Halogenated polyphosphoric acid ester polyol, prepolymer, method for producing the same, and polyurea elastomer composition, polyurea elastomer and use thereof

Abstract

The present invention relates to the technical field of chemical materials, and discloses a halogenated polyphosphate ester polyol, a prepolymer and its preparation method, as well as a polyurea elastomer composition, a polyurea elastomer and its use. The structural unit of the halogenated polyphosphate ester polyol contains a halogenated phenyl phosphate group structure and one or more linking groups, the halogenated phenyl phosphate group has a structure represented by formula (1), and the linking group has a structure represented by formula (2). [Formula 1] JPEG2024535443000030.jpg71169 (n is 1 to 10, R 1 is a substituted or unsubstituted benzene ring, -C(O)-R 2 -C(O)-, substituted or unsubstituted alkenylene, R 2 is a substituted or unsubstituted C 1 ~C 9 is one or more selected from the group consisting of linear or branched alkylene, substituted or unsubstituted benzene ring, and substituted or unsubstituted alkenylene; 1 , X 2 , X 3 , X 4 and X 5 are the same or different, each being H and / or halogen, and not being H at the same time.

Description

Detailed Description of the Invention

[0001] [Cross - reference to Related Applications] This application claims the benefit of Chinese Patent Applications 202111151784.4, 202111151790.X, and 202111154238.6, filed on September 29, 2021, the contents of which are incorporated herein by reference.

[0002] [Technical Field] The present invention relates to the technical field of chemical materials, and specifically relates to halogenated polyphosphoric acid ester polyols, prepolymers and their manufacturing methods, as well as polyurea elastomer compositions, polyurea elastomers and their uses.

[0003] [Background Art] Polyurea elastomer (abbreviated as PUA) is a polymer produced by the reaction of an isocyanate - terminated prepolymer (Component A) and an amino compound component (Component R). PUA is excellent in strength and elasticity, and also excellent in water resistance, chemical resistance, and aging resistance, and is widely used in fields such as aerospace, military products, and petrochemicals. However, PUA is generally a flammable organic polymer material with an oxygen index (LOI) of 16 - 18%, and it is very flammable when exposed to an open flame. Therefore, the flame - retardant properties of PUA materials are an important factor restricting their development.

[0004] In recent years, scientific researchers have conducted a lot of research on the flame - retardant modification of PUA. Generally, conventional flame - retardant modifications are used to improve the flame - retardant properties of PUA materials by adding a large amount of inorganic flame retardants such as antimony trioxide, magnesium hydroxide, and aluminum hydroxide. However, the addition amount of this inorganic flame retardant is large, its dispersibility in PUA materials is poor, and the mechanical properties of the materials are significantly reduced. Conventional organic flame retardants such as pentabromodiphenyl ether, triphenyl phosphate, and ammonium polyphosphate have good dispersibility in PUA materials, but are easy to leak and lose, resulting in a decrease in the flame - retardant properties of the materials and environmental pollution.

[0005] CN104130685A discloses a reactive non-halogen flame-retardant spray polyurethane elastomer paint and its manufacturing method. In this paint, phosphate polyols of industrial products such as tris(dipropylene glycol) phosphite, diethyl-N,N-bis(2-hydroxyethyl) aminomethyl phosphate, and dimethyl-N,N-bis(2-hydroxyethyl) aminomethyl phosphate are used. Such conventional phosphate flame retardants have a large usage amount. In that application, to exhibit an excellent flame-retardant effect, the usage amount is 40%.

[0006] CN111499834A discloses a flame-retardant polyurethane explosion-proof protection material and its manufacturing method. As a composite flame retardant, a mixture of an additive organic phosphate ester-based flame retardant and a reactive non-halogen phosphorus-containing polyol is used. The additive organic phosphate ester-based flame retardant is one or two of dimethyl methyl phosphate, diethyl ethyl phosphate, dimethyl propyl phosphate, triethyl phosphate, phthalic anhydride ester, and tris(butoxyethyl) phosphate. The reactive non-halogen phosphorus-containing polyol is one or two of tris(dipropylene glycol) phosphite, diethyl-N,N-bis(2-hydroxyethyl) aminomethyl phosphate, and dimethyl-N,N-bis(2-hydroxyethyl) aminomethyl phosphate. This composite flame retardant has a large usage amount and the flame-retardant effect is not ideal.

[0007] CN106117501A discloses a flame-retardant polyurethane polyol and its manufacturing method. A polyurethane-type polyol is synthesized using isocyanate, hydrazine hydrate, and polyether polyol. It has good self-extinguishing characteristics when removed from fire, but there is no data regarding its application to polyurethane materials.

