Polyurethane elastomer for submarine cable bending limiter and preparation method thereof

Abstract

The present invention belongs to the technical field of polyurethane elastomers, and specifically relates to a polyurethane elastomer for submarine cable bend limiters and a preparation method thereof. The polyurethane elastomer for submarine cable bend limiters is composed of a polymer component and a prepolymer component. The polymer component includes the following raw materials: small molecule polyols, small molecule polyol amines, polyether polyol 1, polyether polyol 2, polyether polyol 3, aromatic diol chain extenders, organic metal catalysts, and glass fiber powder. The prepolymer component includes the following raw materials: polytetramethylene ether glycol, special polyphenylene ether polyol, MDI type isocyanate, and glass fiber powder. The polyurethane elastomer for submarine cable bend limiters provided by the present invention has excellent mechanical properties, good high temperature resistance and hydrolysis resistance, and meets the market demand for high-performance submarine cable bend limiter materials. The present invention also provides a preparation method thereof, and the preparation process is simple.

Description

Technical Field

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

[0002] Submarine cable bend limiters are devices used to protect submarine communication cables. They prevent excessive bending caused by excessive force during installation, transportation, and operation, thereby extending the cable's service life 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 face various complex marine environments, making the long-term safety and reliability of submarine cables 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 mechanical strength requirements 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 can maintain a high performance retention rate when the submarine cable is heated; the bend limiter is located below the water surface and must ensure that it can be in long-term contact with seawater and has excellent anti-hydrolysis and anti-fatigue properties.

[0004] CN110922556A discloses a polyurethane elastomer material resistant to seawater corrosion and a preparation method thereof. The material comprises two components, A and B. Component A comprises glycerol polyether polyol, toughening polyether polyol, chain extender, catalyst, and hydrophobic nanopowder, and component B comprises a polyisocyanate curing agent. The high specific surface area and low surface energy characteristics of the hydrophobic nanopowder significantly enhance the hydrophobicity, mechanical strength, and seawater corrosion resistance of the polyurethane elastomer material. The material exhibits a contact angle of 105-128°, a tensile strength of 28-48 MPa, and a weight loss of only 1-6% due to seawater corrosion. Furthermore, the material exhibits enhanced wear resistance and low wear loss. However, no further testing of the mechanical properties after seawater corrosion is performed. Furthermore, the porous hydrophobic nanopowder readily absorbs non-polar dirt (such as oil) in seawater, which can accelerate aging and decomposition of the product.

[0005] CN118562091A discloses a cast polyurethane elastomer and a preparation method thereof. Material A comprises polytetramethylene glycol, polycaprolactone diol, liquefied MDI, and hydrogenated MDI. Material B comprises polytetramethylene glycol, 1,4-butanediol (BOD), 4,4'-methylenebis(2-chloroaniline) (MOCA), an antioxidant, a light stabilizer, etc., which are mixed, cast, and vulcanized to produce a polyurethane elastomer. Liquefied MDI replaces solid MDI, and MOCA and BDO collaborate in chain extension to regulate the curing time. Meanwhile, polycaprolactone is introduced to enhance performance. The product exhibits excellent mechanical properties, high resilience, low permanent set at break, and excellent seawater resistance. However, the ester bonds in polycaprolactone are easily hydrolyzed in marine environments, resulting in a rapid decrease in the product's mechanical properties and an inability to guarantee its lifespan. 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 submarine cable bend limiters. The product has excellent mechanical properties, good high temperature resistance and hydrolysis resistance, and meets the market demand for high-performance submarine cable bend limiter materials; the present invention also provides a preparation method thereof, and the preparation process is simple.

