Flame-retardant silane modified polyether resin and preparation method thereof

Abstract

The invention relates to flame-retardant silane modified polyether resin and a preparation method thereof. The flame-retardant silane modified polyether resin comprises a component A and a component B, the component A is prepared from the following raw materials in parts by mass: 100 to 140 parts of newly-prepared polyether polyol, 0.5 to 2.5 parts of stannous octoate, 0.5 to 5 parts of a flame retardant, 2 to 10 parts of a silane coupling agent, 30 to 50 parts of polytetrahydrofuran glycol, 15 to 30 parts of triethyl phosphate, 1 to 5 parts of an antioxidant, 1 to 5 parts of a weather-resistant agent, 8 to 15 parts of toluene diisocyanate, 1 to 3 parts of dibutyltin dilaurate and 0.4 to 0.6 part of a catalyst; and the component B is prepared from the following raw materials in parts by mass. According to the flame-retardant silane modified polyether resin and the preparation method thereof, by adding 5 parts of triethyl phosphate in the reaction process and adding 10-30 parts of toluene diisocynate, under the condition that a small dosage of flame retardant is added into the modified polyether resin, the flame retardant property of a polymer can meet the UL94V0 level requirement; and on the premise of not influencing the mechanical properties and weather resistance of the polymer, the hydrophobicity, oil resistance and other properties of the polymer can be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of wire and cable, and specifically to a flame-retardant silane-modified polyether resin and a preparation method thereof. Background Art

[0002] With the development of social economy, the requirements for wire and cable materials are getting higher and higher. In addition to good mechanical properties and electrical properties, wire and cable materials should also have good oil resistance, heat resistance, cold resistance, ozone resistance, light resistance, etc., so as to meet the actual use requirements and ensure safe production. With the development of flame-retardant materials, the modification of wire and cable materials with new flame retardants has become a research hotspot.

[0003] For the flame retardancy of wire and cable materials, it is common to directly mix and granulate high molecular materials such as polyolefins with ammonium polyphosphate, triphenylcyclic boroxine, etc., and then the granulated material is blended with polyolefins, ethylene vinyl acetate, methyl methacrylate, etc. to obtain a modified cable material with better flame retardancy and higher mechanical properties. Although the blending of such granulated materials with high molecular materials has good flame retardancy and high mechanical properties, the compatibility with the matrix material is poor, resulting in poor tensile strength, tear strength, etc. of the material, and the flame retardancy of the cable material prepared by this method cannot meet the use requirements and the flame retardant level is low. At present, the method of compounding flame-retardant masterbatch with matrix material to prepare wire and cable materials cannot meet the social requirements for flame retardancy, and the mechanical properties of the materials are poor, the weather resistance is low, and problems such as cracking, yellowing, and easy migration of flame-retardant materials are likely to occur, resulting in a narrow range of use of the materials and a short service life.

[0004] Patent No. CN113249381A, patent name is a modified silicone rubber flame retardant and its preparation method and modified silicone rubber, which discloses a flame retardant for modified silicone rubber, a preparation method and a formula of modified silicone rubber. The characteristics of this formula are: first, the nitrogen-containing flame retardant aluminum diethyl phosphinate, inorganic filler and flame retardant aid are ball-milled and mixed, and then the ball-milled mixture and polyether silicone rubber are kneaded to obtain modified flame-retardant silicone rubber. Although the flame retardancy of the flame-retardant silicone rubber prepared by this method is improved, the mechanical properties are poor, it is extremely easy to break during actual use, easy to generate dust, and the service life is short, and the practicability is poor.

[0005] In summary, the existing flame-retardant high-temperature-resistant cable materials have low flame retardant grade, poor physical and mechanical properties, serious thermal cracking phenomenon, low tensile strength and elongation at break, easy to crack, easy to generate dust, and short service life, resulting in limited use of cable materials. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the present invention provides a flame-retardant silane-modified polyether resin and a preparation method thereof, which solve the problems raised in the background art.

[0007] To achieve the above object, the present invention provides the following technical solution: A flame-retardant silane-modified polyether resin, comprising component A and component B;

[0008] By mass parts, the raw material formula of component A includes: 100-140 parts of freshly prepared polyether polyol, 0.5-2.5 parts of stannous octoate, 0.5-5 parts of flame retardant, 2-10 parts of silane coupling agent, 30-50 parts of polytetrahydrofuran diol, 15-30 parts of triethyl phosphate, 1-5 parts of antioxidant, 1-5 parts of weathering agent, 8-15 parts of toluene diisocyanate, 1-3 parts of dibutyltin dilaurate, 0.4-0.6 parts of catalyst;

[0009] By mass parts, the raw material formula of component B includes: 100-140 parts of freshly prepared polyether polyol, 0.5-2.5 parts of stannous octoate, 10-30 parts of toluene diisocyanate, 10-35 parts of triethyl phosphate, 0.1-8 parts of catalyst.