[0008] CN111218199A discloses a spray polyurethane waterproof and anticorrosive material with an inherent flame-retardant structure and its manufacturing method. The mass percentages of phthalic anhydride polyester polyol, nano-SiO2, and coupling agent in the composite flame retardant are 50 - 70%, 20 - 40%, and 1 - 3% respectively, which can achieve a better flame-retardant effect, but their usage amounts are large.

[0009] CN111171687A discloses a flame-retardant polyurethane paint and its manufacturing method. The flame retardant used is a selenium-containing triazine-based polymer flame retardant compound, and the flame-retardant grade may reach V-0 grade, but there is little research on the mechanical properties of the material.

[0010] Therefore, the research and development of flame-retardant polyurethane materials with higher mechanical properties and better flame retardancy have high research and application value.

[0011] [Summary of the Invention] [Problems to be Solved by the Invention] The object of the present invention is to solve the defect in the prior art that the flame retardancy of polyurethane materials is poor, and to provide a halogenated polyphosphoric acid ester polyol, a prepolymer and its manufacturing method, as well as a polyurethane elastomer composition, a polyurethane elastomer and its use. This polyurethane elastomer has high mechanical properties, excellent flame retardancy, and good comprehensive properties.

[0012] [Means for Solving the Problems] To achieve the above object, the first aspect of the present invention is A halogenated polyphosphoric acid ester polyol whose structural unit contains a halogenated phenyl phosphate group structure and one or more linking groups, The halogenated phenyl phosphate group has a structure represented by formula (1), The linking group has a structure represented by formula (2). [Chemical Formula] (Here, n is from 1 to 10, R1 is one or more of a substituted or unsubstituted benzene ring, -C(O)-R2-C(O)-, and a substituted or unsubstituted alkenylene, R2 is one or more selected from a substituted or unsubstituted C1-C9 linear or branched alkylene, a substituted or unsubstituted benzene ring, and a substituted or unsubstituted alkenylene, X1, X2, X3, X4, and X5 are the same or different, each being H and / or a halogen, and not being H simultaneously.)

[0013] The second aspect of the present invention provides a prepolymer containing a structural unit derived from the halogenated polyphosphate ester polyol.

[0014] The third aspect of the present invention is Step (D-1) of contacting the halogenated polyphosphate ester polyol with a polyether polyol to cause a dehydration reaction to obtain an intermediate product, and Step (D-2) of contacting the intermediate product with an isocyanate for prepolymerization to obtain a prepolymer, and provides a method for producing a prepolymer.

[0015] The fourth aspect of the present invention is a halogenated polyphosphate ester polyurethane elastomer composition containing component A and component B, wherein component A is the prepolymer, and component B is a halogenated polyphosphate ester polyurethane elastomer composition containing an amino-terminated polyether, an organosilane, and a chain extender.

[0016] The fifth aspect of the present invention provides a polyurethane elastomer having an oxygen index of 23% or more, a tensile strength of 18 MPa or more, and an elongation at break of 200% or more.

[0017] The sixth aspect of the present invention provides the use of the halogenated polyphosphate ester polyurethane elastomer in the fields of building waterproofing, structural reinforcement, or damping / vibration isolation.

[0018] [Advantages of the Invention] According to the above technical solution, the halogenated polyphosphoric acid ester polyurethane elastomer manufactured by the present invention contains a halogenated polyphosphoric acid ester-based polyol flame-retardant structure in its molecular chain structure, has high mechanical performance and flame retardancy, a tensile strength of 18 MPa or more, an elongation at break of 200% or more, does not require the addition of an additional flame retardant, and an oxygen index of 23% or more.

[0019] [Brief Description of the Drawings] [Fig. 1] Infrared spectrum of the halogenated polyphosphoric acid ester polyurethane elastomer manufactured in Example 1. [Fig. 2] GPC spectrum of the halogenated polyphosphoric acid ester polyol manufactured in each of Example 1, Example 2, and Example 3. [Fig. 3] Infrared spectrum of the halogenated polyphosphoric acid ester polyol manufactured in each of Example 1, Example 2, and Example 3. [Fig. 4] Digital photograph of the halogenated polyphosphoric acid ester polyurethane elastomer manufactured in Example 3. [Fig. 5] Schematic diagram of the tensile performance curve of the halogenated polyphosphoric acid ester polyurethane elastomer manufactured in Examples 1 to 3. [Fig. 6] Schematic diagram of the comparison of the combustion of the halogenated polyphosphoric acid ester polyurethane elastomer manufactured in Example 1 of the present invention and the polyurethane elastomer manufactured in Comparative Example 1.

