQEE-L, bismuth isooctanoate, dibutyltin di(isooctylmaleate), and 1000 mesh glass fiber powder are put into a reaction kettle and mixed uniformly under vacuum to obtain a polymer component; (2) Prepolymer component: Heat PTMEG650 to 130°C, then add special polyphenylene ether polyol NORYLAP2001G and stir until melted, cool to 58°C, then add MDI type isocyanate into the reactor in batches, keep stirring at 85°C for 1 hour to obtain a prepolymer with an -NCO content of 27.0wt.%, finally add 1000 mesh glass fiber powder, continue to stir evenly, and obtain a prepolymer component; (3) The polymer component and the prepolymer component are heated to 40°C, mixed evenly in a mass ratio of 100:96, poured into a mold at 70°C, and post-vulcanized at 70°C for 14 hours after the mold is opened to obtain a polyurethane elastomer for a submarine cable bending limiter.

[0032] Example 4 The polyurethane elastomer for the submarine cable bending limiter is composed of a polymer component and a prepolymer component in a mass ratio of 100:83, and the polymer component includes the following raw materials in mass fractions: Diethylene glycol: 6 parts; Triisopropanolamine: 6 parts; MN-700: 25 parts; 10LD8005: 35 parts; INOVOL C204: 18 parts; XYlink HQEE-L: 10 pieces; Bismuth isooctanoate: 0.02 parts; 1250 mesh glass fiber powder: 15 parts; The prepolymer component includes the following raw materials in parts by weight: PTMEG250: 6.4 parts; Special polyphenylene ether polyol NORYL AP2001G: 2.8 parts; MDI type isocyanate MDI-100: 45.4 parts; MDI type isocyanate liquefied MDI: 45.4 parts; 1250 mesh glass fiber powder: 15 parts.

[0033] The method for preparing the polyurethane elastomer for the submarine cable bending limiter comprises the following steps: (1) Polymer component: Diethylene glycol, triisopropanolamine, MN-700, 10LD8005, INOVOL C204, XYlink HQEE-L, bismuth isooctanoate, and 1250 mesh glass fiber powder are put into a reactor and mixed uniformly under vacuum to obtain a polymer component; (2) Prepolymer component: Heat PTMEG250 to 115°C, then add special polyphenylene ether polyol NORYLAP2001G and stir until melted, cool to 57°C, then add MDI type isocyanate into the reactor in batches, keep stirring at 75°C for 1.5 hours to obtain a prepolymer with an -NCO content of 26.0 wt.%, finally add 1250 mesh glass fiber powder, continue to stir evenly, and obtain a prepolymer component; (3) The polymer component and the prepolymer component were heated to 38°C, mixed evenly in a mass ratio of 100:83, poured into a mold at 60°C, and post-vulcanized at 85°C for 10 hours after the mold was opened to obtain a polyurethane elastomer for a submarine cable bending limiter.

[0034] Example 5 The polyurethane elastomer for the submarine cable bending limiter is composed of a polymer component and a prepolymer component in a mass ratio of 100:105, and the polymer component includes the following raw materials in mass fractions: Methylpropanediol: 2 parts; 1,4-Butanediol: 3 parts; Diisopropanolamine: 8 parts; DV-125: 20 parts; 10LD8007: 33 parts; INOVOL C220: 14 parts; XYlink HER-L: 20 copies; Dibutyltin di(isooctylmaleate): 0.02 parts; 1000 mesh glass fiber powder: 20 parts; The prepolymer component includes the following raw materials in parts by weight: PTMEG 250: 9.3 parts; Special polyphenylene ether polyol NORYL N190: 3 parts; MDI type isocyanate MDI-100: 61.5 parts; MDI type isocyanate liquefied MDI: 26.2 parts; 1250 mesh glass fiber powder: 20 parts.

[0035] The method for preparing the polyurethane elastomer for the submarine cable bending limiter comprises the following steps: (1) Polymer component: methyl propanediol, 1,4-butanediol, diisopropanolamine, DV-125, 10LD8007, INOVOL C220, XYlink HER-L, dibutyltin di(isooctylmaleate), and 1000 mesh glass fiber powder are put into a reaction kettle and mixed evenly under vacuum to obtain a polymer component; (2) Prepolymer component: Heat PTMEG250 to 110°C, then add special polyphenylene ether polyol NORYLN190 and stir until melted, cool to 56°C, then add MDI type isocyanate into the reactor in batches, keep stirring at 84°C for 1.5 hours to obtain a prepolymer with an -NCO content of 25.0 wt.%, finally add 1250 mesh glass fiber powder, continue to stir evenly, and obtain a prepolymer component; (3) The polymer component and the prepolymer component were heated to 32°C, mixed evenly in a mass ratio of 100:105, poured into a mold at 70°C, and post-vulcanized at 80°C for 14 hours after the mold was opened to obtain a polyurethane elastomer for a submarine cable bending limiter.

