CN113717371B - Preparation method of low-viscosity reactive flame-retardant polyether polyol, reactive flame-retardant heat-conducting polyurethane electronic pouring sealant and preparation method thereof - Google Patents

Preparation method of low-viscosity reactive flame-retardant polyether polyol, reactive flame-retardant heat-conducting polyurethane electronic pouring sealant and preparation method thereof Download PDF

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CN113717371B
CN113717371B CN202111002930.7A CN202111002930A CN113717371B CN 113717371 B CN113717371 B CN 113717371B CN 202111002930 A CN202111002930 A CN 202111002930A CN 113717371 B CN113717371 B CN 113717371B
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retardant
reactive flame
polyether polyol
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pouring sealant
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CN113717371A (en
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李健
戈欢
孙兆任
李剑锋
栾森
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Shandong Inov New Material Co Ltd
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Shandong Inov New Material Co Ltd
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
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    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
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    • C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers

Abstract

The invention relates to a preparation method of low-viscosity reactive flame-retardant polyether polyol, reactive flame-retardant heat-conducting polyurethane electronic pouring sealant and a preparation method thereof, and belongs to the technical field of polyurethane electronic pouring sealants. The invention takes low molecular weight polyether, bisphenol A polyether and halogen-containing aromatic alcohol/phenol as composite initiator, and reacts with alkylene oxide in polymerization under the action of bimetallic catalyst to obtain low viscosity reactive flame-retardant polyether polyol. The pouring sealant comprises a component A, a component B and a component C, wherein the component A comprises diisocyanate, isocyanate group cage type polysilsesquioxane, polypropylene oxide polyether polyol, polytetrahydrofuran ether polyol and plasticizer; the component B comprises a chain extender, a reactive flame-retardant polyether polyol, a defoamer polyether polyol, a heat-conducting filler, a polyoxypropylene polyether polyol, a catalyst and an antioxidant; the pouring sealant prepared by the invention has excellent flame retardant property and heat conducting property; the invention also provides a simple and easy preparation method.

Description

Preparation method of low-viscosity reactive flame-retardant polyether polyol, reactive flame-retardant heat-conducting polyurethane electronic pouring sealant and preparation method thereof
Technical Field
The invention relates to a preparation method of low-viscosity reactive flame-retardant polyether polyol, reactive flame-retardant heat-conducting polyurethane electronic pouring sealant and a preparation method thereof, and belongs to the technical field of polyurethane electronic pouring sealants.
Background
Polyurethane elastomer is widely used in sports, medical treatment, automobile, building and other fields due to its excellent properties such as wide range of performance controllability, ultraviolet resistance, wear resistance, solvent resistance and the like. Polyurethane elastomers can be classified into casting type and thermoplastic type according to the process. As one of casting polyurethane, the polyurethane pouring sealant can be cured and formed at room temperature through a simple pouring technology, and the excellent insulativity ensures the normal operation of batteries, electronic elements and matched devices thereof. However, the chemical bond in the polyurethane chain segment is mainly a hydrocarbon bond, the bond energy is low and is easy to break, and the polyurethane material is classified as inflammable material according to the combustion grade; meanwhile, the polyurethane pouring sealant cannot effectively conduct heat generated in the working process of the electronic element, and the service performance of the polyurethane pouring sealant is reduced. Therefore, the preparation of the heat-conducting and flame-retardant electronic pouring sealant becomes a research hot spot.
The flame retardant is divided into an additive flame retardant and a reactive flame retardant, and the additive flame retardant electronic pouring sealant improves the flame retardant property mainly by adding phosphate esters or low-molecular-weight halogen with larger fraction. CN111732927a provides a high-hardness flame-retardant polyurethane electronic pouring sealant and a preparation method thereof, phosphate (component a) and chlorinated paraffin-52 (component B) are adopted as flame retardants, and the flame retardant grade of the pouring sealant can reach V0. Both the phosphate and the chlorinated paraffin-52 are added flame retardants, and have mobility and the danger of corroding electronic devices; when the proportion of the phosphate is higher, the toughness of the material is reduced; CN111704886a discloses a two-component high-toughness flame-retardant polyurethane electronic pouring sealant and a preparation method thereof, and the same adopts additive flame retardants such as tri (2-chloropropyl) phosphate, tri (2-carboxyethyl) phosphine, isopropyl diphenyl phosphate, chlorinated paraffin-52, chlorinated paraffin-42 and the like to achieve V-0 level flame retardance; CN107216846A adopts dibromo neopentyl glycol and resorcinol (bis-diphenyl phosphate) mixture flame-retardant polyurethane electronic pouring sealant, and dibromo neopentyl glycol is high in price and high in melting point (114-116 ℃), and is not used for industrial popularization.