[0020] [Modes for Carrying Out the Invention] The endpoints and any values within the ranges disclosed in this specification are not limited to the exact ranges or values, and should be understood to include values close to these ranges or values. In the case of numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this specification.

[0021] The first aspect of the present invention contains a halogenated phenyl phosphate group structure and one or more linking groups as structural units, The phenyl phosphate halide group has a structure represented by formula (1), The linking group has a structure represented by formula (2), and a halogenated polyphosphoric ester polyol is provided.

Chemical formula

[0022] According to the present invention, the linking group has a structure represented by formula (3). -O-R3-O-C(O)-R2-C(O)-O-R3-O- Formula (3) (where R2 is an alkylene having 2 to 6 carbon atoms containing a carbon-carbon double bond, preferably

Chemical formula

Chemical formula

[0023] According to the present invention, preferably, the linking group represented by formula (3) is one or more selected from the structures represented by formula (4) or formula (5), [Chemical formula] Here, X and X' are the same or different, each being an atom of H and / or a halogen and not being H at the same time.)

[0024] According to the present invention, preferably, X and X' are each a bromine, chlorine, iodine, or fluorine atom.

[0025] In addition, in the present invention, when m = 1, it is a special case, and an oligomer can be obtained under polymerization conditions.

[0026] According to the present invention, preferably, the alkylene is a linear or branched C1-C7 alkylene, and more preferably, the alkylene is a linear or branched C1-C6 alkylene.

[0027] According to the present invention, more preferably, the halogenated polyphosphate ester polyol contains one or more of the structural units represented by formula (6) and formula (7). [Chemical formula] (Here, X and X' are the same or different, each being an atom of H and / or a halogen and not being H at the same time.)

[0028] According to the present invention, preferably, X and X' are each a bromine, chlorine, iodine, or fluorine atom.

[0029] According to the present invention, even more preferably, the halogenated polyphosphate ester polyol contains one or more of the structural units represented by formula (8)-(12). [Chemical formula]

[0030] According to the present invention, in the halogenated polyphosphoric acid ester polyol, the number average molecular weight is 1000 to 50000, preferably 1000 to 48000, and the hydroxyl value is 2.5 to 115 mg KOH / g, preferably 2.8 to 112 mg KOH / g.

[0031] In the present invention, in a preferred specific embodiment according to the present invention, the method for producing a halogenated polyphosphoric acid ester polyol is Stannous octanoate C 16 H 30 In the presence of O4Sn and dichloroethane C2H4Cl2, phosphorus oxychloride POCl3 and a halogenated phenol represented by the formula (13) are brought into contact to carry out a first reaction to obtain phenylphosphoric acid as an intermediate product represented by the formula (14) in step (1-1); The dichloroethane C2H4Cl2 solution containing the phenylphosphoric acid is dropped into a mixed solution containing a diol represented by the formula (15), dichloroethane and triethylamine C6H4N to carry out a second reaction, and then washing, drying and filtration treatments are carried out to obtain a halogenated polyphosphoric acid ester polyol represented by the formula (16) in step (1-2).

Chemical formula

Chemical formula

[0032] According to the present invention, since the linking group is consistent with the description of the structure represented by the formula (3), it will not be described in detail here.

[0033] In a more preferred specific embodiment according to the present invention, the method for producing the halogenated polyphosphate polyol is performing a first reaction by bringing phosphorus oxychloride, dichloroethane, stannous octoate, and halogenated phenol into contact to obtain phenylphosphoric acid as an intermediate product in step (1-1); performing a second reaction by dropping the dichloroethane solution containing phenylphosphoric acid into a mixed solution containing diol, dichloroethane, and triethylamine, and then performing washing, drying, and filtration treatments to obtain a halogenated polyphosphate polyol in step (1-2).

Chemical formula

[0034] In the present invention, stannous octoate is a catalyst, phosphorus oxychloride and halogenated phenol are reactants, dichloroethane is a solvent, and phosphorus oxychloride and halogenated phenol perform the first reaction to produce phenylphosphoric acid as an intermediate product. Phenylphosphoric acid and diol perform the second reaction to produce a halogenated polyphosphate polyol (polyphosphate ester).

[0035] According to the present invention, the halogenated phenol is one or more selected from p-bromophenol, dibromophenol, tribromophenol, tetrabromophenol, pentabromophenol, trichlorophenol, pentachlorophenol, trifluorophenol, and triiodophenol, and preferably, the halogenated phenol is one or more selected from p-bromophenol, tribromophenol, and pentabromophenol.