[0010] Further, the freshly prepared polyether polyol has a viscosity of 200-2000 mm2 / s at 25°C;

[0011] The silane coupling agent is one or a combination of two of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltri-β-methoxyethylsilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, bis(methoxyethoxy)methylvinylsilane, γ-methacryloxypropyltriethoxysilane, methyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane.

[0012] Further, the catalyst is one or a combination of two of dibutyltin dilaurate, 1,3-diacetoxydibutyltin, diethyltin dilaurate, stannous octoate, diacetoxydibutyltin, dioctyltin dilaurate, dimethylamine, triethylamine, tributylamine, bis(dimethylaminoethyl)ether, triethylenediamine, N,N-dimethylcyclohexylamine, N,N-dimethylethanolamine, triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triethylamine, N-methylmorpholine, N-phenyl-methylmorpholine, triethanolamine, triethylenediamine, bis(dimethylaminoethyl)ether, bis(diethylaminoethyl)ether and dimethylaminopentanol.

[0013] Further, the amounts of the silane coupling agent and the flame retardant are 1-1.5 parts;

[0014] The dosage of the silane coupling agent and triethyl phosphate is 3 - 5 parts.

[0015] Furthermore, the viscosity of the polytetrahydrofuran diol is 50 - 700 mm2 / s.

[0016] A preparation method of a flame - retardant silane - modified polyether resin, comprising the following steps: S1, Pour 100 - 140 parts of newly prepared polyether polyol into a reaction kettle, dehydrate it under vacuum conditions until the water content is lower than 0.03%, cool it to 45 - 55 °C and reserve it to obtain dehydrated polyether polyol;

[0017] S2, Lower the temperature in the reaction kettle to room temperature, add the dehydrated polyether polyol in S1, start stirring, maintain the temperature at 30 - 50 °C, add stannous octoate accounting for 1 - 1.5% of the mass of stannous octoate in the raw material formula and 4 - 6 parts by mass of tetrahydrofuran under vacuum pumping conditions, and continue stirring for 1 - 2 h after feeding to obtain polyether polyol A;

[0018] S3, Under the condition of 70 - 90 °C, mix triethyl phosphate and 2 - 6 parts by mass of stannous octoate, stir until it is clear and transparent, then add it to polyether polyol A in S2. Control the feeding time of polyether polyol A and triethyl phosphate at 4 - 6 h, and continue stirring for 1 - 2 h after feeding to obtain intermediate product A;

[0019] S4, Under the condition of 75 - 85 °C, continue to mix the remaining stannous octoate and polyether polyol A to obtain intermediate product B;

[0020] S5, Then cool the intermediate product B in S4, add the silane coupling agent accounting for 1 - 1.5% of the mass of the silane coupling agent in the raw material formula and 4 - 6 parts of trimethylbenzene ethylene glycol for feeding, and continue stirring for 1 - 2 h after feeding to obtain intermediate product C;

[0021] S6, Cool the intermediate product C, add the antioxidant accounting for 1 - 1.5% of the mass of the antioxidant in the raw material formula and 2 - 4 parts of catalyst under vacuum pumping conditions, continue stirring for 1 - 2 h, then continue to add the weathering agent accounting for 1 - 1.5% of the mass of the weathering agent in the raw material formula, and continue stirring for 1 - 2 h until the material reaction is complete to obtain polyether polyol D;

[0022] S7, Under the condition of 50 - 80 °C, add toluene diisocyanate accounting for 1 - 2% of the mass of toluene diisocyanate in the raw material formula and dibutyltin dilaurate accounting for 1 - 1.5% of the mass of dibutyltin dilaurate in the raw material formula to polyether polyol D, and stir for 1 - 2 h to obtain polyether polyol E;

[0023] S8. At 80 - 90 °C, add the remaining toluene diisocyanate to polyether polyol E, react for 2 - 3 h with the temperature controlled at 80 - 90 °C, and then cool down to 50 °C to obtain Component A;

[0024] S9. Pour the newly prepared polyether polyol into the reaction kettle, dehydrate it under vacuum conditions until the water content is lower than 0.03%, and cool down to 45 - 55 °C for standby to obtain dehydrated polyether polyol;

[0025] S10. Add the dehydrated polyether polyol in S9 to the reaction kettle, stir for 30 min, heat up to 80 - 90 °C, and add stannous octoate for the first feeding; after the first feeding, add triethyl phosphate, continue stirring for 30 - 60 min after feeding is completed with the temperature controlled at 80 - 100 °C, and add the catalyst again; continue stirring for 30 - 60 min after the catalyst is added with the temperature controlled at 80 - 100 °C to obtain Component B.