[0007] The polyurethane elastomer for a submarine cable bend limiter of the present invention is composed of a polymer component and a prepolymer component in a mass ratio of 100:(83-107), wherein the polymer component includes the following raw materials in parts by mass:

[0008] Small molecule polyols: 5-8 parts;

[0009] Small molecule polyol amine: 6-8 parts;

[0010] Polyether polyol 1: 10-25 parts;

[0011] Polyether polyol 2: 30-37 parts;

[0012] Polyether polyol 3: 10-24 parts;

[0013] Aromatic diol chain extender: 10-31 parts;

[0014] Organic metal catalyst: 0.01-0.03 parts;

[0015] Glass fiber powder: 10-20 parts;

[0016] The prepolymer component includes the following raw materials in parts by weight:

[0017] Polytetramethylene ether glycol: 6.1-18.7 parts;

[0018] Special polyphenylene ether polyol: 2.8-4.9 parts;

[0019] MDI isocyanate: 76.6-90.8 parts;

[0020] Glass fiber powder: 10-20 parts.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] The mesh number of the glass fiber powder is 1000-1250 mesh, and preferably one of the 1000 mesh and 1250 mesh alkali-free glass fiber powders commercially available from Shenzhen Yataida Technology Co., Ltd., or a mixture of the two mesh numbers in any proportion.

[0025] The small molecule polyol is one or two of 1,4-butanediol, diethylene glycol and methyl propylene glycol.

[0026] The small molecule polyol amine is one or two of diisopropanolamine, triisopropanolamine and triethanolamine.

[0027] The aromatic diol chain extender is one or both of XYlink HQEE-L and XYlink HER-L.

[0028] The organic metal catalyst is one or two of bismuth isooctanoate and dibutyltin di(isooctylmaleate).

[0029] The polytetramethylene ether glycol is one or two of PTMEG250, PTMEG650 and PTMEG1000.

[0030] The special polyphenylene ether polyol is one or both of NORYL AP2001G and NORYL N190.

[0031] 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).

[0032] The method for preparing the polyurethane elastomer for the submarine cable bend limiter comprises the following steps:

[0033] (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 reactor and mixed uniformly under vacuum to obtain the polymer component;

[0034] (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 into 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 and continue stirring to obtain a prepolymer component;

[0035] (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 a temperature of 70-90°C for 10-16 hours after the mold is opened to obtain a polyurethane elastomer for submarine cable bending limiters.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) The polyurethane elastomer for submarine cable bend limiter of the present invention is prepared by adding a liquid aromatic diol chain extender containing benzene rings to the polymer component, and adding a special polyphenylene ether polyol containing multiple benzene rings to the prepolymer component. The effects of the benzene rings in the two components make the product have excellent high temperature resistance and low water absorption rate, while increasing the hydrolysis resistance of the product.

[0038] (2) The polyurethane elastomer for 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, solving 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 limiter.

[0039] (3) The polyurethane elastomer for the submarine cable bend 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, reducing internal stress and increasing support.

[0040] (4) The preparation method of the polyurethane elastomer for submarine cable bend limiter of the present invention is simple in 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℃, tensile strength ≥17MPa, and it has the characteristics of low water absorption and hydrolysis resistance, meeting the market demand for high-performance submarine cable bend limiter materials. DETAILED DESCRIPTION

[0041] The present invention will be further described below with reference to the following examples and comparative examples. Unless otherwise specified, the raw materials used in the examples and comparative examples are all conventional commercially available raw materials, and the process methods used in the examples and comparative examples are all conventional methods in the art unless otherwise specified.

[0042] The raw materials used in the examples and comparative examples are described as follows:

[0043] DV-125: number average molecular weight 375, functionality 3, Shandong Bluestar Dongda Co., Ltd.

[0044] MN-500: number average molecular weight 500, functionality 3, Shandong Bluestar Dongda Co., Ltd.

[0045] MN-700: number average molecular weight 700, functionality 3, Shandong Bluestar Dongda Co., Ltd.

[0046] MN-3050D: number average molecular weight 3000, functionality 3, Shandong Bluestar Dongda Co., Ltd.

[0047] 10LD8001: number average molecular weight 8000, functionality 4.6, Shandong Bluestar Dongda Co., Ltd.

[0048] 10LD8005: number average molecular weight 9000, functionality 4.5, Shandong Bluestar Dongda Co., Ltd.

[0049] 10LD8007: number average molecular weight 8000, functionality 4.3, Shandong Bluestar Dongda Co., Ltd.