[0036] According to the present invention, the diol is one or more selected from ethylene glycol, propylene glycol, butanediol, pentylene glycol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, ethylene glycol maleate polyol, ethylene terephthalate polyol, ethylene glycol dichloromaleate polyol, and ethylene tetrachloroterephthalate polyol. Preferably, the diol is one or more selected from ethylene glycol, butanediol, hexanediol, ethylene glycol maleate polyol, ethylene terephthalate polyol, ethylene glycol dichloromaleate polyol, and ethylene tetrachloroterephthalate polyol.

[0037] According to the present invention, the molar ratio of the usage amounts of phosphorus oxychloride, the halogenated phenol, the diol, and the triethylamine is 1:(0.8 - 1.0):(2.0 - 2.2):(0.8 - 1.2).

[0038] According to the present invention, based on the usage amount of the halogenated phenol, the usage amount of stannous octoate is 0.1 - 0.5% by weight.

[0039] According to the present invention, in step (1 - 1), the usage amount of dichloroethane is not particularly limited. In the present invention, it is only necessary to dissolve the reactants, phosphorus oxychloride and the halogenated phenol. In step (1 - 2), the usage amount of dichloroethane in the dichloroethane solution containing the intermediate product is not particularly limited. In the present invention, it is only necessary to dissolve the intermediate product. In step (1 - 2), the usage amount of dichloroethane in the mixed solution containing the diol, dichloroethane and triethylamine is not particularly limited. In the present invention, preferably, the volume ratio of the usage amounts of dichloroethane and the diol may be 1:(1 - 2).

[0040] According to the present invention, triethylamine is a pH adjuster and may be maintained at neutral.

[0041] According to the present invention, in step (1-2), the conditions for the dropping are 1 to 2 drops per second. In the present invention, emphasizing the dropping is for better controlling the heat release of the reaction.

[0042] According to the present invention, in step (1), the conditions for the first reaction include a temperature of 0 to 20°C and a time of 1 to 24 hours, preferably a temperature of 0 to 20°C and a time of 2 to 8 hours.

[0043] According to the present invention, in step (2), the conditions for the second reaction include a temperature of 0 to 20°C and a time of 1 to 24 hours, preferably a temperature of 0 to 20°C and a time of 2 to 16 hours.

[0044] In a more preferred specific embodiment according to the present invention, the method for producing the halogenated polyphosphoric acid ester polyol is as follows: Add phosphorus oxychloride, dichloroethane, and stannous octoate to a reaction kettle, and under the conditions of 0 to 20°C and nitrogen, drop halogenated phenol at 1 to 2 drops per second. After reacting for 2 to 8 hours, suction-dry the reaction solvent to obtain an intermediate product in step (1-1); Add diol, dichloroethane, and triethylamine to a reaction kettle, and under the conditions of 0 to 20°C and nitrogen, drop a dichloroethane solution of the intermediate product at 1 to 2 drops per second. After the dropping is completed, raise the temperature and reflux for 8 hours. Add a 2 mol / L dilute hydrochloric acid solution and a saturated sodium chloride aqueous solution to wash until neutral, dry with anhydrous magnesium sulfate, filter, and suction-filter the solvent to obtain the halogenated polyphosphoric acid ester polyol in step (1-2).

[0045] The second aspect of the present invention provides a prepolymer containing a structural unit based on the halogenated polyphosphoric acid ester polyol.

[0046] According to the present invention, the number average molecular weight of the prepolymer is 1500 to 50000.

[0047] According to the present invention, the prepolymer is obtained by prepolymerizing a halogenated polyphosphate ester polyol, a polyether polyol, and an isocyanate. Preferably, the content of NCO in the prepolymer is 10 to 20% by weight, preferably 13 to 20% by weight.

[0048] According to the present invention, preferably, based on the total weight of the prepolymer, the content of the isocyanate is 20 to 70% by weight, the content of the polyether polyol is 20 to 70% by weight, and the content of the halogenated polyphosphate ester polyol is 5 to 20% by weight. Preferably, based on the total weight of the component A, the content of the isocyanate is 25 to 65% by weight, the content of the polyether polyol is 25 to 55% by weight, and the content of the halogenated polyphosphate ester polyol is 5 to 20% by weight. More preferably, based on the total weight of the prepolymer, the content of the isocyanate is 30 to 60% by weight, the content of the polyether polyol is 25 to 30% by weight, and the content of the halogenated polyphosphate ester polyol is 10 to 20% by weight.

[0049] A third aspect of the present invention is Step (D-1) of bringing the halogenated polyphosphate ester polyol into contact with the polyether polyol to cause a dehydration reaction to obtain an intermediate product; Step (D-2) of bringing the intermediate product into contact with an isocyanate to perform prepolymerization to obtain a prepolymer, and provides a method for producing a prepolymer.