[0026] Further, the vacuum condition in S1 is 10 mmHg;

[0027] The stirring speed in S2 is 50 - 65 r / min;

[0028] The mixing time in S3 is 0.5 - 1 h;

[0029] The mixing time in S4 is 0.5 - 1 h;

[0030] The mixing time in S5 is 3 - 6 h;

[0031] The mixing time in S6 is 0.5 - 1 h;

[0032] The mixing time in S7 is 0.5 - 1 h.

[0033] Further, it also includes S11. Mix Component A in S8 and Component B in S10 at a mass ratio of 2 - 2.5:1 to prepare the silicate - modified polyether resin.

[0034] An application of the flame - retardant silane - modified polyether resin, the application of the flame - retardant silane - modified polyether resin in wire and cable;

[0035] The preparation method of the flame - retardant silane - modified polyether resin includes the following steps:

[0036] S1. Pour 100 - 140 parts of the newly prepared polyether polyol into the reaction kettle, dehydrate it under vacuum conditions until the water content is lower than 0.03%, and cool down to 45 - 55 °C for standby to obtain dehydrated polyether polyol;

[0037] S2. Cool down the temperature in the reaction kettle to room temperature, add the dehydrated polyether polyol in S1, start stirring, maintain the temperature at 30 - 50 °C, and add stannous octoate accounting for 1 - 1.5% of the mass of stannous octoate in the raw material formula and 4 - 6 parts by mass of trimethylbenzene ethylene glycol under vacuum conditions. After feeding, continue stirring for 1 - 2 h to obtain polyether polyol A;

[0038] S3. Under the condition of 70 - 90 °C, mix triethyl phosphate and 2 - 6 parts by mass of stannous octoate, stir until clear and transparent, and then add it to polyether polyol A in S2. Control the feeding time of polyether polyol A and triethyl phosphate at 4 - 6 h. After feeding, continue stirring for 1 - 2 h to obtain intermediate product A;

[0039] S4. Under the condition of 75 - 85 °C, continue to mix the remaining stannous octoate and polyether polyol A to obtain intermediate product B;

[0040] S5. Then cool down intermediate product B in S4, add silane coupling agent accounting for 1 - 1.5% of the mass of silane coupling agent in the raw material formula and 4 - 6 parts of trimethylbenzene ethylene glycol for feeding. After feeding, continue stirring for 1 - 2 h to obtain intermediate product C;

[0041] S6. Cool down intermediate product C, add antioxidant accounting for 1 - 1.5% of the mass of antioxidant in the raw material formula and 2 - 4 parts of catalyst under vacuum conditions, degas for 0.5 - 1 h under the conditions of 100 - 150 °C and a vacuum degree of -0.01 Mpa, continue to add weathering agent accounting for 1 - 1.5% of the mass of weathering agent in the raw material formula, and continue stirring for 1 - 2 h until the material reaction is complete to obtain polyether polyol D;

[0042] S7. Under the condition of 50 - 80 °C, add toluene diisocyanate accounting for 1 - 2% of the mass of toluene diisocyanate in the raw material formula and dibutyltin dilaurate accounting for 1 - 1.5% of the mass of dibutyltin dilaurate in the raw material formula to polyether polyol D, and stir for 1 - 2 h to obtain polyether polyol E;

[0043] S8. Under the condition of 80 - 90 °C, add the remaining toluene diisocyanate to polyether polyol E, react for 2 - 3 h, control the temperature at 80 - 90 °C, and then cool down to 50 °C to obtain component A;

[0044] S9. Pour the newly prepared polyether polyol into the reaction kettle, dehydrate under vacuum until the water content is less than 0.03%, cool down to 45 - 55 °C for standby to obtain dehydrated polyether polyol;

[0045] S10. Add the dehydrated polyether polyol in S9 into the reaction kettle, stir for 30 min, heat up to 80 - 90 °C, and add stannous octoate for the first feeding; after the first feeding, add triethyl phosphate, continue to stir for 30 - 60 min after feeding, control the temperature at 80 - 100 °C, and add the catalyst again; continue to stir for 30 - 60 min after adding the catalyst, control the temperature at 80 - 100 °C to obtain Component B.

[0046] S11. Mix Component A in S8 and Component B in S10 at a mass ratio of 2 - 2.5:1 to prepare the silicate-modified polyether resin.

[0047] Further, the vacuum condition in S1 is 10 mmHg;

[0048] The stirring speed in S2 is 50 - 65 r / min;

[0049] The mixing time in S3 is 0.5 - 1 h;

[0050] The mixing time in S4 is 0.5 - 1 h;

[0051] The mixing time in S5 is 0.5 - 1 h;

[0052] The mixing time in S6 is 0.5 - 1 h;

[0053] The mixing time in S7 is 0.5 - 1 h.