[0050] INOVOL C204: number average molecular weight 400, functionality 2, Shandong INOVOL New Materials Co., Ltd.

[0051] INOVOL C210: number average molecular weight 1000, functionality 2, Shandong INOVOL New Materials Co., Ltd.

[0052] INOVOL C220: number average molecular weight 2000, functionality 2, Shandong INOVOL New Materials Co., Ltd.

[0053] INOVOL C240: number average molecular weight 4000, functionality 2, Shandong INOVOL New Materials Co., Ltd.

[0054] XYlink HQEE-L: 4-hydroxyethyloxyethyl-1-hydroxyethylphenylenediether, Suzhou Xiangyuan New Materials Co., Ltd.

[0055] XYlink HER-L: 3-hydroxyethyloxyethyl-1-hydroxyethylphenylenediether, Suzhou Xiangyuan New Materials Co., Ltd.

[0056] PTMEG 250: number average molecular weight 250, functionality 2, Hyosung Chemical (Jiaxing) Co., Ltd.

[0057] PTMEG 650: number average molecular weight 650, functionality 2, Hyosung Chemical (Jiaxing) Co., Ltd.

[0058] PTMEG 1000: number average molecular weight 1000, functionality 2, Hyosung Chemical (Jiaxing) Co., Ltd.

[0059] NORYL AP2001G: industrial grade, Saudi Basic Industries Corporation;

[0060] NORYL N190: industrial grade, Saudi Basic Industries Corporation;

[0061] Glass fiber powder: 1000 mesh, alkali-free, Shenzhen Yataida Technology Co., Ltd.

[0062] Glass fiber powder: 1250 mesh, alkali-free, Shenzhen Yataida Technology Co., Ltd.

[0063] Calcined talc: 1250 mesh, Hebei Leijiang New Material Technology Co., Ltd.

[0064] Example 1

[0065] The polyurethane elastomer for submarine cable bend limiters is composed of a polymer component and a prepolymer component in a mass ratio of 100:100. The polymer component includes the following raw materials in parts by mass:

[0066] Methylpropanediol: 5 parts;

[0067] Diisopropanolamine: 2 parts;

[0068] Triisopropanolamine: 5 parts;

[0069] MN-500: 15 parts;

[0070] 10LD8001: 30 parts;

[0071] INOVOL C210: 23 parts;

[0072] XYlink HQEE-L: 20 copies;

[0073] Bismuth isooctanoate: 0.02 parts;

[0074] 1250 mesh glass fiber powder: 10 parts;

[0075] 1000 mesh glass fiber powder: 5 parts;

[0076] The prepolymer component includes the following raw materials in parts by weight:

[0077] PTMEG1000: 18.7 parts;

[0078] Special polyphenylene ether polyol NORYL AP2001G: 4 parts;

[0079] Special polyphenylene ether polyol NORYL N190: 0.7 parts;

[0080] MDI isocyanate MDI-100: 61.3 parts;

[0081] MDI type isocyanate liquefied MDI: 15.3 parts;

[0082] 1250 mesh glass fiber powder: 15 parts.

[0083] The method for preparing the polyurethane elastomer for the submarine cable bend limiter comprises the following steps:

[0084] (1) Polymer component: Methylpropanediol, 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;

[0085] (2) Prepolymer component: PTMEG1000 was heated to 120°C, and then special polyphenylene ether polyol NORYLAP2001G and NORYL N190 were added and stirred until melted. The temperature was then lowered to 60°C, and MDI type isocyanate was added to the reactor in batches. The mixture was stirred at 80°C for 1.5 hours to obtain a prepolymer with an -NCO content of 23.0 wt.%. Finally, 1250 mesh glass fiber powder was added and the mixture was stirred evenly to obtain the prepolymer component.

[0086] (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 submarine cable bending limiters.