[0050] The inventors of the present invention have produced a halogenated polyphosphate ester polyol by using a halogen-containing functional group-modified polyphosphate ester. As a result, this polyphosphate ester polyol has flame retardancy due to halogen in addition to the dehydration flame retardant effect by the phosphate ester. Preferably, the hydroxy groups of the halogenated polyphosphate ester polyol segment retain the prepolymerization activity with isocyanate. Therefore, by prepolymerizing such a halogenated polyphosphate ester polyol, a polyether polyol, and an isocyanate, it has been found that the produced halogenated polyphosphate ester polyurethane elastomer can improve the flame retardant performance while maintaining good mechanical properties.

[0051] According to the present invention, the conditions for the dehydration reaction include a temperature of 60 to 120°C and a time of 0.5 to 1.5 h. Preferably, the halogenated polyphosphate ester polyol and the polyether polyol are dehydrated in advance, dehydrated under vacuum conditions at 60 to 120°C for 0.5 to 1.5 h, then cooled to 40 to 60°C, and later used for the defoaming reaction with isocyanate.

[0052] According to the present invention, the conditions for the prepolymerization include a temperature of 40 to 90°C and a time of 1 to 3 h, preferably a temperature of 60 to 80°C and a time of 1 to 2 h.

[0053] According to the present invention, based on the total weight of the prepolymer, the amount of the isocyanate used is 20 to 70% by weight, the amount of the polyether polyol used is 20 to 70% by weight, and the amount of the halogenated polyphosphate ester polyol used is 5 to 20% by weight. Preferably, based on the total weight of component A, the amount of the isocyanate used is 25 to 65% by weight, the amount of the polyether polyol used is 25 to 55% by weight, and the amount of the halogenated polyphosphate ester polyol used is 5 to 20% by weight. More preferably, based on the total weight of the prepolymer, the amount of the isocyanate used is 30 to 60% by weight, the amount of the polyether polyol used is 25 to 30% by weight, and the amount of the halogenated polyphosphate ester polyol used is 10 to 20% by weight.

[0054] A fourth aspect of the present invention provides a halogenated polyphosphate ester polyurethane elastomer composition containing component A and component B, wherein component A is the prepolymer, and component B contains an amino-terminated polyether, an organosilane, and a chain extender.

[0055] According to the present invention, in terms of the isocyanate index, the ratio of component A to component B is (1 to 1.2):1, preferably (1 to 1.05):1.

[0056] In addition, according to the present invention, the "isocyanate index" means the molar ratio of isocyanate to amino.

[0057] According to the present invention, the halogenated polyphosphate ester polyurethane elastomer includes an isocyanate structural unit represented by formula (17) by isocyanate and a halogenated polyphosphate ester polyol structural unit by the halogenated polyphosphate ester polyol, [Chemical formula] (wherein R 10 is an aromatic or aliphatic isocyanate residue.)

[0058] According to the present invention, based on the total weight of the component A, the content of the isocyanate is 20 to 70% by weight, the content of the polyether polyol is 20 to 70% by weight, and the content of the halogenated polyphosphate ester polyol is 5 to 20% by weight. Preferably, based on the total weight of the component A, the usage amount of the isocyanate is 25 to 65% by weight, the usage amount of the polyether polyol is 25 to 55% by weight, and the usage amount of the halogenated polyphosphate ester polyol is 5 to 20% by weight. More preferably, based on the total weight of the prepolymer, the content of the isocyanate is 30 to 60% by weight, the content of the polyether polyol is 25 to 30% by weight, and the usage amount of the halogenated polyphosphate ester polyol is 10 to 20% by weight.

[0059] According to the present invention, based on the total weight of the component B, the content of the amino-terminated polyether is 18 to 80% by weight, the content of the organosilane is 0.2 to 2% by weight, and the content of the chain extender is 20 to 35% by weight. Preferably, based on the total weight of the component B, the content of the amino-terminated polyether is 24 to 65% by weight, the content of the organosilane is 0.2 to 1% by weight, and the content of the chain extender is 20 to 30% by weight.

[0060] According to the present invention, the isocyanate is one or more selected from toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, polymethylene polyphenyl polyisocyanate, liquefied diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, cyclohexane dimethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

[0061] According to the present invention, the polyether polyol is one or more selected from polytetrahydrofuran diol, polyoxypropylene ether polyol, polyoxyethylene polyol, hydroxy-terminated polybutadiene, polypropylene glycol, polyethylene glycol, fatty acid triglyceride, polycaprolactone polyol, polycarbonate diol, and 1,4-butanediol.