[0036] Comparative Example 1 This comparative example is the same as Example 2, except that the prepolymer component includes the following raw materials in parts by weight: PTMEG250: 3.5 parts; PTMEG650: 7.1 parts; MDI type isocyanate MDI-100: 26.8 parts; MDI type isocyanate liquefied MDI: 62.6 parts; 1250 mesh glass fiber powder: 10 parts; The remaining components and the preparation method of the polyurethane elastomer for the submarine cable bending limiter are the same as those in Example 2.

[0037] Comparative Example 2 This comparative example is the same as Example 4, except that 10LD8005 in the polymer component is replaced by INOVOL C240 ​​of the same mass fraction, and the remaining components and the preparation method of the polyurethane elastomer for the submarine cable bending limiter are the same as those in Example 4.

[0038] Comparative Example 3 This comparative example is the same as Example 3, except that XYlink HQEE-L in the polymer component is replaced with DV-125 of the same mass fraction, and the remaining components and the preparation method of the polyurethane elastomer for the submarine cable bending limiter are the same as those in Example 3.

[0039] Comparative Example 4 This comparative example is the same as Example 4, except that the 1250 mesh glass fiber powder in the polymer component and the prepolymer component is removed, and the remaining components and the preparation method of the polyurethane elastomer for the submarine cable bending limiter are the same as those in Example 4.

[0040] Comparative Example 5 This comparative example is the same as Example 2, except that INOVOL C220 in the polymer component is replaced by MN-3050D of the same mass fraction, and the remaining components and the preparation method of the polyurethane elastomer for the submarine cable bending limiter are the same as those in Example 2.

[0041] Comparative Example 6 This comparative example is the same as Example 4, except that the 1250 mesh glass fiber powder in the polymer component and the prepolymer component is replaced with 1250 mesh calcined talcum powder of equal mass, and the remaining components and the preparation method of the polyurethane elastomer for the submarine cable bending limiter are the same as those in Example 4.

[0042] The performance of the polyurethane elastomer for the submarine cable bending limiter obtained in Examples 1-5 and Comparative Examples 1-6 was tested. The tensile strength was measured using a UN-7001-LS servo universal material tensile testing machine produced by High Speed ​​Rail Testing Instrument Co., Ltd. according to GB / T1040.1-2018 standard. The Shore D hardness was measured according to GB / T531.1-2008 standard. The DIN abrasion was measured according to GB / T9867-2008 standard. The hydrolysis resistance was measured according to GB / T1690-2010 standard, and the tensile strength change rate was calculated after the sample was subjected to wet heat treatment. The test conditions were as follows: the test temperature was 80°C, the sample was immersed in seawater, taken out after continuous wet heat treatment for 8 weeks, and placed at room temperature for 2 hours before mechanical performance testing, and the tensile strength retention rate before and after wet heat treatment was calculated. When testing the water absorption rate, the material was cut into Type I specimens according to GB / T528-2009 standard, and the surface moisture was wiped dry after being immersed in distilled water for 48 hours to test the mass change rate after immersion.

[0043] The performance test results of Examples 1-5 and Comparative Examples 1-6 are shown in Tables 1 and 2.

[0044] Table 1 Performance test table of Examples 1-5

[0045] Table 2 Performance test table of comparative examples 1-6

[0046] Tables 1 and 2 are performance test results of polyurethane elastomer materials for submarine cable bending limiters obtained in Examples 1-5 of the present invention and Comparative Examples 1-6. From the comparison between Example 2 and Comparative Example 1, it can be found that the addition of special polyphenylene ether polyol can significantly improve the hardness, tensile strength, high temperature hardness and high temperature tensile strength of the material, and at the same time can reduce the water absorption rate of the material and improve the hydrolysis resistance of the material. This is mainly due to the fact that it is a polyphenyl ring structure containing ether bonds, which makes the material more rigid and flexible, and also reduces the hydrophilicity of the material.

[0047] Comparing the data of Example 4 and Comparative Example 2, 10LD8005, as a high-activity, high-functionality, high-molecular-weight polyether polyol, has a high-functionality structure that can promote the formation of a cross-linked network structure in the material and strengthen the connection between molecular chains, thereby improving the hardness, tensile strength and thermal stability of the material compared to traditional difunctional polyether polyols.

[0048] Comparing the data of Example 3 and Comparative Example 3, XYlink HQEE-L has a lower molecular weight and a single benzene ring structure in its structure. When it acts as a hard segment structure in the polyurethane material, it increases the microphase separation and heat resistance of the material, and significantly improves the hardness, tensile strength and high-temperature performance of the material. At the same time, due to the high electron cloud density of the benzene ring, it is difficult for the hydrogen atoms in the water molecules to approach the electron cloud of the benzene ring through dipole interactions. Therefore, the water absorption rate of the material is lower and the hydrolysis resistance is better.