[0087] Example 2

[0088] The polyurethane elastomer for submarine cable bend limiters is composed of a polymer component and a prepolymer component in a mass ratio of 100:107. The polymer component includes the following raw materials in parts by mass:

[0089] 1,4-Butanediol: 5 parts;

[0090] Triethanolamine: 7 parts;

[0091] DV-125: 10 parts;

[0092] 10LD8001: 20 parts;

[0093] 10LD8005: 17 parts;

[0094] INOVOL C220: 10 parts;

[0095] XYlink HQEE-L: 25 copies;

[0096] XYlink HER-L: 6 servings;

[0097] Dibutyltin di(isooctylmaleate): 0.01 parts;

[0098] 1250 mesh glass fiber powder: 10 parts;

[0099] The prepolymer component includes the following raw materials in parts by weight:

[0100] PTMEG250: 1.8 parts;

[0101] PTMEG650: 5.5 parts;

[0102] Special polyphenylene ether polyol NORYL AP2001G: 4.9 parts;

[0103] MDI isocyanate MDI-100: 26.8 parts;

[0104] MDI type isocyanate liquefied MDI: 62.5 parts;

[0105] 1250 mesh glass fiber powder: 10 parts.

[0106] The method for preparing the polyurethane elastomer for the submarine cable bend limiter comprises the following steps:

[0107] (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 were put into a reactor and mixed uniformly under vacuum to obtain the polymer component;

[0108] (2) Prepolymer component: PTMEG250 and PTMEG650 were heated to 110°C, and then the special polyphenylene ether polyol NORYL AP2001G was added and stirred until melted. The temperature was then lowered to 55°C, and MDI type isocyanate was added to the reactor in batches. The mixture was stirred at 78°C for 2 h to obtain a prepolymer with an -NCO content of 25.0 wt.%. Finally, 1250 mesh glass fiber powder was added and the mixture was stirred evenly to obtain the prepolymer component.

[0109] (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 submarine cable bending limiters.

[0110] Example 3

[0111] The polyurethane elastomer for submarine cable bend limiters is composed of a polymer component and a prepolymer component in a mass ratio of 100:96. The polymer component includes the following raw materials in parts by mass:

[0112] Diethylene glycol: 6 parts;

[0113] 1,4-Butanediol: 2 parts;

[0114] Triisopropanolamine: 8 parts;

[0115] MN-500: 6 parts;

[0116] MN-700: 6 parts;

[0117] 10LD8005: 30 parts;

[0118] INOVOL C204: 18 parts;

[0119] INOVOL C210: 6 parts;

[0120] XYlink HQEE-L: 18 copies;

[0121] Dibutyltin di(isooctylmaleate): 0.02 parts;

[0122] Bismuth isooctanoate: 0.01 parts;

[0123] 1000 mesh glass fiber powder: 20 parts;

[0124] The prepolymer component includes the following raw materials in parts by weight:

[0125] PTMEG650: 6.1 parts;

[0126] Special polyphenylene ether polyol NORYL AP2001G: 4.1 parts;

[0127] MDI isocyanate MDI-100: 44.9 parts;

[0128] MDI type isocyanate liquefied MDI: 44.9 parts;

[0129] 1000 mesh glass fiber powder: 20 parts.

[0130] The method for preparing the polyurethane elastomer for the submarine cable bend limiter comprises the following steps:

[0131] (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 reactor and mixed uniformly under vacuum to obtain a polymer component;

[0132] (2) Prepolymer component: PTMEG650 was heated to 130°C, and then the special polyphenylene ether polyol NORYLAP2001G was added and stirred until melted. The temperature was then lowered to 58°C, and MDI type isocyanate was added to the reactor in batches. The mixture was stirred at 85°C for 1 hour to obtain a prepolymer with an -NCO content of 27.0 wt.%. Finally, 1000 mesh glass fiber powder was added and the mixture was stirred evenly to obtain the prepolymer component.

[0133] (3) The polymer component and the prepolymer component were 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 was opened to obtain a polyurethane elastomer for submarine cable bending limiters.