[0062] According to the present invention, the amino-terminated polyether is one or more selected from amino-terminated polyether T5000, T3000, T403, D4000, D2000, D400, and D230.

[0063] According to the present invention, the chain extender is one or more selected from diethyltoluenediamine, dimethylthiotoluenediamine, N,N-dialkylmethyldiamine, N,N-dialkylphenylenediamine, and isophoronediamine.

[0064] According to the present invention, the organosilane is one or more selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2,3-epoxy)propyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane, and preferably, the organosilane is one or more selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-(2,3-epoxy)propyltrimethoxysilane. In the present invention, using the organosilane has the effect of improving the interfacial wettability of the material. Also, adding the organosilane to component B instead of adding it during the production of component A is for improving the interfacial performance between the material and the substrate.

[0065] The fifth aspect of the present invention provides a polyurea elastomer having an oxygen index of 23% or more, a tensile strength of 18 MPa or more, and an elongation at break of 200% or more. Preferably, the oxygen index is 23 to 28%, the tensile strength is 18 to 30 MPa, and the elongation at break is 280 to 400%.

[0066] According to the present invention, step (1) of preliminarily polymerizing by bringing a halogenated polyphosphate ester polyol, a polyether polyol, an optional diluent, and an isocyanate into contact to obtain component A; step (2) of carrying out a polymerization reaction by bringing the component A into contact with the component B containing an amino-terminated polyether, an organosilane, and a chain extender at an isocyanate index of (1 to 1.2):1. Further provided is a method for producing a halogenated polyphosphate ester polyurea elastomer including these steps.

[0067] According to the present invention, preferably, the component A further contains a diluent, and based on the total weight of the component A, the usage amount of the diluent is 0 to 15% by weight, preferably 2 to 12% by weight.

[0068] According to the present invention, based on the total weight of the component A, the usage amount of the isocyanate is 20 to 70% by weight, the usage amount of the polyether polyol is 20 to 70% by weight, the usage amount of the halogenated polyphosphate ester polyol is 5 to 20% by weight, and the usage amount of the diluent is 0 to 15% by weight. Preferably, based on the total weight of the component A, the usage amount of the isocyanate is 25 to 65% by weight, the usage amount of the polyether polyol is 25 to 55% by weight, the usage amount of the halogenated polyphosphate ester polyol is 5 to 20% by weight, and the usage amount of the diluent is 2 to 12% by weight. More preferably, based on the total weight of the component A, the usage amount of the isocyanate is 30 to 60% by weight, the usage amount of the polyether polyol is 25 to 30% by weight, the usage amount of the halogenated polyphosphate ester polyol is 10 to 20% by weight, and the usage amount of the diluent is 2 to 12% by weight. In the present invention, limiting the usage amount of each component within the aforementioned range has the advantage that the material maintains both mechanical properties and flame retardancy.

[0069] According to the present invention, the component A is a prepolymer. In the present invention, the component A has a number average molecular weight of 1500 to 50000, and the NCO content in the component A is 10 to 20% by weight, preferably 12 to 20% by weight.

[0070] According to the present invention, the diluent is one or more selected from toluene diphenyl phosphate, 2-ethylhexyl diphenyl ester, propylene carbonate, ethyl carbonate, dibutyl phthalate, 2-chloroethyl ester, and acetone.

[0071] According to the present invention, the component B further includes a filler and an auxiliary agent.

[0072] According to the present invention, the filler is one or more selected from bentonite, montmorillonite, calcium carbonate, silica, carbon nanotubes, graphene, carbon fiber, glass fiber, aluminum hydroxide, magnesium hydroxide, and cellulose. Preferably, the filler is one or more selected from montmorillonite, silica, carbon nanotubes, aluminum hydroxide, and magnesium hydroxide.

[0073] According to the present invention, the auxiliary agent is one or more selected from a colorant, an ultraviolet absorber, a leveling agent, an antifoaming agent, a diluent, and a dispersant. The colorant is a white paste and / or a black paste manufactured by Xin Nuo An Co., Ltd. The ultraviolet absorber is an ultraviolet inhibitor HM. The leveling agent is a BYK leveling agent. The antifoaming agent is a BYK antifoaming agent. The dispersant is a BYK dispersant. The diluent is propylene carbonate.

[0074] According to the present invention, based on the total weight of component B, the usage amount of the amino-terminated polyether is 18 to 80% by weight, the usage amount of the chain extender is 20 to 35% by weight, and the usage amount of the organosilane is 0.2 to 2% by weight. Preferably, based on the total weight of component B, the usage amount of the amino-terminated polyether is 24 to 65% by weight, the usage amount of the chain extender is 20 to 30% by weight, and the usage amount of the organosilane is 0.2 to 1% by weight.

