A phosphorus-containing polyurethane silicone wax, its preparation method and application

Abstract

This invention provides a phosphorus-containing polyurethane silicone wax, its preparation method, and its application. The preparation method includes the following steps: reacting a macromolecular polyol, a polyisocyanate, and an isocyanate-terminated polysiloxane at a first set temperature for a first set time to obtain an organosilicon polyurethane prepolymer; mixing and stirring the organosilicon polyurethane prepolymer with a chain extender, and after stirring, obtaining a pre-chain-extended organosilicon-modified polyurethane prepolymer; and end-capping and curing the pre-chain-extended organosilicon-modified polyurethane prepolymer with an end-capping agent to obtain the phosphorus-containing polyurethane silicone wax. The macromolecular polyol includes polyester polyols and phosphorus-containing polyols; the end-capping agent includes higher amines and / or higher alcohols with ≥16 carbon atoms. The phosphorus-containing polyurethane silicone wax is prepared using the above-described preparation method. This phosphorus-containing polyurethane silicone wax organically combines organosilicon and phosphate esters and can be used as a flame retardant and feel-enhancing agent to modify rubber and plastic materials, showing broad application prospects.

Description

Technical Field

[0001] This invention belongs to the field of organosilicon technology, specifically relating to a phosphorus-containing polyurethane silicone wax, its preparation method, and its application. Background Technology

[0002] Polyurethane materials are widely used in various fields due to their excellent physical and mechanical properties, wear resistance, high elasticity and toughness, and good processing performance. However, in certain special applications, such as wire and cable sheathing and building materials, higher requirements are placed on the flame retardant properties of the materials. Traditional flame retardant methods often achieve this by adding halogenated flame retardants, but these halogenated flame retardants produce toxic gases during combustion, posing a threat to the environment and human health. Therefore, the development of halogen-free flame-retardant polyurethane materials has become a current research hotspot.

[0003] Phosphorus-based flame retardants are environmentally friendly flame retardants that generate non-volatile substances such as phosphoric acid and metaphosphoric acid during combustion. These substances coat the material surface, forming a protective layer that effectively prevents combustion and does not produce toxic gases. Introducing phosphorus-based flame retardants into polyurethane materials can significantly improve their flame retardancy. CN103874735A discloses a migration-free, halogen-free flame-retardant thermoplastic polyurethane composition comprising 10 to 89 wt% of a continuous resin phase containing thermoplastic polyurethane based on the total weight of the composition; 1 to 10 wt% of an aromatic organophosphate flame retardant with a melting point of at least 50°C based on the total weight of the composition; and 10 to 89 wt% of an inorganic hydrate flame retardant based on the total weight of the composition. Based on the total weight of the composition, these compositions include no more than 10 wt% of a liquid organic flame retardant with a melting point of 25°C or lower. This method is simple to prepare and has good flame-retardant effects, but a drawback is that the phosphate ester is prone to migration and precipitation, easily leading to oil seepage.

[0004] Silicone-containing polyurethane materials, as organosilicon compounds, possess low surface energy and resistance to high and low temperatures. Combining silicone-containing polyurethane with phosphate ester materials not only further improves the processing and surface properties of the materials, but also allows the organosilicon segments to enrich the phosphate ester segments on the material surface, thus greatly enhancing the utilization rate of the phosphate ester groups. Simultaneously, the polyurethane segments effectively prevent the precipitation of phosphate esters.

[0005] CN116948137A discloses a method for preparing a waterborne flame-retardant polyurethane with both hard and soft segments. The method includes placing a phosphorus-containing flame-retardant polyester polyol, a polyether polyol, hydroxyl silicone oil, and antioxidant 1010 in a container for vacuum dehydration for 45 minutes, then cooling to 70°C. Isophorone diisocyanate and hexamethylene diisocyanate are added to the container for a prepolymerization reaction. The temperature is then lowered to 60°C, and 1,4-butanediol, dimethylolpropionic acid, trimethylolpropane, and a catalyst are added sequentially to the container. Small-molecule flame-retardant diol and hydroxyl-terminated polybutadiene acrylonitrile are then added dropwise for chain extension reactions. The intrinsically flame-retardant waterborne polyurethane resin obtained by this method combines flame retardancy with flexibility.

[0006] CN114891184A discloses a silicone-modified polyurethane elastomer, its preparation method, and its applications. The preparation method includes mixing a polymeric polyol, a hydroxyl-terminated linear polysiloxane, a halogen-free flame retardant, a plasticizer, optionally a lubricant, optionally a catalyst, and optionally an antioxidant, followed by the addition of diisocyanate and a chain extender for reaction. The silicone-modified polyurethane elastomer obtained by this method exhibits good flame retardancy and high thermal stability.

[0007] CN108864399A discloses an organosilicon-modified flame-retardant polyurethane and its preparation. It is obtained by copolymerization of hydroxyalkyl silicone oil, MDI-50, polyether polyol, polyester polyol, amine chain extender and reactive organophosphorus flame retardant. The organosilicon-modified flame-retardant polyurethane has excellent water resistance, weather resistance, heat resistance, flame retardancy and mechanical properties.

[0008] However, the above methods all involve simultaneously copolymerizing hydroxyl-terminated siloxanes and polyester polyols with diisocyanates, resulting in competitive reactions between the polymer polyol and the hydroxyl-terminated linear polysiloxane and the diisocyanate. Since both diisocyanate and polymer polyol are polar raw materials, the diisocyanate preferentially reacts with the polymer polyol, leaving residual hydroxyl-terminated linear polysiloxane, leading to oiliness in the product. Furthermore, the organosilicon-modified flame-retardant polyurethane obtained by these methods also suffers from insufficient lubricity and low utilization of phosphate esters. Summary of the Invention

[0009] To address the shortcomings of existing technologies, the present invention aims to provide a phosphorus-containing polyurethane silicone wax, its preparation method, and its applications. This invention innovatively uses NCO-terminated silicone oil as an organosilicon raw material to synthesize phosphorus-containing polyurethane silicone wax, effectively avoiding the oily product problem caused by incomplete grafting of hydroxyl-terminated polysiloxanes. It achieves an effective combination of phosphate ester groups and organosilicon segments, not only improving the grafting rate of organosilicon segments but also enhancing the utilization rate and flame-retardant effect of phosphate esters. This achieves a synergistic flame-retardant effect between organosilicon and phosphate ester groups, and also provides excellent lubricity.

[0010] To achieve this objective, the present invention adopts the following technical solution:

[0011] In a first aspect, the present invention provides a method for preparing phosphorus-containing polyurethane silicone wax, the method comprising the following steps:

[0012] S1. After reacting component (A) macromolecular polyol, component (B) polyisocyanate, and component (C) isocyanate-terminated polysiloxane at a first set temperature for a first set time, an isocyanate-terminated organosilicon polyurethane prepolymer is obtained.

[0013] S2. Mix the silicone polyurethane prepolymer obtained in step S1 with the chain extender (D). After stirring, a pre-chain extended silicone modified polyurethane prepolymer is obtained.