[0134] Example 4

[0135] The polyurethane elastomer for submarine cable bend limiters is composed of a polymer component and a prepolymer component in a mass ratio of 100:83. The polymer component includes the following raw materials in parts by mass:

[0136] Diethylene glycol: 6 parts;

[0137] Triisopropanolamine: 6 parts;

[0138] MN-700: 25 parts;

[0139] 10LD8005: 35 parts;

[0140] INOVOL C204: 18 parts;

[0141] XYlink HQEE-L: 10 copies;

[0142] Bismuth isooctanoate: 0.02 parts;

[0143] 1250 mesh glass fiber powder: 15 parts;

[0144] The prepolymer component includes the following raw materials in parts by weight:

[0145] PTMEG250: 6.4 parts;

[0146] Special polyphenylene ether polyol NORYL AP2001G: 2.8 parts;

[0147] MDI isocyanate MDI-100: 45.4 parts;

[0148] MDI type isocyanate liquefied MDI: 45.4 parts;

[0149] 1250 mesh glass fiber powder: 15 parts.

[0150] The method for preparing the polyurethane elastomer for the submarine cable bend limiter comprises the following steps:

[0151] (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 the polymer component;

[0152] (2) Prepolymer component: PTMEG250 was heated to 115°C, and then the special polyphenylene ether polyol NORYLAP2001G was added and stirred until melted. The temperature was then lowered to 57°C, and MDI type isocyanate was added to the reactor in batches. The mixture was stirred at 75°C for 1.5 hours to obtain a prepolymer with an -NCO content of 26.0 wt.%. Finally, 1250 mesh glass fiber powder was added and the mixture was stirred evenly to obtain the prepolymer component.

[0153] (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 submarine cable bending limiters.

[0154] Example 5

[0155] The polyurethane elastomer for submarine cable bend limiters is composed of a polymer component and a prepolymer component in a mass ratio of 100:105. The polymer component includes the following raw materials in parts by mass:

[0156] Methylpropanediol: 2 parts;

[0157] 1,4-Butanediol: 3 parts;

[0158] Diisopropanolamine: 8 parts;

[0159] DV-125: 20 parts;

[0160] 10LD8007: 33 parts;

[0161] INOVOL C220: 14 parts;

[0162] XYlink HER-L: 20 copies;

[0163] Dibutyltin di(isooctylmaleate): 0.02 parts;

[0164] 1000 mesh glass fiber powder: 20 parts;

[0165] The prepolymer component includes the following raw materials in parts by weight:

[0166] PTMEG 250: 9.3 parts;

[0167] Special polyphenylene ether polyol NORYL N190: 3 parts;

[0168] MDI isocyanate MDI-100: 61.5 parts;

[0169] MDI type isocyanate liquefied MDI: 26.2 parts;

[0170] 1250 mesh glass fiber powder: 20 parts.

[0171] The method for preparing the polyurethane elastomer for the submarine cable bend limiter comprises the following steps:

[0172] (1) Polymer component: methyl propylene glycol, 1,4-butanediol, diisopropanolamine, DV-125, 10LD8007, INOVOL C220, XYlink HER-L, dibutyltin di(isooctylmaleate), and 1000 mesh glass fiber powder were put into a reactor and mixed uniformly under vacuum to obtain the polymer component;

[0173] (2) Prepolymer component: PTMEG250 was heated to 110°C, and then the special polyphenylene ether polyol NORYLN190 was added and stirred until melted. The temperature was then lowered to 56°C, and MDI type isocyanate was added to the reactor in batches. The mixture was stirred at 84°C for 1.5 hours to obtain a prepolymer with an -NCO content of 25.0 wt.%. Finally, 1250 mesh glass fiber powder was added and the mixture was stirred evenly to obtain the prepolymer component.

[0174] (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 submarine cable bending limiters.

[0175] Comparative Example 1

[0176] This comparative example is the same as Example 2, except that the prepolymer component includes the following raw materials in parts by mass:

[0177] PTMEG250: 3.5 parts;

[0178] PTMEG650: 7.1 parts;

[0179] MDI isocyanate MDI-100: 26.8 parts;

[0180] MDI type isocyanate liquefied MDI: 62.6 parts;

[0181] 1250 mesh glass fiber powder: 10 parts;

[0182] The remaining components and the preparation method of the polyurethane elastomer for the submarine cable bend limiter are the same as those in Example 2.