[0075] According to the present invention, based on the total weight of component B, the usage amount of the filler is 1 to 30% by weight, and the usage amount of the auxiliary agent is 5 to 15% by weight. Preferably, based on the total weight of component B, the usage amount of the filler is 5 to 30% by weight, and the usage amount of the auxiliary agent is 5 to 15% by weight.

[0076] In the present invention, limiting the usage amounts of the respective components within the aforementioned ranges has the advantage that the manufactured polyurethane material is excellent in mechanical properties and flame retardancy.

[0077] According to the present invention, in terms of the isocyanate index, the ratio of the component A to the component B is (1 to 1.2):1, preferably (1 to 1.05):1.

[0078] According to the present invention, since the isocyanate, the halogenated polyphosphoric acid ester polyol, the polyether polyol, any diluent, the amino-terminated polyether, the chain extender, and the organosilane are the same as those described above, they will not be described in detail here.

[0079] According to the present invention, in step (1), the conditions for the prepolymerization include a temperature of 40 to 90°C and a time of 1 to 3 h, preferably a temperature of 60 to 80°C and a time of 1 to 2 h.

[0080] According to the present invention, preferably, the halogenated polyphosphoric acid ester polyol and the polyether polyol are dehydrated in advance and dehydrated under vacuum conditions at 60 to 120°C for 0.5 to 1.5 h. In the present invention, after the defoaming reaction is completed, a temperature reduction treatment is performed, preferably reducing the temperature to 40 to 60°C for use in the subsequent defoaming reaction with isocyanate.

[0081] According to the present invention, preferably, in step (2), the conditions for the contact include a stirring speed of 1000 to 2000 rpm, a temperature of 25 to 60°C, and a time of 30 to 120 min, preferably a stirring speed of 1000 to 1500 rpm, a temperature of 30 to 60°C, and a time of 60 to 80 min.

[0082] According to the present invention, preferably, in step (2), the conditions for the polymerization reaction include a temperature of 60 to 75°C, that is, including performing the polymerization reaction while mixing, preferably at a temperature of 65 to 70°C. In the present invention, spraying is performed using a two-component spray gun, and the amino-terminated polyether participates in the mixed curing reaction of the component A and the component B, and the component A and the component B are mixed and then cured like a two-component adhesive.

[0083] In a preferred specific embodiment according to the present invention, the method for producing the halogenated polyphosphoric acid ester polyurethane elastomer includes the following. (1) Production of component A Add polyether (ester) polyol and halogenated polyphosphate ester polyol into a reaction kettle, dehydrate under vacuum conditions at 60 - 120 °C for 0.5 - 1.5 h, then cool down to 40 - 60 °C, add the corresponding proportion of the isocyanate into the reaction kettle, heat up to 60 - 80 °C, keep warm for 1 - 2 h for reaction, after defoaming, cool down to obtain Component A with an NCO% content of 12 - 20%. Based on the total weight of Component A, the usage amount of the isocyanate is 30 - 60% by weight, the usage amount of the polyether (ester) polyol is 25 - 30% by weight, and the usage amount of the halogenated polyphosphate ester polyol is 10 - 20% by weight. (2) Production of Component B As raw materials, 24 - 65% by mass of amino - terminated polyether, 20 - 30% by mass of chain extender, 5 - 30% by mass of filler, 0.2 - 1% by mass of organosilane, and 5 - 15% by mass of other auxiliaries are put into a reaction kettle, heated up to 30 - 60 °C, stirred for 60 - 80 min under nitrogen conditions to obtain Component B. (3) Production of polyurea material Spray Component A and Component B so that the isocyanate index is 1 - 1.05 to obtain a polyurea material.

[0084] The sixth aspect of the present invention provides the use of the halogenated polyphosphate ester polyurea elastomer in the fields of building waterproofing, structural reinforcement, or damping and vibration control.

[0085] According to the present invention, the building waterproofing includes building roof waterproofing paint and water storage tank waterproofing paint.

[0086] According to the present invention, the structural reinforcement includes building repair paint and wall reinforcement paint.

[0087] According to the present invention, the damping and vibration control includes vibration - damping paint and sound - absorbing paint.

[0088] Hereinafter, the present invention will be described in detail by way of examples.