[0014] S3. The pre-chain extended silicone-modified polyurethane prepolymer obtained in step S2 is subjected to end-capping and curing with component (E) end-capping agent at a second set temperature. After curing, the phosphorus-containing polyurethane silicone wax is obtained.

[0015] The macromolecular polyols include polyester polyols and phosphorus-containing polyols;

[0016] The capping agent comprises higher amines and / or higher alcohols with ≥16 carbon atoms;

[0017] The isocyanate-terminated polysiloxane has a molecular weight of 1000~6000 g / mol.

[0018] More preferably, the isocyanate-terminated polysiloxane has a molecular weight of 2000~6000 g / mol.

[0019] Preferably, the total isocyanate groups contained in components (B) and (C) are the sum of isocyanate groups, and the molar ratio between the total isocyanate groups and the hydroxyl groups contained in component (A) is 1.5 to 3:1.

[0020] The molar ratio between the active hydrogen contained in the chain extender of component (D) and the isocyanate groups contained in the organosilicon polyurethane prepolymer is 1.1~4.1:1.

[0021] The above molar ratio can be determined by the following method:

[0022] The number of isocyanate groups contained in the silicone polyurethane prepolymer is n. NCO（S1） The component (B) contains n moles of isocyanate groups. NCO（B） The isocyanate-terminated polysiloxane component (C) contains n moles of isocyanate groups. NCO（C） The chain extender (D) contains n moles of active hydrogen. H(D)The molar ratio between the active hydrogen contained in the chain extender of component (D) and the isocyanate groups contained in the organosilicon polyurethane prepolymer is n. H(D) :n NCO（S1）。

[0023] The isocyanate group consumed in step S1 can be obtained from the hydroxyl groups contained in component (A), and according to n NCO（B） and n NCO（C） The sum of can be used to calculate n. NCO（S1）。

[0024] In this invention, by adding an excess of isocyanate groups in step S1, when the reaction in step S1 is completed, the hydroxyl groups in the reaction system have been completely consumed, and the system contains isocyanate-terminated silicone polyurethane prepolymer and unreacted isocyanate groups (from component (B) polyisocyanate and / or component (C) isocyanate-terminated polysiloxane); in step S2, chain extension is performed by adding a chain extender, and the total amount of the aforementioned unreacted isocyanate groups is still in excess relative to the active hydrogen of the chain extender, so the aforementioned unreacted isocyanate groups are not completely consumed. After stirring, the system contains isocyanate-terminated pre-chain silicone-modified polyurethane prepolymer, or a mixture of isocyanate-terminated pre-chain silicone-modified polyurethane prepolymer and unreacted isocyanate groups (from component (B) polyisocyanate and / or component (C) isocyanate-terminated polysiloxane). In the subsequent end-capping step, the end-capping agent continues to react with the isocyanate groups in the system.

[0025] Preferably, in step S1, the first set temperature is 70~130℃, and the first set time is 3~10h;

[0026] In step S2, the stirring time is 3-5 minutes;

[0027] In step S3, the end-sealing curing temperature is 50~80℃; the end-sealing curing time is 12~24h.

[0028] Step S3 also includes the step of pulverizing the end-capped and cured phosphorus-containing polyurethane silicone wax.

[0029] Preferably, based on the total mass of components (A), (B), (C), (D), and (E) being 100%, the amount of component (C) added is 18-45%; for example, 18.5%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, etc.

[0030] Preferably, the amount of component (C) added is 38-86% based on the total weight of component (B) and component (C) as 100%; for example, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, etc.

[0031] Preferably, the amount of phosphorus-containing polyol added is 11-13% based on the total mass of components (A), (B), (C), (D), and (E) as 100%; for example, 5.5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, etc.

[0032] Preferably, the amount of the capping agent in component (E) is 9-12% based on the total mass of components (A), (B), (C), (D), and (E) being 100%; for example, 9.5%, 10%, 10.5%, 11%, 11.5%, etc.

[0033] Based on the total mass of the macromolecular polyol in component (A) being 100%, the amount of phosphorus-containing polyol added is 17-31%.

[0034] Preferably, based on the total weight of components (B) and (C) being 100%, the amount of component (C) added is 38.7% to 64.3%;

[0035] Based on the total mass of the macromolecular polyols in component (A) being 100%, the amount of phosphorus-containing polyols added is 21-31%.

[0036] Preferably, the mass ratio of components (A), (B), (C), (D), and (E) is (104~190):(20~70):(60~140):(10~50):(25~50);

[0037] Among them, (104~190) can take values ​​of 110, 112, 115, 118, 120, 122, 125, 128, 130, 132, 135, 138, 140, 142, 145, 148, 150, 152, 155, 158, 160, 162, 165, 168, 170, 172, 175, 178, 180, 182, 185, 188, etc.

[0038] Preferably, the polyester polyol comprises a copolymer of adipic acid and a diol and / or a copolymer of terephthalic acid and a diol; the diol comprises one or more of ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol.

[0039] The chain extender (D) comprises one or more of the following: 1,6-hexanediol, neopentyl glycol, decanediol, 1,4-cyclohexanediol, 1,4-butanediol, diethylene glycol, dimethylolpropionic acid, dimethylolbutyric acid, glycerol, sucrose, glucose, trimethylolpropane, melamine, and 1,3,5-tris(2-hydroxyethyl)cyanuric acid;

[0040] The (E) capping agent includes one or more of n-hexadecyl alcohol, stearyl alcohol, behenyl alcohol, n-trianediol, and octadecylamine.

[0041] Preferably, the molecular weight of the phosphorus-containing polyol is 200-700 g / mol; and the molecular weight of the polyester polyol is 1000-5000 g / mol.

[0042] In this invention, unless otherwise specified, molecular weight refers to number-average molecular weight.

[0043] Preferably, the isocyanate-terminated polysiloxane includes one or more of Silok3062F2, Silok3067F2, Silok3064F, Silok3067F4, and Silok3062F4 from Guangzhou Silok New Materials Co., Ltd.

[0044] Secondly, the present invention provides a phosphorus-containing polyurethane silicone wax, which is prepared by the above-described preparation method.

[0045] Thirdly, the present invention provides an application of the above-mentioned phosphorus-containing polyurethane silicone wax in rubber and plastic modification.