[0054] Compared with the prior art, the technical solution of this application has the following beneficial effects:

[0055] For the flame-retardant silane-modified polyether resin and its preparation method, by adding 5 parts of triethyl phosphate during the reaction process and adding 10 - 30 parts of toluene diisocyanate, under the condition of adding a small dose of flame retardant, the flame-retardant performance of the modified polyether resin can meet the requirements of UL94 V0 grade, and the hydrophobic and oil-resistant properties of the polymer can be improved without affecting the mechanical properties and weather resistance of the polymer. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 It is a schematic flow diagram of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0057] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0058] Example 1

[0059] A flame-retardant silane-modified polyether resin, comprising component A and component B;

[0060] By mass parts, the raw material formula of component A includes: 100-140 parts of freshly prepared polyether polyol, 0.5-2.5 parts of stannous octoate, 0.5-5 parts of flame retardant, 2-10 parts of silane coupling agent, 30-50 parts of polytetrahydrofuran diol, 15-30 parts of triethyl phosphate, 1-5 parts of antioxidant, 1-5 parts of weathering agent, 8-15 parts of toluene diisocyanate, 1-3 parts of dibutyltin dilaurate, 0.4-0.6 parts of catalyst;

[0061] By mass parts, the raw material formula of component B includes: 100-140 parts of freshly prepared polyether polyol, 0.5-2.5 parts of stannous octoate, 10-30 parts of toluene diisocyanate, 10-35 parts of triethyl phosphate, 0.1-8 parts of catalyst.

[0062] Furthermore, the freshly prepared polyether polyol has a viscosity of 200-2000 mm2 / s at 25 °C;

[0063] The silane coupling agent is one or a combination of two of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltri-β-methoxyethylsilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, bis(methoxyethoxy)methylvinylsilane, γ-methacryloxypropyltriethoxysilane, methyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane.

[0064] Even further, the catalyst is one or a combination of two of dibutyltin dilaurate, 1,3-dibutyltin diacetate, diethyltin dilaurate, stannous octoate, dibutyltin diacetate, dioctyltin dilaurate, dimethylamine, triethylamine, tributylamine, bis(dimethylaminoethyl)ether, triethylenediamine, N,N-dimethylcyclohexylamine, N,N-dimethylethanolamine, triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triethylamine, N-methylmorpholine, N-phenyl-methylmorpholine, triethanolamine, triethylenediamine, bis(dimethylaminoethyl)ether, bis(diethylaminoethyl)ether and dimethylaminopentanol.

[0065] In addition, the dosage of the silane coupling agent and the flame retardant is 1 - 1.5 parts; the dosage of the silane coupling agent and triethyl phosphate is 3 - 5 parts, and the viscosity of polytetrahydrofuran diol is 50 - 700 mm2 / s.

[0066] Example 2:

[0067] A preparation method of a flame-retardant silane-modified polyether resin, comprising the following steps:

[0068] S1, Pour 100 kg of newly prepared polyether polyol into a reaction kettle, dehydrate it under vacuum conditions until the water content is lower than 0.03%, cool it down to 45 °C and set aside to obtain dehydrated polyether polyol;

[0069] S2, Lower the temperature in the reaction kettle to room temperature, add the dehydrated polyether polyol in S1, start stirring, the stirring speed is 50 r / min, maintain the temperature at 30 °C, add stannous octoate accounting for 1 - 1.5% of the mass of stannous octoate in the raw material formula and 4 kg of tetrahydrofuran under vacuum conditions for feeding. After feeding, continue stirring for 1 h to obtain polyether polyol A;

[0070] S3, Under the condition of 70 °C, mix triethyl phosphate and 2 parts by mass of stannous octoate, stir until clear and transparent, then add it to polyether polyol A in S2. The feeding time of polyether polyol A and triethyl phosphate is controlled within 4 h. After feeding, continue stirring for 1 h to obtain intermediate product A;

[0071] S4, Under the condition of 75 °C, continue to mix the remaining stannous octoate and polyether polyol A to obtain intermediate product B;

[0072] S5, Then cool down the intermediate product B in S4, add the silane coupling agent accounting for 1% of the mass of the silane coupling agent in the raw material formula and 4 parts of trimethylbenzene ethylene glycol for feeding. After feeding, continue stirring for 1 h to obtain intermediate product C;

[0073] S6, Cool down intermediate product C, add the antioxidant accounting for 1% of the mass of the antioxidant in the raw material formula and 2 parts of catalyst under vacuum conditions, continue stirring for 1 h, then continue to add the weathering agent accounting for 1% of the mass of the weathering agent in the raw material formula, and continue stirring for 1 h until the material reaction is complete to obtain polyether polyol D;

[0074] S7, Under the condition of 50 °C, add toluene diisocyanate accounting for 1% of the mass of toluene diisocyanate in the raw material formula and dibutyltin dilaurate accounting for 1% of the mass of dibutyltin dilaurate in the raw material formula to polyether polyol D, and stir for 1 h to obtain polyether polyol E;

[0075] S8. At 80 °C, add the remaining toluene diisocyanate to polyether polyol E, react for 2 h while controlling the temperature at 80 °C, and then cool down to 50 °C to obtain Component A;