Reactive flame retardant polyethers currently on the market are generally expensive and have many constraints such as high viscosity (tetrabromophthalic anhydride diol viscosity of 80000-125000 mpa.s); the color value is deep (generally amber or brown), which affects the appearance and service performance of the polyurethane material. Therefore, developing low-viscosity reactive flame-retardant polyether polyol for preparing flame-retardant heat-conducting polyurethane electronic pouring sealant is a problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art and providing a preparation method of low-viscosity reactive flame-retardant polyether polyol, which is simple and easy to operate, has no post-treatment process and has moderate viscosity; the reactive flame-retardant heat-conducting polyurethane electronic pouring sealant has excellent flame-retardant property and heat-conducting property; the invention also provides a simple and easy preparation method.
The preparation method of the low-viscosity reactive flame-retardant polyether polyol comprises the steps of taking 1 part of low-molecular-weight polyether, 1-2 parts of bisphenol A polyether and 1-3 parts of halogen-containing aromatic alcohol/phenol as a composite initiator, carrying out polymerization reaction with alkylene oxide under the action of 30-1000ppm of a bimetallic catalyst, and carrying out polymerization for 3-6h at 130-140 ℃ to obtain the low-viscosity reactive flame-retardant polyether polyol.
Preferably, the functionality of the low molecular weight polyether is 2-3, mn is 500-1000.
Preferably, the halogen-containing aromatic alcohol/phenol is one or more of 2, 3-dibromo-4, 5-dihydroxybenzyl alcohol, 2, 4-dichlorobenzyl alcohol, 5-chloro-2-hydroxybenzyl alcohol, 3- (3-bromophenyl) -2-propyn-1-ol, tetrabromobisphenol A, 5-bromo-2-hydroxybenzyl alcohol, or tribromophenol.
The reactive flame-retardant heat-conducting polyurethane electronic pouring sealant prepared by utilizing the low-viscosity reactive flame-retardant polyether polyol comprises a component A and a component B, wherein,
and (3) a component A: comprises diisocyanate, isocyanate-based cage polysilsesquioxane, polypropylene oxide polyether polyol, polytetrahydrofuran ether polyol and plasticizer;
and the component B comprises the following components: comprises a chain extender, a reactive flame-retardant polyether polyol, a defoamer polyether polyol, a heat-conducting filler, a polyoxypropylene polyether polyol, a catalyst and an antioxidant;
the isocyanate-based cage polysilsesquioxane is prepared by reacting diisocyanate and tetrahydrofuran solution of hydroxyl-terminated cage silsesquioxane, wherein the mass percentage of the hydroxyl-terminated cage silsesquioxane is 30-50%, and the reaction temperature is 60-80 ℃; preferably, the mass percentage of the hydroxyl cage type silsesquioxane is 40%.
The functionality of the reactive flame-retardant polyether polyol is 2-3, the hydroxyl value is 56-165mg KOH/g, and the viscosity is 700-15500 mpa.s.
Preferably, the component A comprises the following raw materials in percentage by mass:
preferably, the diisocyanate is one or more of diphenylmethane diisocyanate, HDI, IPDI or toluene diisocyanate. The amount is more preferably 40%.
Preferably, the plasticizer is one or more of dioctyl phthalate, dioctyl sebacate, trioctyl trimellitate, epoxidized soybean oil or dibutyl phthalate. Further preferred is dioctyl phthalate.
Preferably, the polyoxypropylene ether polyol has a number average molecular weight of 1000-6000 and a functionality of 2 or 3.
Preferably, the polytetrahydrofuran ether polyol has a number average molecular weight of 1000 to 2000 and a functionality of 2.
Preferably, the component B comprises the following raw materials in percentage by mass:
preferably, the chain extender is one or more of ethylene glycol, 1, 4-butanediol, diethylene glycol, 1, 3-propanediol, dipropylene glycol or 1, 6-hexanediol. 1, 4-butanediol is further preferred.