[0046] The phosphorus-containing polyurethane silicone wax can be used as a rubber and plastic feel agent or a rubber and plastic flame retardant in rubber and plastic modification.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] This invention yields phosphorus-containing polyurethane silicone wax by reacting macromolecular polyols, polyisocyanates, and isocyanate-terminated polysiloxanes, followed by chain extension, and finally end-capping and curing with a long-chain end-capping agent. Through specific synthetic steps, this invention achieves an effective combination of phosphate groups and organosilicon segments, improving not only the grafting rate of organosilicon segments but also the utilization rate and flame-retardant effect of phosphate esters, realizing a synergistic flame-retardant effect between organosilicon and phosphate groups. The phosphorus-containing polyurethane silicone wax prepared by this method combines the flame-retardant properties of hydroxyphosphate esters with the slip-feel and flame-retardant properties of organosilicon. This phosphorus-containing polyurethane silicone wax can be added to rubber and plastic materials as a flame-retardant and feel-enhancing agent, providing a high-performance modifier for the modification of rubber and plastic materials. The preparation method provided by this invention is simple, feasible, and easy to industrialize, with broad application prospects. Attached Figure Description

[0049] Figure 1 The infrared spectrum of the phosphorus-containing polyurethane silicone wax obtained in Example 1 of this invention is shown. Detailed Implementation

[0050] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0051] The isocyanate-terminated polysiloxanes used below are all from Guangzhou Sloco New Materials Co., Ltd.

[0052] The determination of isocyanate group content was performed according to the method described in HG / T2409-2003 "Determination of Isocyanate Group Content in Polyurethane Prepolymers". Example 1

[0053] This embodiment provides a phosphorus-containing polyurethane silicone wax, which comprises the following raw materials:

[0054] Polyester polyol: 100g

[0055] Phosphorus-containing polyols: 30g

[0056] Isocyanate-based end-capped silicone oil: 133.33g

[0057] Polyisocyanate: 22g

[0058] Chain extender: 10g

[0059] Capping agent: 30g

[0060] The polyester polyol is XCP3000E (EG / AA, Mn=3000g / mol, functionality f1=2).

[0061] The phosphorus-containing polyol is Exolit OP 550 (Mn=660g / mol, functionality f4=2).

[0062] The isocyanate-based end-capping silicone oil is Silok3062F2 (Mn=2000g / mol, functionality f2=2).

[0063] The polyisocyanate is isophorone diisocyanate (IPDI (Mn=222.32g / mol, functionality f3=2)).

[0064] The chain extender is trimethylolpropane (Mn=134g / mol, functionality f5=3).

[0065] The capping agent is n-octadecyl alcohol.

[0066] This embodiment provides a method for preparing phosphorus-containing polyurethane silicone wax, which includes the following steps:

[0067] (1) Dehydration of polyols: 100g XCP3000E and 30g Exolit OP 550 are placed in a reactor and heated to 110°C. The pressure in the reactor is reduced to below 0.1 MPa using a vacuum pump and maintained for 1-2 hours to remove water, thereby obtaining dehydrated polyols.

[0068] (2) Preparation of silicone polyurethane prepolymer: The dehydrated polyol obtained in step (1) was cooled to below 60°C, and 133.33g of Silok3062F2 and 22g of IPDI were added. The mixture was stirred for 30 minutes, and then heated to 100°C and reacted for 4 hours. When the isocyanate content reached or approached the theoretical isocyanate content of 2.55% by titration, the reaction was stopped by cooling to obtain silicone polyurethane prepolymer.

[0069] (3) Chain extension of silicone polyurethane prepolymer: The silicone polyurethane prepolymer obtained in step (2) is transferred into a mixing tank, 10g of trimethylolpropane is added and the mixture is stirred rapidly for 5 minutes to obtain the pre-chain extended silicone polyurethane prepolymer.

[0070] (4) End-capping and ripening: Add 30g of n-octadecyl alcohol to the pre-extended silicone polyurethane prepolymer obtained in step (3), stir well, put it in an oven, and ripen at 80 degrees Celsius for 24 hours to obtain the phosphorus-containing polyurethane silicone wax primary product.

[0071] (5) Phosphorus-containing polyurethane silicone wax powder: The phosphorus-containing polyurethane silicone wax primary product obtained in step (4) is fed into a crusher and crushed into phosphorus-containing polyurethane silicone wax coarse particles. After the phosphorus-containing polyurethane silicone wax coarse particles are fed into a pulverizer and pulverized, phosphorus-containing polyurethane silicone wax powder is obtained.

[0072] Figure 1The image shows the infrared spectrum of the phosphorus-containing polyurethane silicone wax obtained in Example 1 of this invention. Figure 1 The middle is 3421 cm -1 The peak generated at 1737 cm⁻¹ corresponds to the symmetric stretching vibration of NH in the urethane group (-NHCOO-), and is a characteristic absorption peak of the polyurethane structure. -1 The strong absorption peak at 1737 cm⁻¹ originates from the stretching vibration of the carbonyl group (C=O) in the carbamate, with a wavenumber position of 1737 cm⁻¹. -1 The characteristic peak absorption range of ester groups in polyurethane is 1700~1750 cm⁻¹. -1 The complete match proves that the product obtained in Example 1 contains complete carbamate segments;

[0073] Figure 1 The middle is 1064 cm -1 The resulting peak represents the symmetric stretching vibration of the Si-O-Si bonds in the siloxane framework, and its wavenumber position is similar to that of the Si-O-Si vibration of polydimethylsiloxane (PDMS) (approximately 1020~1080 cm⁻¹). -1 The consistency indicates that the siloxane segments have been effectively incorporated into the polymer, 2925 cm. -1 and 2856 cm -1 The peaks generated at the point are a combination of asymmetric stretching of CH3 and symmetric stretching of CH2, which are derived from the methyl and methylene groups of the siloxane side chain. This is consistent with the structural characteristics of long-chain alkyl groups in silicone wax, indicating that the product obtained in Example 1 has a silicone wax structure.

[0074] Figure 1 The middle is 1261 cm -1 The peak produced is a characteristic absorption peak of the P=O bond in the phosphate ester or phosphonate group, with a wavenumber position of 1261 cm⁻¹. -1 The P=O vibration of organophosphorus compounds (such as phosphate esters) (1250~1300 cm⁻¹) -1 The complete consistency indicates that phosphorus has been introduced into the polyurethane silicone wax molecules through chemical bonding, rather than through physical mixing.

[0075] Therefore, by Figure 1 As can be seen, the product obtained in Example 1 of the present invention simultaneously possesses polyurethane segments, silicone wax segments, and phosphate ester structures, proving that the method provided by the present invention successfully synthesizes phosphorus-containing polyurethane silicone wax. Example 2

[0076] This embodiment provides a phosphorus-containing polyurethane silicone wax, which comprises the following raw materials:

[0077] Polyester polyol: 120g

[0078] Phosphorus-containing polyols: 25g

[0079] Isocyanate-based end-capped silicone oil: 110g

[0080] Polyisocyanate: 45g

[0081] Chain extender: 25g

[0082] Capping agent: 40g

[0083] The polyester polyol is XCP24 (EG / AA, Mn=2000g / mol, functionality f1=2).

[0084] The phosphorus-containing polyol is Exolit OP 560 (Mn=280g / mol, functionality f4=2);

[0085] The isocyanate-based end-capped silicone oil is Silok3067F2 (Mn=1850g / mol, functionality f2=2).

[0086] The polyisocyanate is toluene diisocyanate (TDI (Mn=174.156 g / mol, functionality f3=2)).