[0049] Comparing Comparative Example 4 and Comparative Example 6 with Example 4, the addition of glass fiber powder in Example 4 can disperse and transfer stress, thereby reducing the internal stress of the material and increasing the tensile strength. At the same time, the supporting effect of the glass fiber powder in the material increases the heat resistance of the material, making the material more adaptable to harsh use conditions. In addition, compared with spherical or flaky talcum powder of the same mesh size, glass fiber has a lower specific gravity, better mechanical guidance, better thermal conductivity, and lower moisture adsorption. After addition, various mechanical performance data are better, and it is more suitable for submarine cable bending limiter products with complex force and high temperature resistance requirements.

[0050] Comparing Example 5 with Example 2, the polyether polyol with a functionality of 2 and a number average molecular weight of 2000 in the system is replaced with an equal amount of polyether polyol with a functionality of 3 and a number average molecular weight of 3000. Due to the increase in functionality, the flexibility of the material is greatly affected, the elongation at break will be lower than the industry requirement, and the brittleness of the product is too large, resulting in easy breakage during use.

Claims

1. A polyurethane elastomer for a submarine cable bending limiter, characterized in that: The polymer component and the prepolymer component are composed of a mass ratio of 100: (83-107), and the polymer component includes the following raw materials in mass fractions: Small molecule polyol: 5-8 parts; Small molecule polyol amine: 6-8 parts; Polyether polyol 1: 10-25 parts; Polyether polyol 2: 30-37 parts; Polyether polyol 3: 10-24 parts; Aromatic diol chain extender: 10-31 parts; Organic metal catalyst: 0.01-0.03 parts; Glass fiber powder: 10-20 parts; The prepolymer component includes the following raw materials in parts by weight: Polytetramethylene glycol: 6.1-18.7 parts; Special polyphenylene ether polyol: 2.8-4.9 parts; MDI isocyanate: 76.6-90.8 parts; Glass fiber powder: 10-20 parts; The polyether polyol 1 is a polyether polyol with a functionality of ≥3 and a number average molecular weight of ≤700; The polyether polyol 2 is a polyether polyol with a functionality ≥ 3 and a number average molecular weight ≥ 8000; The polyether polyol 3 is a polyether polyol having a functionality of 2 and a number average molecular weight of ≤2000; The special polyphenylene ether polyol is one or both of NORYL AP2001G and NORYL N190; The mesh number of the glass fiber powder is 1000-1250 meshes.

2. The polyurethane elastomer for a submarine cable bending limiter according to claim 1, characterized in that: The small molecule polyol is one or two of 1,4-butanediol, diethylene glycol and methyl propylene glycol.

3. The polyurethane elastomer for a submarine cable bending limiter according to claim 1, characterized in that: The small molecule polyol amine is one or two of diisopropanolamine, triisopropanolamine and triethanolamine.

4. The polyurethane elastomer for a submarine cable bending limiter according to claim 1, characterized in that: The polyether polyol 1 is one or two of DV-125, MN-500 and MN-700; the polyether polyol 2 is one or two of 10LD8001, 10LD8005 and 10LD8007; the polyether polyol 3 is one or two of INOVOL C204, INOVOL C210 and INOVOLC220.

5. The polyurethane elastomer for a submarine cable bending limiter according to claim 1, characterized in that: The aromatic diol chain extender is one or both of XYlink HQEE-L and XYlink HER-L.

6. The polyurethane elastomer for a submarine cable bending limiter according to claim 1, characterized in that: The organic metal catalyst is one or two of bismuth isooctanoate and dibutyltin di(isooctylmaleate).

7. The polyurethane elastomer for a submarine cable bending limiter according to claim 1, characterized in that: The polytetramethylene ether glycol is one or two of PTMEG250, PTMEG650 and PTMEG1000.

8. The polyurethane elastomer for a submarine cable bending limiter according to claim 1, characterized in that: The MDI type isocyanate is a mixture of carbodiimide modified diphenylmethane diisocyanate and MDI-100 in a mass ratio of 1: (0.4-4).

9. A method for preparing the polyurethane elastomer for a submarine cable bending limiter according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) Polymer component: small molecule polyol, small molecule polyol amine, polyether polyol 1, polyether polyol 2, polyether polyol 3, aromatic diol chain extender, organic metal catalyst and glass fiber powder are put into a reaction kettle and mixed uniformly under vacuum to obtain a polymer component; (2) Prepolymer component: Heat polytetramethylene glycol to 110-130°C, then add special polyphenylene ether polyol and stir until melted, cool to 55-60°C, then add MDI type isocyanate to the reactor in batches, keep stirring at 75-85°C for 1-2 hours to obtain a prepolymer with an -NCO content of 23.0-27.0wt.%, finally add glass fiber powder, continue to stir evenly, and obtain a prepolymer component; (3) The polymer component and the prepolymer component are heated to 30-40°C, mixed evenly according to the mass ratio, poured into a mold at 50-70°C, and post-vulcanized at 70-90°C for 10-16h after the mold is opened to obtain a polyurethane elastomer for a submarine cable bending limiter.

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