Preferably, the heat conducting filler is one or more of fibrous high heat conducting carbon powder, scaly high heat conducting carbon powder or alpha-alumina. Further preferred is scaly high thermal conductivity carbon powder.
Preferably, the antioxidant is one or more of 1076, 1010, 1135, 318 or 339.
Preferably, the catalyst is one or more of organotin, organozinc or organozirconium.
Preferably, the defoamer polyether polyol has a number average molecular weight of 1000 to 5000 and a functionality of 1 to 3.
The preparation method of the reactive flame-retardant heat-conducting polyurethane electronic pouring sealant comprises the following steps:
(1) Firstly, reacting the formula amount of polyoxypropylene ether polyol, polytetrahydrofuran ether polyol, diisocyanate, isocyanate polysilsesquioxane and plasticizer for 1-3 hours at 70-85 ℃ to obtain a prepolymer with the isocyanate group content of 7.0-18.0 wt%, thus obtaining a component A;
(2) The component B is obtained by vacuum dehydration of the formula amount of chain extender, polyoxypropylene ether polyol, reactive flame retardant polyether polyol, heat conducting filler, defoamer polyether polyol, catalyst and antioxidant at 100-110 ℃ and below-0.095 MPa until the water content is less than 0.03%;
(3) A, B components are mixed according to the weight ratio of 100:90-120, casting the mixture into a mold with the temperature of 30-35 ℃ for reaction at the temperature of 30-40 ℃ and curing at room temperature to obtain the reactive flame-retardant heat-conducting polyurethane electronic pouring sealant.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts the bimetallic catalyst to prepare the low-viscosity flame-retardant polyether polyol by a one-step method, has no post-treatment process, has simple preparation method, less three-waste emission and moderate viscosity, and is suitable for industrial production; flame-retardant bromine element is introduced into a co-initiator to prepare reaction (structure) flame-retardant polyether, so that small molecule migration is avoided; the introduced benzene ring structure can effectively improve the heat resistance of the polyurethane network;
(2) When the pouring sealant is prepared, the isocyanate modified polysilsesquioxane is utilized, the Si-O structure is doped into the polyurethane network, the high-temperature service performance of the pouring sealant is improved, and the stability of the polyurethane network is obviously improved by taking the cage structure as a crosslinking point;
(3) When the pouring sealant is prepared, the defoamer polyether is added, so that the pouring sealant has good intersolubility, on one hand, a large number of bubbles generated during mixing of the components A/B can be effectively reduced, and on the other hand, the defoaming agent serving as a surfactant can be used for rapidly defoaming;
(4) When the pouring sealant is prepared, the added heat conducting filler uses the heat conducting particles with a two-dimensional structure, so that the heat transfer area can be effectively increased, and the heat conducting property of the electronic pouring sealant is effectively improved.
Detailed Description
The invention is further illustrated below in connection with examples, which are not intended to limit the practice of the invention.
The formula system is used in the invention:
polytetrahydrofuran ether polyol PTMG1000 functionality 2, molecular weight 1000;
polytetrahydrofuran ether polyol PTMG2000 functionality 2, molecular weight 2000.
Polyether polyols are all produced by monowiry New Material Co., ltd, and the specific brands are as follows:
low molecular weight polyether polyols series:
inonol C204 (2 functionality 400 molecular weight);
inonol C207 (2 functionality 700 molecular weight);
inonol C305 (3 functionality 500 molecular weight);
inonol C310 (3 functionality 1000 molecular weight).
Bisphenol a polyether polyol series:
inonol S207H (2 functionality 700 molecular weight);
inonol S210H (2 functionality 1000 molecular weight);
inonol S220H (2 functionality 2000 molecular weight).
Polyoxypropylene ether polyol series:
inonol F3600 (3 functionality 6000 molecular weight);
inonol F330N (3 functionality 5000 molecular weight);
inonol C210 (2 functionality 1000 molecular weight);
inonol C220 (2 functionality 2000 molecular weight);
inonol C230 (2 functionality 3000 molecular weight);
inonol C240A (2 functionality 4000 molecular weight).