[0087] The chain extender is 1,6-hexanediol (Mn = 118.17 g / mol, functionality f5 = 2);

[0088] The capping agent is n-dodecyl alcohol.

[0089] This embodiment provides a method for preparing phosphorus-containing polyurethane silicone wax, which includes the following steps:

[0090] (1) Dehydration of polyols: 120g XCP24 and 25g Exolit OP 560 were placed in a reactor and heated to 120°C. The pressure in the reactor was reduced to below 0.1 MPa using a vacuum pump and maintained for 1.5 hours to remove water, thus obtaining dehydrated polyols.

[0091] (2) Preparation of silicone polyurethane prepolymer: The dehydrated polyol prepolymer was cooled to below 60°C, and 110g Silok3067F2 and 40g TDI were added. The mixture was stirred for 20 minutes, and then heated to 80°C for 5 hours. The reaction was stopped when the isocyanate content reached or approached the theoretical isocyanate content of 4.7% by titration. The silicone polyurethane prepolymer was obtained.

[0092] (3) Chain extension of silicone polyurethane prepolymer: The silicone polyurethane prepolymer was transferred into a mixing tank, and 25g of 1,6-hexanediol was added and stirred rapidly for 5 minutes to obtain the pre-chain extended silicone polyurethane prepolymer.

[0093] (4) End-capping and curing: Add 40 g of n-dodecyl alcohol to the pre-extended silicone polyurethane prepolymer, stir well, put it in an oven, and cure at 60 degrees Celsius for 18 hours to obtain the extended silicone polyurethane prepolymer.

[0094] (5) Polyurethane silicone wax powder: The extended chain silicone polyurethane prepolymer is fed into a crusher and crushed into coarse polyurethane silicone wax particles. The phosphorus-containing polyurethane silicone wax particles are fed into a pulverizer and pulverized to obtain powdered phosphorus-containing polyurethane silicone wax. Example 3

[0095] This embodiment provides a phosphorus-containing polyurethane silicone wax, which comprises the following raw materials:

[0096] Polyester polyol: 150g

[0097] Phosphorus-containing polyols: 40g

[0098] Isocyanate-based end-capped silicone oil: 90g

[0099] Polyisocyanate: 50g

[0100] Chain extender: 50g

[0101] Capping agent: 50g

[0102] The polyester polyol is XCP44 (BG / AA, Mn=2000g / mol, functionality f1=2).

[0103] The phosphorus-containing polyol is Exolit OP 550 (Mn=660g / mol, functionality f4=2).

[0104] The isocyanate-based end-capped silicone oil is Silok3064F (Mn=4500g / mol, functionality f2=2).

[0105] The polyisocyanate is hexamethylene diisocyanate (TDI (Mn=174.156 g / mol, functionality f3=2)).

[0106] The chain extender is neopentyl glycol (Mn=116.17 g / mol, functionality f5=2);

[0107] The capping agent is triacontyl alcohol.

[0108] This embodiment provides a method for preparing phosphorus-containing polyurethane silicone wax, which includes the following steps:

[0109] (1) Dehydration of polyols: 150g XCP44 and 40g Exolit OP 550 were placed in a reactor and heated to 115°C. The pressure in the reactor was reduced to below 0.1 MPa using a vacuum pump and maintained for 2 hours to remove water, thus obtaining dehydrated polyols.

[0110] (2) Preparation of polyurethane modified polyol prepolymer: The dehydrated polyol was cooled to below 55°C, and 90g Silok3064F and 50g HDI were added. The mixture was stirred for 15 minutes, and then heated to 100°C for 6 hours. When the isocyanate content reached or approached the theoretical isocyanate content of 4.62%, the reaction was stopped by cooling to obtain the organosilicon polyurethane prepolymer.

[0111] (3) Chain extension of silicone polyurethane prepolymer: Transfer the silicone polyurethane prepolymer into a mixing tank, add 50g of neopentyl glycol and stir rapidly for 3 minutes to obtain the pre-chain extended silicone polyurethane prepolymer;

[0112] (4) End-capping and curing: Add 50 g of n-trianetriol to the pre-extended polyurethane prepolymer, stir well, place in an oven and cure at 70°C for 20 hours to obtain the phosphorus-containing polyurethane silicone wax primary product.

[0113] (5) Preparation of polyurethane silicone wax powder: The phosphorus-containing polyurethane silicone wax primary product is crushed into coarse particles by a crusher, and then the coarse particles are fed into a pulverizer to be pulverized to obtain powdered phosphorus-containing polyurethane silicone wax. Example 4

[0114] This embodiment provides a phosphorus-containing polyurethane silicone wax, which comprises the following raw materials:

[0115] Polyester polyol: 110g;

[0116] Phosphorus-containing polyols: 33g;

[0117] Isocyanate-based end-capped silicone oil: 80g;

[0118] Polyisocyanate: 30g;

[0119] Chain extender: 30g;

[0120] Capping agent: 40g.

[0121] The polyester polyol is XCP3000H (HD / AA, Mn=3000g / mol, functionality f1=2).

[0122] The phosphorus-containing polyol is Exolit OP 550 (Mn=660g / mol, functionality f4=2).

[0123] The isocyanate-based end-capping silicone oil is Silok3067F4 (Mn=6000g / mol, functionality f2=2).

[0124] The polyisocyanate is methylcyclohexyl diisocyanate (HTDI (Mn=139.19g / mol, functionality f3=2)).

[0125] The chain extender is neopentyl glycol (Mn=116.17g / mol, functionality f5=2).

[0126] The capping agent is octadecylamine.

[0127] This embodiment provides a method for preparing phosphorus-containing polyurethane silicone wax, which includes the following steps:

[0128] (1) Dehydration of polyols: Mix 110g of XCP3000H and 33g of Exolit OP 550 and add them to the reactor; heat to 110°C, use a vacuum pump to reduce the pressure in the reactor to below 0.1 MPa, and maintain this state for 1 to 2 hours to remove the water in the polyol prepolymer and obtain a dehydrated polyol mixture.

[0129] (2) Preparation of silicone polyurethane prepolymer: After cooling the dehydrated polyol to below 60°C, add 80g of Silok3067F4 and 30g of HTDI; stir for 30 minutes to ensure uniform mixing of raw materials. Then heat to 110°C and react at this temperature for 6 hours. Monitor the isocyanate (NCO) content by titration. When the isocyanate content reaches or approaches the theoretical isocyanate content of 2.64%, cool down to end the reaction and obtain silicone polyurethane prepolymer;

[0130] (3) Chain extension of silicone polyurethane prepolymer: The obtained silicone polyurethane prepolymer is transferred to a mixing tank, 30g of cyclohexanediol is added as a chain extender, and the mixture is stirred rapidly for 35 minutes to ensure that the chain extender is evenly dispersed in the prepolymer, thus obtaining the pre-chain extended silicone polyurethane prepolymer.