[0183] Comparative Example 2

[0184] This comparative example is the same as Example 4, except that 10LD8005 in the polymer component is replaced with INOVOL C240 ​​of the same mass fraction. The remaining components and the preparation method of the polyurethane elastomer for submarine cable bend limiter are the same as those in Example 4.

[0185] Comparative Example 3

[0186] This comparative example is the same as Example 3, except that XYlink HQEE-L in the polymer component is replaced with DV-125 of equal weight fraction, and the remaining components and the preparation method of the polyurethane elastomer for submarine cable bend limiter are the same as those in Example 3.

[0187] Comparative Example 4

[0188] 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 bend limiter are the same as those in Example 4.

[0189] Comparative Example 5

[0190] This comparative example is the same as Example 2, except that INOVOL C220 in the polymer component is replaced with MN-3050D of equal weight fraction. The remaining components and the preparation method of the polyurethane elastomer for submarine cable bend limiter are the same as those in Example 2.

[0191] Comparative Example 6

[0192] 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 talc powder of equal mass, and the remaining components and the preparation method of the polyurethane elastomer for the submarine cable bend limiter are the same as those in Example 4.

[0193] The performance of the polyurethane elastomer used for the submarine cable bend 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 ​​Railway 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, and after continuous wet heat treatment for 8 weeks, it was taken out 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. For the water absorption test, the material was cut into Type I specimens according to GB / T528-2009 standard, soaked in distilled water for 48 hours, and then the surface moisture was wiped dry to test the mass change rate after immersion.

[0194] The performance test results of Examples 1-5 and Comparative Examples 1-6 are shown in Tables 1 and 2.

[0195] Table 1 Performance test table of Examples 1-5

[0196]

[0197] Table 2 Performance test table of comparative examples 1-6

[0198]

[0199] Tables 1 and 2 present the performance test results of polyurethane elastomer materials for submarine cable bend limiters obtained in Examples 1-5 and Comparative Examples 1-6 of the present invention. A comparison of Example 2 and Comparative Example 1 reveals that the addition of the specialty polyphenylene ether polyol significantly improves the material's hardness, tensile strength, high-temperature hardness, and high-temperature tensile strength, while also reducing its water absorption and improving its hydrolysis resistance. This is primarily due to its polyphenylene ring structure containing ether bonds, which imparts both increased rigidity and flexibility to the material while also reducing its hydrophilicity.

[0200] Comparing the data of Example 4 and Comparative Example 2, 10LD8005, as a highly active, highly functional, and high molecular weight polyether polyol, has a high functionality structure that can promote the formation of a cross-linked network structure in the material compared to traditional difunctional polyether polyols, thereby strengthening the connection between molecular chains and improving the hardness, tensile strength, and thermal stability of the material.

[0201] 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.

[0202] 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.

[0203] Comparing Comparative 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 requirements, and the brittleness of the product is too large, resulting in the product being easily broken during use.

Claims

1. A polyurethane elastomer for a submarine cable bend 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 parts by mass: Small molecule polyols: 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 ether 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 one or both of 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 INOVOL C220; the special polyphenylene ether polyol is one or two of NORYL AP2001G and NORYL N190; The mesh number of the glass fiber powder is 1000-1250 meshes.

2. The polyurethane elastomer for submarine cable bend 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 submarine cable bend 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 bend limiter according to claim 1, wherein: The aromatic diol chain extender is one or both of XYlink HQEE-L and XYlink HER-L.

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

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

7. The polyurethane elastomer for a submarine cable bend 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).

8. A method for preparing the polyurethane elastomer for submarine cable bend limiter according to any one of claims 1 to 7, 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 reactor and mixed uniformly under vacuum to obtain the 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 into 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 and continue stirring to 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 a temperature of 70-90°C for 10-16 hours after the mold is opened to obtain a polyurethane elastomer for submarine cable bending limiters.

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