Defoamer polyether polyol series:
INOVOL S01X；
INOVOL S02X；
INOVOL S1200。
example 1
Preparing reactive flame-retardant polyether polyol:
adding 305 150g of INOVOL C, 150g of bisphenol A polyether S207H and 330g of tribromophenol into a pressure-resistant container, heating to 110 ℃ for dehydration for 2H after nitrogen replacement for 3 times, heating to 135 ℃ for dropwise adding 40g of propylene oxide for initiation, slowly feeding 360g of propylene oxide after the pressure is reduced to minus 0.06MPa, controlling the pressure in the reaction process to be less than 0.30MPa, carrying out internal pressure reaction for 2H, removing monomers for 0.5H, and discharging.
The polyether hydroxyl number was tested at 110mg KOH/g and the viscosity at 824 mpa.s.
Preparing polyurethane electronic pouring sealant:
the component A comprises the following components in percentage by mass: MDI 40%, isocyanate polysilsesquioxane 10%, PTMG1000 10%, C210 10%, F330N 10%, C230 5%, dioctyl phthalate 15%, reacting at 80 ℃ for 1 hour to obtain a prepolymer having an isocyanate content of 11%;
and the component B comprises the following components in percentage by mass: 15% of reactive flame-retardant polyether polyol, 10% of chain extender 1,4 butanediol, 20% of fibrous high-heat-conductivity carbon powder, 20% of defoamer polyether S01X 10%, F3600 15%, C230, C240A 14% and dibutyltin dilaurate: 0.2%, antioxidant 1076:0.8%, vacuum dehydrating at 100 ℃ and below-0.095 MPa until the water content is less than 0.03%.
The mass ratio of the component A to the component B is 100:110, mixing at 40 ℃, casting into a mold at 30 ℃ for reaction after mixing, and curing at room temperature for 7 days to obtain the polyurethane elastomer preparation test.
Example 2
Preparing reactive flame-retardant polyether polyol:
adding 310 100g of INOVOL C, 265g of bisphenol A polyether S210H, 50g of tribromophenol, and 265g of 2,4 dichlorobenzyl alcohol into a pressure-resistant container, heating to 110 ℃ for dehydration for 2H after nitrogen replacement for 3 times, heating to 132 ℃ and dropwise adding 62g of propylene oxide for initiation, slowly feeding 388g of propylene oxide after the pressure is reduced to-0.04 MPa, controlling the pressure in the reaction process to be less than 0.30MPa, carrying out internal pressure reaction for 2H, removing monomers for 0.5H, and discharging.
The polyether hydroxyl number was 153mg KOH/g and the viscosity was 602 mpa.s.
Preparing polyurethane electronic pouring sealant:
the component A comprises the following components in percentage by mass: HDI 38%, isocyanate polysilsesquioxane 12%, PTMG1000 15%, C220 10%, F330N 8%, C230%, plasticizer 8%; reacting at 80 ℃ for 1.5 hours to obtain a prepolymer with 14.4 percent of isocyanate;
and the component B comprises the following components in percentage by mass: 20% of reactive flame-retardant polyether polyol, 12% of chain extender 1,4 butanediol, 15% of fibrous high-heat-conductivity carbon powder, 15% of defoamer polyether S02X 8%, F3600 13%, C230 13%, C240A 10%, C240A 8% and catalyst dibutyltin dilaurate: 0.3%, antioxidant 1010:0.7%, and vacuum dehydrating at 100 ℃ and below-0.095 MPa until the water content is less than 0.03%.
The mass ratio of the component A to the component B is 100:100, mixing at 40 ℃, casting into a mold at 30 ℃ for reaction after mixing, and curing at room temperature for 7 days to obtain the polyurethane elastomer preparation test.
Example 3
Preparing reactive flame-retardant polyether polyol:
adding 204 100g of INOVOL C, 120g of bisphenol A polyether S220H, 300g of tetrabromobisphenol A into a pressure-resistant container, heating to 110 ℃ for dehydration for 2H after nitrogen replacement for 3 times, heating to 130 ℃ for dropwise adding 50g of propylene oxide for initiation, slowly feeding 850g of propylene oxide after the pressure is reduced to-0.07 MPa, controlling the pressure in the reaction process to be less than 0.30MPa, carrying out internal pressure reaction for 2H, removing monomers for 0.5H, and discharging.
The polyether has a hydroxyl number of 80mg KOH/g and a viscosity of 6420 mpa.s.