[0131] (4) End-capping and curing of pre-extended chain organosilicon polyurethane prepolymer: 40 g of octadecylamine was added to the pre-extended chain polyurethane prepolymer and stirred until it was cured in a constant temperature environment of 80°C for 24 hours to further promote the cross-linking and stabilization of the molecular chain and obtain the phosphorus-containing polyurethane silicone wax primary product.

[0132] (5) Preparation of polyurethane silicone wax powder: The phosphorus-containing polyurethane silicone wax primary product is introduced into a crusher and crushed into coarse polyurethane silicone wax particles. The coarse particles are then introduced into a pulverizer for further pulverization to obtain a uniformly sized powder of phosphorus-containing polyurethane silicone wax. Example 5

[0133] This embodiment provides a phosphorus-containing polyurethane silicone wax, which comprises the following raw materials:

[0134] Polyester polyol: 80g

[0135] Phosphorus-containing polyols: 24g

[0136] Isocyanate-based end-capped silicone oil: 90g

[0137] Polyisocyanate: 20g

[0138] Chain extender: 30g

[0139] Capping agent: 25g

[0140] The polyester polyol is XCP1000H (HD / AA, Mn=1000g / mol, functionality f1=2).

[0141] The phosphorus-containing polyol is Exolit OP 550 (Mn=660g / mol, functionality f4=2).

[0142] The isocyanate-based end-capped silicone oil is Silok3080F2 (Mn=1000g / mol, functionality f2=2).

[0143] The polyisocyanate is isophorone diisocyanate (IPDI (Mn=222.32g / mol, functionality f3=2)).

[0144] The chain extender is decanediol (Mn=174.28g / mol, functionality f5=2);

[0145] The capping agent is n-hexadecyl alcohol.

[0146] This embodiment provides a method for preparing phosphorus-containing polyurethane silicone wax, which includes the following steps:

[0147] (1) Dehydration of polyol prepolymer: 80g of XCP1000H and 24g of Exolit OP 550 were mixed and added to the reactor, heated to 120°C, and the pressure in the reactor was reduced to below 0.1 MPa using a vacuum pump and maintained at this state for 1 hour to remove the water in the polyol prepolymer and obtain dehydrated polyol prepolymer;

[0148] (2) Preparation of polyurethane modified polyol prepolymer: Cool the dehydrated polyol prepolymer to below 60°C, add 90g of Silok3080F2 and 20g of IPDI, stir for 30 minutes to ensure uniform mixing of raw materials; then heat to 110°C and react at this temperature for 6 hours; monitor the content of isocyanate (NCO) by titration, and when the content reaches or approaches the theoretical isocyanate content of 1.54%, cool down to end the reaction and obtain the organosilicon polyurethane prepolymer;

[0149] (3) Chain extension of silicone polyurethane prepolymer: The obtained silicone polyurethane prepolymer is transferred to a mixing tank, and 30g of decanediol is added as a chain extender. The mixture is stirred rapidly for 5 minutes to ensure that the chain extender is evenly dispersed in the prepolymer, thus obtaining the pre-chain extended silicone polyurethane prepolymer.

[0150] (4) End-capping and maturation of pre-extended silicone polyurethane prepolymer: Add 25 g of n-hexadecyl alcohol to the pre-extended silicone polyurethane prepolymer, stir well, and mature in a constant temperature environment of 80°C for 24 hours to further promote the cross-linking and stabilization of the molecular chain and obtain extended silicone polyurethane prepolymer.

[0151] (5) Preparation of polyurethane silicone wax powder: The matured extended chain silicone polyurethane prepolymer is introduced into a crusher and crushed into coarse polyurethane silicone wax particles. The coarse particles are then introduced into a pulverizer for further pulverization to obtain a uniformly sized powder containing phosphorus polyurethane silicone wax. Example 6

[0152] This embodiment provides a phosphorus-containing polyurethane silicone wax, which comprises the following raw materials:

[0153] Polyester polyol: 130g

[0154] Phosphorus-containing polyols: 40g

[0155] Isocyanate-based end-capped silicone oil: 80g

[0156] Polyisocyanate: 70g

[0157] Chain extender: 20g

[0158] Capping agent: 40g

[0159] The polyester polyol is XCP3000H (HD / AA, Mn=3000g / mol, functionality f1=2).

[0160] The phosphorus-containing polyol is Exolit OP 560 (Mn=280g / mol, functionality f4=2);

[0161] The isocyanate-based end-capping silicone oil is Silok3067F4 (Mn=6000g / mol, functionality f2=2).

[0162] The polyisocyanate is methylcyclohexyl diisocyanate (HTDI (Mn=139.19g / mol, functionality f3=2)).

[0163] The chain extender is 1,3,5-tris(2-hydroxyethyl)cyanuric acid;

[0164] The capping agent is n-dodecyl alcohol.

[0165] This embodiment provides a method for preparing phosphorus-containing polyurethane silicone wax, which includes the following steps:

[0166] (1) Dehydration of polyol prepolymer: 130g of XCP3000H and 40g of Exolit OP 560 were mixed and added to the reactor, heated to 120°C, and the pressure in the reactor was reduced to below 0.1 MPa using a vacuum pump and maintained at this state for 1 hour to remove water from the polyol and obtain dehydrated polyol prepolymer.

[0167] (2) Preparation of polyurethane modified polyol prepolymer: Cool the dehydrated polyol prepolymer to below 60°C, add 80g of Silok3067F4 and 70g of HMDI, stir for 30 minutes to ensure uniform mixing of raw materials; then heat to 120°C and react at this temperature for 6 hours. Monitor the content of isocyanate (NCO) by titration. When the content of isocyanate reaches or approaches the theoretical content of 2.47%, cool down to end the reaction and obtain the organosilicon polyurethane prepolymer.

[0168] (3) Chain extension of silicone polyurethane prepolymer: The obtained silicone polyurethane prepolymer is transferred to a mixing tank, and 20g of 1,3,5-tris(2-hydroxyethyl)cyanuric acid is added as a chain extender. The mixture is stirred rapidly for 5 minutes to ensure that the chain extender is evenly dispersed in the prepolymer, thus obtaining the pre-chain extended silicone polyurethane prepolymer.

[0169] (4) End-capping and maturation of pre-extended silicone polyurethane prepolymer: Add 40 g of n-dodecyl alcohol to the pre-extended silicone polyurethane prepolymer, stir well, and place in a constant temperature environment of 80°C for 24 hours to further promote the cross-linking and stabilization of the molecular chain, and obtain extended silicone polyurethane prepolymer.

[0170] (5) Preparation of polyurethane silicone wax powder: The matured extended chain silicone polyurethane prepolymer is fed into a crusher and crushed into coarse polyurethane silicone wax particles. The coarse particles are fed into a pulverizer for further pulverization to obtain phosphorus-containing polyurethane silicone wax powder with uniform particle size. Example 7

[0171] This embodiment provides a phosphorus-containing polyurethane silicone wax, which comprises the following raw materials:

[0172] Polyester polyol: 110g

[0173] Phosphorus-containing polyols: 30g

[0174] Isocyanate-based end-capped silicone oil: 100g

[0175] Polyisocyanate: 30g

[0176] Chain extender: 30g

[0177] Capping agent: 30g

[0178] The polyester polyol is XCPA2000HL (HD / PA, Mn=2000g / mol, functionality f1=2).