[0076] S9. Pour the newly prepared polyether polyol into the reaction kettle, dehydrate it under vacuum until the water content is lower than 0.03%, cool down to 45 - 55 °C for standby to obtain dehydrated polyether polyol;

[0077] S10. Add the dehydrated polyether polyol in S9 to the reaction kettle, stir for 30 min, heat up to 80 °C, and add stannous octoate for the first feeding; after the first feeding, add triethyl phosphate, continue to stir for 30 min after feeding, control the temperature at 80 °C, and add the catalyst again; continue to stir for 30 min after adding the catalyst, control the temperature at 80 °C to obtain Component B;

[0078] S11. Mix Component A in S8 and Component B in S10 at a mass ratio of 2:1 to prepare the silicate - modified polyether resin.

[0079] The viscosity of the newly prepared polyether polyol at 25 °C is 300 mm2 / s; the silane coupling agent is vinyltriethoxysilane; the catalyst is dibutyltin dilaurate; the amount of triethyl phosphate is 15 kg.

[0080] Test the silicate - modified polyether resin prepared in this example, and its measured viscosity is 1500 mPa·s. The viscosity of the newly prepared polyether polyol provided by the present invention at 25 °C is 300 mm2 / s, indicating that the performance of the polyether polyol prepared by the present invention has not been lost;

[0081] It should be noted that the vacuum condition in S1 is 10 mmHg; the stirring speed in S2 is 50 r / min; the mixing time in S3 is 0.5 h; the mixing time in S4 is 0.5 h; the mixing time in S5 is 3 h; the mixing time in S6 is 0.5 h; the mixing time in S7 is 0.5 h.

[0082] In addition, the above - mentioned preparation method further includes S11. Mix Component A in S8 and Component B in S10 at a mass ratio of 2 - 2.5:1 to prepare the silicate - modified polyether resin.

[0083] Example 3:

[0084] A preparation method of a flame - retardant silane - modified polyether resin, characterized by comprising the following steps:

[0085] S1. Pour 140 parts of the newly prepared polyether polyol into the reaction kettle, dehydrate it under vacuum until the water content is lower than 0.03%, cool down to 55 °C for standby to obtain dehydrated polyether polyol;

[0086] S2, lower the temperature in the reactor to room temperature, add the dehydrated polyether polyol in S1, start stirring, maintain the temperature at 50 °C, and add stannous octoate and 4 - 6 parts by mass of tetrahydrofuran, each accounting for 0.5% of the mass in the raw material formula, under vacuum conditions. After feeding, continue stirring for 2 h to obtain polyether polyol A;

[0087] S3, under the condition of 90 °C, mix triethyl phosphate and 6 parts by mass of stannous octoate, stir until clear and transparent, and then add it to polyether polyol A in S2. Control the feeding time of polyether polyol A and triethyl phosphate within 6 h. After feeding, continue stirring for 2 h to obtain intermediate product A;

[0088] S4, under the condition of 85 °C, continue to mix the remaining stannous octoate and polyether polyol A to obtain intermediate product B;

[0089] S5, cool down the intermediate product B in S4, add silane coupling agent and 6 parts of trimethylbenzene ethylene glycol, each accounting for 1.5% of the mass in the raw material formula, under vacuum conditions. After feeding, continue stirring for 2 h to obtain intermediate product C;

[0090] S6, cool down intermediate product C, add antioxidant and 4 parts of catalyst, each accounting for 1.5% of the mass in the raw material formula, under vacuum conditions. After continuing to stir for 2 h, continue to add light stabilizer, each accounting for 1.5% of the mass in the raw material formula, and continue stirring for 2 h until the reaction of the material is complete to obtain polyether polyol D;

[0091] S7, under the condition of 80 °C, add toluene diisocyanate and dibutyltin dilaurate, each accounting for 2% and 1.5% of the mass in the raw material formula, to polyether polyol D, and stir for 2 h to obtain polyether polyol E;

[0092] S8, under the condition of 80 - 90 °C, add the remaining toluene diisocyanate to polyether polyol E, react for 3 h, control the temperature at 90 °C, and then cool down to 50 °C to obtain component A;

[0093] S9, pour the newly prepared polyether polyol into the reactor, dehydrate it under vacuum conditions until the water content is less than 0.03%, cool down to 55 °C for standby to obtain dehydrated polyether polyol;

[0094] S10, add the dehydrated polyether polyol in S9 to the reactor, stir for 30 min, heat up to 90 °C, and add stannous octoate for the first feeding; after the first feeding, add triethyl phosphate. After feeding, continue stirring for 60 min, control the temperature at 100 °C, and add the catalyst again; after adding the catalyst, continue stirring for 60 min, control the temperature at 100 °C to obtain component B.