Preparing polyurethane electronic pouring sealant:
the component A comprises the following components in percentage by mass: MDI-50%, isocyanate polysilsesquioxane 11%, PTMG2000 10%, C210 7%, F330N 10%, C220%, plasticizer 17%; reacting at 80 ℃ for 1.5 hours to obtain a prepolymer with 10.6 percent of isocyanate;
and the component B comprises the following components in percentage by mass: 22% of reactive flame-retardant polyether polyol, 9% of chain extender 1,4 butanediol, 18% of fibrous high-heat-conductivity carbon powder, 18% of defoamer polyether S01X 9%, F3600 16%, C230 16%, C240A 9% and catalyst dibutyltin dilaurate: 0.2%, antioxidant 1135:0.8%. Vacuum dewatering at 105 deg.C and below-0.095 MPa until the water content is less than 0.03%.
The mass ratio of the component A to the component B is 100:100, mixing at 40 ℃, casting into a mold at 30 ℃ for reaction after mixing, and curing at room temperature for 7 days to obtain the polyurethane elastomer preparation test.
Comparative example 1
Adding 305 125g of INOVOL C and 175g of bisphenol A polyether S207H into a pressure-resistant container, carrying out nitrogen substitution for 3 times, heating to 110 ℃ for dehydration for 2 hours, heating to 135 ℃ for dropwise adding 37g of propylene oxide for initiation, slowly feeding 300g of propylene oxide after the pressure is reduced to minus 0.06MPa, controlling the pressure in the reaction process to be less than 0.30MPa, carrying out internal pressure reaction for 2 hours, removing monomers for 0.5 hour, and discharging.
The polyether hydroxyl number was tested at 111mg KOH/g and the viscosity at 730 mpa.s.
Preparing polyurethane electronic pouring sealant:
the component A comprises the following components in percentage by mass: MDI 40%, isocyanate polysilsesquioxane 10%, PTMG1000 10%, C210 10%, F330N 10%, C230 5%, dioctyl phthalate 15%, reacting at 80 ℃ for 1 hour to obtain a prepolymer having an isocyanate content of 11%;
and the component B comprises the following components in percentage by mass: 15% of reactive flame-retardant polyether polyol, 10% of chain extender 1,4 butanediol, 20% of fibrous high-heat-conductivity carbon powder, 20% of defoamer polyether S01X 10%, F3600 15%, C230, C240A 14% and dibutyltin dilaurate: 0.2%, antioxidant 1076:0.8%, vacuum dehydrating at 100 ℃ and below-0.095 MPa until the water content is less than 0.03%.
The mass ratio of the component A to the component B is 100:110, mixing at 40 ℃, casting into a mold at 30 ℃ for reaction after mixing, and curing at room temperature for 7 days to obtain the polyurethane elastomer preparation test.
Comparative example 2
Preparing polyurethane electronic pouring sealant:
the component A comprises the following components in percentage by mass: HDI 42%, PTMG1000 15%, C220%, F330N 11%, C23012%, plasticizer 8%; reacting at 80 ℃ for 1.5 hours to obtain a prepolymer with 14.4 percent of isocyanate;
and the component B comprises the following components in percentage by mass: 20% of reactive flame-retardant polyether polyol (flame-retardant polyether polyol synthesized in example 2), 12% of chain extender 1,4 butanediol, 15% of fibrous high-heat-conductivity carbon powder, 15% of defoamer polyether S02X 8%, F3600 13%, C230, C240A 10%, C240A 8% of catalyst dibutyltin dilaurate: 0.3%, antioxidant 1010:0.7%, and vacuum dehydrating at 100 ℃ and below-0.095 MPa until the water content is less than 0.03%.
Hardness is measured according to GB/T531.1-2008 standard;
viscosity was determined according to GB/T12008.8-1992 standard;
flame retardant rating is tested according to UL-94 standard;
the thermal conductivity was measured according to GB/T3139-2005 standard.
Table 1 test results for examples and comparative products
The foregoing embodiments have described the technical solutions and advantages of the present invention in detail, and it should be understood that the foregoing embodiments are merely illustrative of the present invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like that fall within the principles of the present invention should be included in the scope of the invention.