[0179] The phosphorus-containing polyol is Exolit OP 550 (Mn=660g / mol, functionality f4=2).

[0180] The isocyanate-based end-capped silicone oil is Silok3062F4 (Mn=2500g / mol, functionality f2=2).

[0181] The polyisocyanate is 4,4'-diphenylmethane diisocyanate (MDI (Mn=250.26 g / mol, functionality f3=2)).

[0182] The chain extender is dimethylolpropionic acid (Mn=134.13g / mol, functionality f5=2).

[0183] The capping agent is n-octadecyl alcohol.

[0184] This embodiment provides a method for preparing phosphorus-containing polyurethane silicone wax, which includes the following steps:

[0185] (1) Dehydration of polyol prepolymer: 110g of XCPA2000HL and 30g of Exolit OP 550 were mixed and added to the reactor, heated to 110°C, and the pressure in the reactor was reduced to below 0.1 MPa using a vacuum pump and maintained at this state for 1 hour to remove the water in the polyol prepolymer and obtain dehydrated polyol prepolymer;

[0186] (2) Preparation of polyurethane modified polyol prepolymer: Cool the dehydrated polyol prepolymer to below 60°C, add 100g of Silok3062F4 and 30g of MDI, stir for 30 minutes to ensure uniform mixing of raw materials; then heat to 80°C and react at this temperature for 4 hours. Monitor the content of isocyanate (NCO) by titration. When the content of isocyanate reaches or approaches the theoretical isocyanate content of 1.85%, cool down to end the reaction and obtain the organosilicon polyurethane prepolymer.

[0187] (3) Chain extension of silicone polyurethane prepolymer: The obtained silicone polyurethane prepolymer is transferred to a mixing tank, and 30g of dimethylolpropionic acid is added as a chain extender. The mixture is stirred rapidly for 5 minutes to ensure that the chain extender is evenly dispersed in the prepolymer, thus obtaining the pre-chain extended silicone polyurethane prepolymer.

[0188] (4) End-capping and maturation of pre-extended silicone polyurethane prepolymer: Add 30 g of n-octadecyl alcohol to the pre-extended silicone polyurethane prepolymer, stir well, and mature in a constant temperature environment of 80°C for 24 hours to further promote the cross-linking and stabilization of the molecular chain and obtain extended silicone polyurethane prepolymer.

[0189] (5) Preparation of polyurethane silicone wax powder: The matured extended chain silicone polyurethane prepolymer is introduced into a crusher and crushed into coarse polyurethane silicone wax particles. The coarse particles are then introduced into a pulverizer for further pulverization to obtain phosphorus-containing polyurethane silicone wax powder with uniform particle size. Example 8

[0190] This embodiment provides a phosphorus-containing polyurethane silicone wax, which comprises the following raw materials:

[0191] Polyester polyol: 110g

[0192] Phosphorus-containing polyols: 30g

[0193] Isocyanate-based end-capped silicone oil: 100g

[0194] Polyisocyanate: 30g

[0195] Chain extender: 30g

[0196] Capping agent: 30g

[0197] The polyester polyol is XCPA2000HL (HD / PA, Mn=2000g / mol, functionality f1=2).

[0198] The phosphorus-containing polyol is Exolit OP 550 (Mn=660g / mol, functionality f4=2).

[0199] The isocyanate-based end-capped silicone oil is Silok3062F4 (Mn=2500g / mol, functionality f2=2).

[0200] The polyisocyanate is 4,4'-diphenylmethane diisocyanate (MDI (Mn=250.26 g / mol, functionality f3=2)).

[0201] The chain extender is dimethylolpropionic acid (Mn=134.13g / mol, functionality f5=2).

[0202] The capping agent is triacontyl alcohol.

[0203] This embodiment provides a method for preparing phosphorus-containing polyurethane silicone wax, which includes the following steps:

[0204] (1) Dehydration of polyol prepolymer: 90g FLPPA1000N and 25g Exolit OP 560 are placed in a reactor and heated to 110°C. The pressure inside the reactor is reduced to below 0.1 MPa using a vacuum pump and maintained in this state for 1 hour to obtain dehydrated polyol prepolymer.

[0205] (2) Preparation of polyurethane modified polyol prepolymer: Cool the dehydrated polyol prepolymer to below 60°C, then add 110g Silok3062F2 and 41g XDI. First stir for 10 minutes to ensure uniform mixing, then heat to 100°C and react at this temperature for 5 hours. Monitor the content of isocyanate (NCO) by titration. When the content of isocyanate reaches or approaches the theoretical content, cool down to end the reaction and obtain the organosilicon polyurethane prepolymer.

[0206] (3) Chain extension of silicone polyurethane prepolymer: Transfer the silicone polyurethane prepolymer to a mixing tank, add 25g of melamine as a chain extender, stir rapidly for 5 minutes until the mixture is uniform, and obtain the pre-chain extended silicone polyurethane prepolymer.

[0207] (4) End-capping and curing of pre-extended silicone polyurethane prepolymer: 30 g of n-trianetriol was added to the pre-extended silicone polyurethane prepolymer and cured in a constant temperature environment of 60°C for 18 hours to obtain the extended silicone polyurethane prepolymer.

[0208] (5) Preparation of polyurethane silicone wax powder: The matured extended chain organosilicon polyurethane prepolymer is introduced into a crusher and crushed into coarse polyurethane silicone wax particles. Then the coarse particles are introduced into a pulverizer for pulverization, and finally phosphorus-containing polyurethane silicone wax powder is obtained. Example 9

[0209] The only difference between this embodiment and Embodiment 1 is that the amount of Exolit OP 550 added is changed to 40g and the amount of XCP3000E added is changed to 90g. Example 10

[0210] The only difference between this embodiment and Embodiment 1 is that the amount of isocyanate-based end-capped silicone oil added is changed to 140g and the amount of IPDI added is changed to 15g. Example 11

[0211] The only difference between this embodiment and Embodiment 1 is that the amount of isocyanate-based end-capped silicone oil added is changed to 60g and the amount of IPDI added is changed to 95g. Example 12

[0212] The only difference between this embodiment and Embodiment 1 is that the isocyanate-based end-capping silicone oil used in this invention is a low molecular weight isocyanate-based end-capping silicone oil (Silok3080F2, Mn=1000), while other parameters remain unchanged. Comparative Example 1

[0213] This comparative example provides a phosphorus-containing polyurethane silicone wax, which comprises the following raw materials:

[0214] Polyester polyol: 100g

[0215] Phosphorus-containing polyols: 30g

[0216] Dihydroxyl-terminated silicone oil: 133.3g

[0217] Polyisocyanate: 52g

[0218] Chain extender: 10g

[0219] Capping agent: 30g

[0220] The polyester polyol is XCP3000E (EG / AA, Mn=3000g / mol, functionality f1=2).