[0095] Among them, the vacuum condition in S1 is 10 mmHg; the stirring speed in S2 is 65 r / min;

[0096] The mixing time in S3 is 1 h; the mixing time in S4 is 1 h; the mixing time in S5 is 6 h; the mixing time in S6 is 1 h; the mixing time in S7 is 1 h.

[0097] Example 4:

[0098] An application of a flame-retardant silane-modified polyether resin, characterized in that the flame-retardant silane-modified polyether resin is applied in wire and cable;

[0099] The preparation method of the flame-retardant silane-modified polyether resin includes the following steps:

[0100] S1, Pour 120 parts of newly prepared polyether polyol into the reaction kettle, dehydrate it under vacuum conditions until the water content is lower than 0.03%, cool it to 50 °C and set aside to obtain dehydrated polyether polyol;

[0101] S2, Lower the temperature in the reaction kettle to room temperature, add the dehydrated polyether polyol in S1, start stirring, maintain the temperature at 45 °C, add stannous octoate accounting for 1.25% of the mass of stannous octoate in the raw material formula and 5 parts by mass of trimethylbenzene ethylene glycol under vacuum conditions for feeding. After feeding, continue stirring for 1 h to obtain polyether polyol A;

[0102] S3, Under the condition of 80 °C, mix triethyl phosphate and 4 parts by mass of stannous octoate, stir until clear and transparent, then add it to polyether polyol A in S2. The feeding time of polyether polyol A and triethyl phosphate is controlled within 5 h. After feeding, continue stirring for 1.5 h to obtain intermediate product A;

[0103] S4, Under the condition of 80 °C, continue to mix the remaining stannous octoate and polyether polyol A to obtain intermediate product B;

[0104] S5, Then cool the intermediate product B in S4, add silane coupling agent accounting for 1.25% of the mass of silane coupling agent in the raw material formula and 5 parts of trimethylbenzene ethylene glycol for feeding. After feeding, continue stirring for 1.5 h to obtain intermediate product C;

[0105] S6, Cool the intermediate product C, add antioxidant accounting for 1.25% of the mass of antioxidant in the raw material formula and 3 parts of catalyst under vacuum conditions, degas for 1 h at 125 °C and a vacuum degree of -0.01 Mpa, continue to add weathering agent accounting for 1.25% of the mass of weathering agent in the raw material formula, and continue stirring for 1 - 2 h until the material reacts completely to obtain polyether polyol D;

[0106] S7. At 75 °C, add to the polyether polyol D toluene diisocyanate and dibutyltin dilaurate in amounts of 1.5% by mass of the toluene diisocyanate and 1.5% by mass of the dibutyltin dilaurate in the raw material formulation, and stir for 1.5 h to obtain polyether polyol E;

[0107] S8. At 85 °C, add the remaining toluene diisocyanate to the polyether polyol E, react for 2.5 h, control the temperature at 85 °C, and then cool down to 50 °C to obtain Component A;

[0108] S9. Pour the newly prepared polyether polyol into the reaction kettle, dehydrate it under vacuum until the water content is less than 0.03%, and cool down to 50 °C for standby to obtain dehydrated polyether polyol;

[0109] S10. Add the dehydrated polyether polyol in S9 to the reaction kettle, stir for 30 min, heat up to 80 - 90 °C, and add stannous octoate for the first feeding; after the first feeding, add triethyl phosphate, continue stirring for 50 min after feeding, control the temperature at 90 °C, and add the catalyst again; continue stirring for 50 min after adding the catalyst, control the temperature at 90 °C to obtain Component B;

[0110] S11. Mix Component A in S8 and Component B in S10 at a mass ratio of 2.3:1 to prepare the silicate - modified polyether resin.

[0111] Among them, the vacuum condition in S1 is 10 mmHg; the stirring speed in S2 is 55 r / min; the mixing time in S3 is 0.8 h; the mixing time in S4 is 0.7 h; the mixing time in S5 is 0.6 h; the mixing time in S6 is 0.7 h; the mixing time in S7 is 0.7 h; the mixing time in S6 is 0.8 h.

[0112] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "including", "comprising" or any other variant thereof is intended to cover non - exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. Without further limitation, an element defined by the statement "including a..." does not exclude the existence of additional identical elements in the process, method, article or device including the said element.

[0113] Although embodiments of the present invention have been shown and described, those of ordinary skill in the art will appreciate that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A flame retardant silane-modified polyether resin, characterized in that: It includes component A and component B; The raw material formula of component A includes, by weight: 100-140 parts of newly prepared polyether polyol, 0.5-2.5 parts of stannous octoate, 0.5-5 parts of flame retardant, 2-10 parts of silane coupling agent, 30-50 parts of polytetrahydrofuran diol, 15-30 parts of triethyl phosphate, 1-5 parts of antioxidant, 1-5 parts of weathering agent, 8-15 parts of toluene diisocyanate, 1-3 parts of dibutyltin dilaurate, and 0.4-0.6 parts of catalyst; In terms of weight percentage, the raw material formula of component B includes: 100-140 parts of newly prepared polyether polyol, 0.5-2.5 parts of stannous octoate, 10-30 parts of toluene diisocyanate, 10-35 parts of triethyl phosphate, and 0.1-8 parts of a catalyst.