Claims (5)

1. A preparation method of a low-viscosity reactive flame-retardant polyether polyol is characterized by comprising the following steps:
taking low molecular weight polyether, bisphenol A polyether and halogen-containing aromatic alcohol/phenol as composite initiator, and carrying out polymerization reaction with alkylene oxide under the action of a bimetallic catalyst to obtain the low-viscosity reactive flame-retardant polyether polyol;
the halogen-containing aromatic alcohol/phenol is one or more of 2, 3-dibromo-4, 5-dihydroxybenzyl alcohol, 2, 4-dichlorobenzyl alcohol, 5-chloro-2-hydroxybenzyl alcohol, 3- (3-bromophenyl) -2-propyn-1-ol, tetrabromobisphenol A, 5-bromo-2-hydroxybenzyl alcohol or tribromophenol;
the functionality of the low molecular weight polyether is 2-3, mn is more than or equal to 500 and less than or equal to 1000;
the functionality of the reactive flame-retardant polyether polyol is 2-3, the hydroxyl value is 56-165mg KOH/g, and the viscosity is 700-15500 mpa.s.
2. A reactive flame retardant, thermally conductive polyurethane electronic casting glue prepared from the low viscosity reactive flame retardant polyether polyol prepared by the method of claim 1, characterized in that: the composite material comprises a component A and a component B, wherein the weight ratio of the component A, B is 100:90-120;
the component A comprises the following raw materials in percentage by mass:
10 to 42 percent of diisocyanate
7-12% of isocyanate group cage type polysilsesquioxane
8-28% of polyoxypropylene polyether polyol
Polytetrahydrofuran ether polyol 10-32%
10-25% of plasticizer;
the component B comprises the following raw materials in percentage by mass:
chain extender 5-15%
6-35% of reactive flame-retardant polyether polyol
3-10% of defoamer polyether polyol
5-20% of heat conducting filler
15-55% of polyoxypropylene polyether polyol
Catalyst 0.1-0.5%
0.1 to 1.5 percent of antioxidant;
the isocyanate-based cage polysilsesquioxane is prepared by reacting diisocyanate and tetrahydrofuran solution of hydroxyl-terminated cage silsesquioxane, wherein the mass percentage of the hydroxyl-terminated cage silsesquioxane is 30-50%, and the reaction temperature is 60-80 ℃;
the functionality of the reactive flame-retardant polyether polyol is 2-3, the hydroxyl value is 56-165mg KOH/g, and the viscosity is 700-15500 mpa.s;
the chain extender is one or more of ethylene glycol, 1, 4-butanediol, diethylene glycol, 1, 3-propanediol, dipropylene glycol or 1, 6-hexanediol;
the heat conducting filler is one or more of fibrous high heat conducting carbon powder, scaly high heat conducting carbon powder or alpha-alumina;
the antioxidant is one or more of 1076, 1010, 1135, 318 or 339;
the catalyst is one or more of organotin, organozinc or organozirconium.
3. The reactive flame-retardant heat-conducting polyurethane electronic pouring sealant according to claim 2, wherein: the diisocyanate is one or more of diphenylmethane diisocyanate, HDI, IPDI or toluene diisocyanate;
the plasticizer is one or more of dioctyl phthalate, dioctyl sebacate, trioctyl trimellitate, epoxidized soybean oil or dibutyl phthalate.
4. The reactive flame-retardant heat-conducting polyurethane electronic pouring sealant according to claim 2, wherein: the number average molecular weight of the polyoxypropylene ether polyol is 1000-6000 and the functionality is 2 or 3.
5. A method for preparing the reactive flame-retardant heat-conducting polyurethane electronic pouring sealant according to any one of claims 2 to 4, which is characterized in that: the method comprises the following steps:
(1) Firstly, reacting the formula amount of polyoxypropylene ether polyol, polytetrahydrofuran ether polyol, diisocyanate, isocyanate polysilsesquioxane and plasticizer for 1-3 hours at 70-85 ℃ to obtain a prepolymer with the isocyanate group content of 7.0-18.0 wt%, thus obtaining a component A;
(2) The component B is obtained by vacuum dehydration of the formula amount of chain extender, polyoxypropylene ether polyol, reactive flame retardant polyether polyol, heat conducting filler, defoamer polyether polyol, catalyst and antioxidant at 100-110 ℃ and below-0.095 MPa until the water content is less than 0.03%;
(3) A, B components are mixed according to the weight ratio of 100:90-120, casting the mixture into a mold with the temperature of 30-35 ℃ for reaction at the temperature of 30-40 ℃ and curing at room temperature to obtain the reactive flame-retardant heat-conducting polyurethane electronic pouring sealant.
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