[0221] The phosphorus-containing polyol is Exolit OP 550 (Mn=660g / mol, functionality f4=2).

[0222] The hydroxyl-terminated silicone oil is Silok 8815 (Mn=1750g / mol, functionality f=2);

[0223] The polyisocyanate is isophorone diisocyanate (IPDI (Mn=222.32g / mol, functionality f3=2)).

[0224] The chain extender is trimethylolpropane (Mn=134 g / mol, functionality f5=3);

[0225] The capping agent is n-octadecyl alcohol.

[0226] This comparative example provides a method for preparing a phosphorus-containing polyurethane silicone wax, which includes the following steps:

[0227] (1) Dehydration of polyols: 100g XCP3000E, 30g Exolit OP 550 and dihydroxy-terminated silicone oil Silok8815 are placed in a reactor, heated to 110°C, and the pressure in the reactor is reduced to below 0.1 MPa by a vacuum pump and maintained for 1 to 2 hours to remove water, thereby obtaining dehydrated polyols;

[0228] (2) Preparation of silicone polyurethane prepolymer: The dehydrated polyol obtained in step (1) is cooled to below 60°C, 52g of IPDI is added, the mixture is stirred for 30min, then heated to 100°C and reacted for 4 hours. When the isocyanate content reaches or is close to the theoretical isocyanate content of 2.1%, the reaction is stopped by cooling to obtain silicone polyurethane prepolymer.

[0229] (3) Chain extension of silicone polyurethane prepolymer: The silicone polyurethane prepolymer obtained in step (2) is transferred into a mixing tank, 10g of trimethylolpropane is added and the mixture is stirred rapidly for 5 minutes to obtain the pre-chain extended silicone polyurethane prepolymer.

[0230] (4) End-capping and ripening: Add 30g of n-octadecyl alcohol to the pre-extended silicone polyurethane prepolymer obtained in step (3), stir well, put it in an oven, and ripen at 80 degrees Celsius for 24 hours to obtain the phosphorus-containing polyurethane silicone wax primary product.

[0231] (5) Phosphorus-containing polyurethane silicone wax powder: The phosphorus-containing polyurethane silicone wax primary product obtained in step (4) is fed into a crusher and crushed into phosphorus-containing polyurethane silicone wax coarse particles. The phosphorus-containing polyurethane silicone wax coarse particles are fed into a pulverizer and pulverized to obtain phosphorus-containing polyurethane silicone wax powder. Comparative Example 2

[0232] The only difference between this comparative example and Example 1 is that this comparative example does not include phosphorus-containing polyol (Exolit OP550), and the amount of polyester polyol is increased to 130g. All other parameters remain the same as in Example 1. Comparative Example 3

[0233] The only difference between this comparative example and Example 1 is that a short-chain capping agent (methanol, Mn=32) is used instead of n-octadecyl alcohol in this comparative example. All other parameters remain the same as in Example 1. Comparative Example 4

[0234] The only difference between this comparative example and Example 1 is that the molecular weight of the isocyanate-based end-capped silicone oil in this comparative example is 7000 g / mol. All other parameters remain the same as in Example 1.

[0235] This comparative example provides a method for preparing a phosphorus-containing polyurethane silicone wax, which includes the following steps:

[0236] (1) Dehydration of polyols: 100g XCP3000E and 30g Exolit OP 550 are placed in a reactor and heated to 110°C. The pressure in the reactor is reduced to below 0.1 MPa using a vacuum pump and maintained for 1-2 hours to remove water, thereby obtaining dehydrated polyols.

[0237] (2) Preparation of silicone polyurethane prepolymer: The dehydrated polyol obtained in step (1) was cooled to below 60°C, and 133.33g of Silok3062F2 and 22g of IPDI were added. The mixture was stirred for 30 minutes, and then heated to 100°C and reacted for 4 hours. When the isocyanate content reached or approached the theoretical isocyanate content of 2.55% by titration, the reaction was stopped by cooling to obtain silicone polyurethane prepolymer.

[0238] (3) Chain extension of silicone polyurethane prepolymer: The silicone polyurethane prepolymer obtained in step (2) is transferred into a mixing tank, 10g of trimethylolpropane is added and the mixture is stirred rapidly for 5 minutes to obtain the pre-chain extended silicone polyurethane prepolymer.

[0239] (4) End-capping and ripening: Add 30g of n-octadecyl alcohol to the pre-extended silicone polyurethane prepolymer obtained in step (3), stir well, put it in an oven, and ripen at 80 degrees Celsius for 24 hours to obtain the phosphorus-containing polyurethane silicone wax primary product.

[0240] The initial product of phosphorus-containing polyurethane silicone wax is too soft and contains silicone oil, making it impossible to undergo crushing and pulverizing steps, thus failing to obtain phosphorus-containing polyurethane silicone wax powder.

[0241] Performance testing

[0242] 1. Preparation of test strips

[0243] The phosphorus-containing polyurethane silicone waxes obtained in Examples 1-12 and Comparative Examples 1-4 were used to prepare samples with TPU substrate (Kunsheng Polymer Materials (Fujian) Co., Ltd. S185ALL (hardness 85A, melt index 12 g / 10min)) according to the following processing steps and conditions. The amount of phosphorus-containing polyurethane silicone wax added was 6 wt%.

[0244] S1. Twin-screw extrusion granulation:

[0245] Temperature range: 200℃, screw speed: 200 rpm, feeding rate: 5 kg / h.

[0246] S2. Injection molding:

[0247] Injection molding machine parameters: barrel temperature 210℃, mold temperature 40℃, holding pressure 60 MPa, cooling time 30 seconds.

[0248] 2. The test was conducted according to the following test method, and the test results are shown in Table 1.

[0249] (1) LOI value (limiting oxygen index)

[0250] Test standard: GB / T 2406-2008

[0251] Test conditions: Sample size 100×6.5×3 mm³, oxygen-nitrogen mixed gas flow rate 10 L / min, test temperature 23±2℃.

[0252] (2) UL94 vertical flammability rating

[0253] Test standard: ASTM D635

[0254] Test conditions: Sample size 125×13×3 mm³, flame height 20 mm, burning time 10 seconds, record burning drips and self-extinguishing time.

[0255] (3) Coefficient of friction

[0256] Testing standard: GB / T 10006-2021

[0257] Test instruments and conditions: MXD01 friction coefficient meter, load 200 g, sliding speed 100 mm / min, test temperature 25℃.

[0258] (4) Tensile strength and elongation at break

[0259] Test standard: GB / T 1040-2006

[0260] Test instruments and conditions: Universal testing machine (model: Instron 5967), tensile speed 50 mm / min, and specimen size ISO 527-2 1A dumbbell-shaped specimen.

[0261] (5) TGA decomposition temperature

[0262] Test instruments and conditions: Thermogravimetric analyzer (model: TA Q500), nitrogen flow rate 50 mL / min, heating rate 10℃ / min, record the temperature when the material loses 5% of its weight.