2. The flame retardant silane-modified polyether resin according to claim 1, characterized in that: The viscosity of the newly prepared polyether polyol at 25° C. is 200-2000 mm2 / s; The silane coupling agent is one or a combination of two of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri(2-methoxyethoxy)silane, vinyl triβ-methoxyethylsilane, methyl vinyl dimethoxysilane, methyl vinyl diethoxysilane, diethoxymethyl vinyl silane, dimethoxymethyl vinyl silane, di(methoxyethoxy)methyl vinyl silane, γ-methacryloxypropyl triethoxysilane, methyl trimethoxysilane, γ-methacryloxypropyl methyl diethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-glycidyl ether oxypropyl trimethoxysilane or γ-glycidyl ether oxypropyl triethoxysilane.

3. The flame retardant silane-modified polyether resin according to claim 1, characterized in that: The catalyst is one or a combination of two of dibutyltin dilaurate, dibutyltin 1,3-diacetate, diethyltin dilaurate, stannous octoate, dibutyltin diacetate, dioctyltin dilaurate, dimethylamine, triethylamine, tributylamine, bis(dimethylaminoethyl) ether, triethylenediamine, N,N-dimethylcyclohexylamine, N,N-dimethylethanolamine, triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triethylamine, N-methylmorpholine, N-phenyl-methylmorpholine, triethanolamine, triethylenediamine, bis(dimethylaminoethyl) ether, bis(diethylaminoethyl) ether and dimethylaminopentanol.

4. The flame retardant silane-modified polyether resin according to claim 1, characterized in that: The amount of the silane coupling agent and the flame retardant is 1-1.5 parts; The usage of the silane coupling agent and triethyl phosphate is 3-5 parts.

5. The flame retardant silane-modified polyether resin according to claim 1, characterized in that: The viscosity of the polytetrahydrofuran diol is 50-700mm2 / s.

6. A method for preparing a flame retardant silane-modified polyether resin, characterized in that: The following steps are involved: S1, pouring 100-140 parts of the newly prepared polyether polyol into a reaction kettle, dehydrating under vacuum conditions until the water content is less than 0.03%, cooling to 45-55° C. for standby use, to obtain a dehydrated polyether polyol; S2, lowering the temperature in the reaction kettle to room temperature, adding the dehydrated polyether polyol in S1, starting stirring, maintaining the temperature at 30-50° C., adding stannous octoate accounting for 1-1.5% of the mass of stannous octoate in the raw material formula and 4-6 parts by mass of tetrahydrofuran under vacuum conditions, and continuing stirring for 1-2 hours after the addition of the materials to obtain polyether polyol A; S3, at 70-90 degrees Celsius, triethyl phosphate and 2-6 parts by mass of stannous octoate are mixed, stirred until clear and transparent, and then added to the polyether polyol A in S2, the feeding time of polyether polyol A and triethyl phosphate is controlled at 4-6 hours, and stirring is continued for 1-2 hours after the feeding is completed to obtain an intermediate product A; S4, continuing to mix the remaining stannous octoate and polyether polyol A at 75-85° C. to obtain an intermediate product B; S5, cooling the intermediate product B in S4, adding 1-1.5% by weight of the silane coupling agent in the raw material formula and 4-6 parts of trimethylol glycol, and stirring for 1-2 hours after the addition of the materials, to obtain an intermediate product C; S6, cooling the intermediate product C, adding an antioxidant accounting for 1-1.5% by weight of the antioxidant in the raw material formula and 2-4 parts of a catalyst under vacuum conditions, continuing to stir for 1-2 hours, and then continuing to add a weathering agent accounting for 1-1.5% by weight of the weathering agent in the raw material formula, and continuing to stir for 1-2 hours until the materials react completely to obtain a polyether polyol D; S7, adding toluene diisocyanate accounting for 1-2% by weight of toluene diisocyanate in the raw material formula and dibutyl tin dilaurate accounting for 1-1.5% by weight of dibutyl tin dilaurate in the raw material formula to polyether polyol D at 50-80° C., stirring for 1-2 hours to obtain polyether polyol E; S8, adding the remaining toluene diisocyanate to the polyether polyol E at 80-90° C., reacting for 2-3 hours, controlling the temperature at 80-90° C., and then cooling to 50° C. to obtain component A; S9, pouring the newly prepared polyether polyol into a reaction kettle, dehydrating it under vacuum conditions until the water content is less than 0.03%, cooling it to 45-55° C. for standby use, to obtain a dehydrated polyether polyol; S10, adding the dehydrated polyether polyol in S9 into the reaction kettle, stirring for 30 minutes, heating to 80-90°C, adding stannous octoate for initial feeding; adding triethyl phosphate after the initial feeding, continuing to stir for 30-60 minutes after the feeding is completed, controlling the temperature at 80-100°C, and adding the catalyst again; continuing to stir for 30-60 minutes after the catalyst is added, controlling the temperature at 80-100°C, and obtaining component B.