[0263] Table 1

[0264]

[0265] The data in Table 1 shows that:

[0266] The phosphorus-containing polyurethane silicone wax provided in this embodiment of the invention can impart good flame retardancy, heat resistance, abrasion resistance and mechanical properties to TPU substrates.

[0267] A comparison of Examples 1 and 12 shows that when the molecular weight Mn of the isocyanate-terminated silicone oil is not less than 2000, the resulting phosphorus-containing polyurethane silicone wax exhibits better thermal stability, abrasion resistance, and flame retardancy. When the molecular weight Mn of the isocyanate-terminated silicone oil is low, the coefficient of friction increases and the decomposition temperature decreases, indicating that both thermal stability and abrasion resistance decrease.

[0268] A comparison of Example 1 and Comparative Example 1 shows that when hydroxyl-terminated polysiloxane is used as the organosilicon prepolymer, since both diisocyanate and polyester polyol are polar raw materials, diisocyanate will preferentially react with polyester polyol. The hydroxyl-terminated polysiloxane may not be completely integrated into the polymer molecular chain, resulting in a decrease in the performance of the obtained phosphorus-containing polyurethane silicone wax. The LOI value of the TPU test strip containing this phosphorus-containing polyurethane silicone wax decreased from 29.5% to 23.3%, failed UL94, and the tensile strength decreased by 58%.

[0269] A comparison between Example 1 and Comparative Example 2 shows that the raw materials used in Comparative Example 2 do not contain phosphorus-containing polyols, resulting in a decrease in the flame retardant properties of the product. The LOI value of the TPU test strip containing this product plummeted from 29.5% to 20.1%, failing UL94.

[0270] A comparison of Example 1 and Comparative Example 3 shows that the product obtained by using a short-chain end-capping agent (methanol) in Comparative Example 3 exhibits a decline in various properties. The TGA decomposition temperature of the TPU test strip containing this product decreased by 55°C, and the elongation at break decreased by 39%, demonstrating the importance of long-chain end-capping agents for the thermal stability and ductility of this phosphorus-containing polyurethane silicone wax.

[0271] As can be seen from Example 6, the phosphorus-containing polyurethane silicone wax obtained by using both high-phosphorus polyol and high-molecular-weight silicone oil has better performance. The LOI value of the TPU test strip with the addition of this phosphorus-containing polyurethane silicone wax can reach 32.5%, and the coefficient of friction is as low as 0.09, with the best overall performance.

[0272] However, as can be seen from Comparative Example 4, when the molecular weight of isocyanate-based silicone oil is too large, the resulting phosphorus-containing polyurethane silicone wax will soften and silicone oil will precipitate out, making it impossible to grind into powder.

[0273] The applicant declares that this invention illustrates a phosphorus-containing polyurethane silicone wax, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product, additions of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this invention.

Claims

1. A method for preparing a phosphorus-containing polyurethane silicone wax, characterized in that, The preparation method includes the following steps: S1. After reacting component (A) macromolecular polyol, component (B) polyisocyanate, and component (C) isocyanate-terminated polysiloxane at a first set temperature for a first set time, an isocyanate-terminated organosilicon polyurethane prepolymer is obtained. S2. Mix the silicone polyurethane prepolymer obtained in step S1 with the chain extender (D). After stirring, a pre-chain extended silicone modified polyurethane prepolymer is obtained. S3. The pre-chain extended silicone-modified polyurethane prepolymer obtained in step S2 is capped and cured with component (E) capping agent. After curing, the phosphorus-containing polyurethane silicone wax is obtained. The macromolecular polyols include polyester polyols and phosphorus-containing polyols; The capping agent comprises higher amines and / or higher alcohols with ≥16 carbon atoms; The isocyanate-terminated polysiloxane has a number average molecular weight of 1000~6000 g / mol.

2. The method for preparing phosphorus-containing polyurethane silicone wax according to claim 1, characterized in that, The total isocyanate groups contained in components (B) and (C) are taken as the sum of isocyanate groups, and the molar ratio between the total isocyanate groups and the hydroxyl groups contained in component (A) is 1.5 to 3:

1.

3. The method for preparing phosphorus-containing polyurethane silicone wax according to claim 1, characterized in that, In step S1, the first set temperature is 70~130℃, and the first set time is 3~10h; In step S2, the stirring time is 3-5 minutes; In step S3, the end-sealing curing temperature is 50~80℃; the end-sealing curing time is 12~24h; Step S3 also includes the step of pulverizing the cured phosphorus-containing polyurethane silicone wax.

4. The method for preparing phosphorus-containing polyurethane silicone wax according to claim 1, characterized in that, Based on the total mass of components (A), (B), (C), (D), and (E) being 100%, the amount of component (C) added is 18-45%. Based on the total weight of components (B) and (C) being 100%, the amount of component (C) added is 38-86%.

5. The method for preparing phosphorus-containing polyurethane silicone wax according to claim 1, characterized in that, Based on the total mass of components (A), (B), (C), (D), and (E) being 100%, the amount of phosphorus-containing polyol added is 11-13%. Based on the total mass of components (A), (B), (C), (D), and (E) being 100%, the amount of capping agent added in component (E) is 9-12%. Based on the total mass of the macromolecular polyol in component (A) being 100%, the amount of phosphorus-containing polyol added is 17-31%.

6. The method for preparing phosphorus-containing polyurethane silicone wax according to claim 1, characterized in that, Based on the total weight of components (B) and (C) being 100%, the amount of component (C) added is 38.7% to 64.3%. Based on the total mass of the macromolecular polyol in component (A) being 100%, the amount of phosphorus-containing polyol added is 21-31%.

7. The method for preparing phosphorus-containing polyurethane silicone wax according to claim 1, characterized in that, The polyester polyol includes copolymers of adipic acid and diols and / or copolymers of terephthalic acid and diols; the diols include one or more of ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol. The chain extender of component (D) includes one or more of 1,6-hexanediol, neopentyl glycol, decanediol, 1,4-cyclohexanediol, 1,4-butanediol, diethylene glycol, dimethylolpropionic acid, dimethylolbutyric acid, glycerol, sucrose, glucose, trimethylolpropane, melamine, and 1,3,5-tris(2-hydroxyethyl)cyanuric acid; The terminator of component (E) includes one or more of n-hexadecyl alcohol, stearyl alcohol, behenyl alcohol, n-trianediol, and octadecylamine.

8. The method for preparing phosphorus-containing polyurethane silicone wax according to claim 1, characterized in that, The number-average molecular weight of the phosphorus-containing polyol is 200~700 g / mol; The number-average molecular weight of the polyester polyol is 1000~5000 g / mol.

9. A phosphorus-containing polyurethane silicone wax, characterized in that, The phosphorus-containing polyurethane silicone wax is prepared according to the preparation method described in any one of claims 1 to 8.

10. The application of the phosphorus-containing polyurethane silicone wax as described in claim 9 in the modification of rubber and plastics.

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