7. The method for preparing the flame retardant silane-modified polyether resin according to claim 6, characterized in that: The vacuum condition in S1 is 10 mmHg; The stirring speed in S2 is 50-65r / min; The mixing time in S3 is 0.5-1h; The mixing time in S4 is 0.5-1h; The mixing time in S5 is 3-6h; The mixing time in S6 is 0.5-1h; The mixing time in S7 is 0.5-1 h.

8. The method for preparing the flame retardant silane-modified polyether resin according to claim 7, characterized in that: The method further comprises S11, mixing the component A in S8 and the component B in S10 at a mass ratio of 2-2.5:1 to prepare a silicate-modified polyether resin.

9. An application of a flame retardant silane-modified polyether resin, characterized in that: Application of the flame retardant silane modified polyether resin in wires and cables; The preparation method of the flame retardant silane modified polyether resin comprises the following steps: S1, pouring 100-140 parts of the newly prepared polyether polyol into a reaction kettle, dehydrating under vacuum conditions until the water content is less than 0.03%, cooling to 45-55° C. for standby use, to obtain a dehydrated polyether polyol; S2, lowering the temperature in the reaction kettle to room temperature, adding the dehydrated polyether polyol in S1, starting stirring, maintaining the temperature at 30-50° C., adding stannous octoate accounting for 1-1.5% of the mass of stannous octoate in the raw material formula and 4-6 parts by mass of trimethylol glycol under vacuum conditions, and continuing stirring for 1-2 hours after the addition of the materials to obtain polyether polyol A; S3, at 70-90 degrees Celsius, triethyl phosphate and 2-6 parts by mass of stannous octoate are mixed, stirred until clear and transparent, and then added to the polyether polyol A in S2, the feeding time of polyether polyol A and triethyl phosphate is controlled at 4-6 hours, and stirring is continued for 1-2 hours after the feeding is completed to obtain an intermediate product A; S4, continuing to mix the remaining stannous octoate and polyether polyol A at 75-85° C. to obtain an intermediate product B; S5, cooling the intermediate product B in S4, adding 1-1.5% by weight of the silane coupling agent in the raw material formula and 4-6 parts of trimethylol glycol, and stirring for 1-2 hours after the addition of the materials, to obtain an intermediate product C; S6, cooling the intermediate product C, adding an antioxidant accounting for 1-1.5% by weight of the antioxidant in the raw material formula and 2-4 parts of a catalyst under vacuum conditions, degassing for 0.5-1h at 100-150°C and a vacuum degree of -0.01Mpa, continuing to add a weathering agent accounting for 1-1.5% by weight of the weathering agent in the raw material formula, and continuing to stir for 1-2h until the material reaction is complete to obtain polyether polyol D; S7, adding toluene diisocyanate accounting for 1-2% by weight of toluene diisocyanate in the raw material formula and dibutyl tin dilaurate accounting for 1-1.5% by weight of dibutyl tin dilaurate in the raw material formula to polyether polyol D at 50-80° C., stirring for 1-2 hours to obtain polyether polyol E; S8, adding the remaining toluene diisocyanate to the polyether polyol E at 80-90° C., reacting for 2-3 hours, controlling the temperature at 80-90° C., and then cooling to 50° C. to obtain component A; S9, pouring the newly prepared polyether polyol into a reaction kettle, dehydrating it under vacuum conditions until the water content is less than 0.03%, cooling it to 45-55° C. for standby use, to obtain a dehydrated polyether polyol; S10, adding the dehydrated polyether polyol in S9 into the reaction kettle, stirring for 30 minutes, heating to 80-90°C, adding stannous octoate for initial feeding; adding triethyl phosphate after the initial feeding, continuing stirring for 30-60 minutes after the feeding is completed, controlling the temperature at 80-100°C, and adding the catalyst again; continuing stirring for 30-60 minutes after the catalyst is added, controlling the temperature at 80-100°C, and obtaining component B; S11, mixing the component A in S8 and the component B in S10 at a mass ratio of 2-2.5:1 to prepare a silicate-modified polyether resin.

10. The use of the flame retardant silane modified polyether resin according to claim 9, characterized in that: The vacuum condition in S1 is 10 mmHg; The stirring speed in S2 is 50-65r / min; The mixing time in S3 is 0.5-1h; The mixing time in S4 is 0.5-1h; The mixing time in S5 is 0.5-1h; The mixing time in S6 is 0.5-1h; The mixing time in S7 is 0.5-1 h.

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