[0089] Hereinafter, in the examples and comparative examples, (1) Performance test Number average molecular weight test: For the room temperature GPC test, it was measured using a GPC-2414 gel permeation chromatograph manufactured by Waters. The test temperature was 30 °C, tetrahydrofuran was used as the mobile phase solvent, the liquid flow rate was 1.0 ml / min, and the molecular weight was calibrated using a polystyrene standard sample; Hydroxyl value test: Measured by the standard phthalic anhydride-pyridine reflux method. (2) Derived from raw materials Diphenylmethane-4,4'-diisocyanate and toluene diisocyanate raw materials are commercially available products with the trade names MDI-50 and TDI-80 manufactured by Wanhua Chemical Company. Amino-terminated polyether raw materials are commercially available products with the trade names D2000, T5000, and D400 manufactured by Huntsman. Polyoxypropylene ether polyol, polytetrahydrofuran diol, polycaprolactone diol, halogenated phenol, stannous octoate, small molecule diol, phosphorus oxychloride, and silane raw materials are commercially available products manufactured by Maclean Chemical Reagent Company. In the following examples and comparative examples, unless otherwise specified, % represents weight %. Example 1

[0090] In this example, the halogenated polyphosphate ester polyurethane elastomer produced by the method of the present invention will be described. (1) Production of halogenated polyphosphate ester polyol 1) 0.1 mol of phosphorus oxychloride, 60 ml of dichloroethane, and 0.1 g of stannous octoate were added to a three-necked flask. Under the conditions of 0 °C and nitrogen, 40 ml of a dichloroethane solution of 0.1 mol of pentabromophenol was added dropwise at a rate of 1-2 drops / second. After reacting for 4 h, the reaction solvent was suction-dried to obtain an intermediate product P1. 2) 0.22 mol of ethylene glycol maleate polyol, 100 ml of dichloroethane, and 0.1 mol of triethylamine were added to a three-necked flask. Under the conditions of 0 °C and nitrogen, 50 ml of a dichloroethane solution of P1 was added dropwise at a rate of 1-2 drops / second. 3) After the dropping was completed, the temperature was raised and refluxed for 8 h. Dilute hydrochloric acid solution of 2 mol / L and saturated sodium chloride aqueous solution were added for washing until neutral, dried over anhydrous magnesium sulfate, filtered, and the solvent was suction filtered to obtain halogenated polyphosphoric acid ester polyol PO1. Figure 3 is the infrared spectrum of the halogenated polyphosphoric acid ester polyol produced in Example 1. Clearly from Figure 3, the infrared spectrum of the resulting halogenated polyphosphoric acid ester polyol PO1 is shown in Figure 3. As can be seen from Figure 3, the infrared spectrum of the halogenated polyphosphoric acid ester polyol of Example 1 has an infrared absorption peak of phosphate ester (1257 cm -1 ), an infrared absorption peak of double bond (1726 cm -1 ), and an absorption peak of benzene ring (1624 cm -1 ). The GPC spectrum of the resulting halogenated polyphosphoric acid ester polyol PO1 is shown in Figure 2. As can be seen from Figure 2, the halogenated polyphosphoric acid ester polyol of Example 1 is a high molecular weight polymer with a unimodal distribution. The halogenated polyphosphoric acid ester polyol PO1 has a number average molecular weight of 3000 and a hydroxyl value of 36 mg KOH / g. From the infrared spectrum and the raw materials and reaction conditions, it was found that the halogenated polyphosphoric acid ester polyol PO1 has the following structural formula.

Chemical formula

Chemical formula

[0091] In this example, a halogenated polyphosphoric acid ester polyurea elastomer produced by the method of the present invention will be described. (1) Production of Halogenated Polyphosphoric Acid Ester Polyol 1) 0.1 mol of phosphorus oxychloride, 60 ml of dichloroethane, and 0.1 g of stannous octoate were added to a three-necked flask, and under the conditions of 0 °C and nitrogen, a 40 ml dichloroethane solution of 0.1 mol of p-chlorophenol was dropped at 1 - 2 drops / second, and after reacting for 4 h, the reaction solvent was suction-dried to obtain an intermediate product P2. (2) 0.25 mol of ethylene tetrachloroterephthalate, 100 ml of dichloroethane, and 0.1 mol of triethylamine were added to a three-necked flask, and 50 ml of a dichloroethane solution of P2 was added dropwise at 0 °C under nitrogen conditions at a rate of 1 - 2 drops / second. (3) After completion of the dropwise addition, the temperature was raised and refluxed for 8 h, washed with a 2 mol / L dilute hydrochloric acid solution and a saturated sodium chloride aqueous solution until neutral, dried over anhydrous magnesium sulfate, filtered, and the solvent was suction filtered to obtain a halogenated polyphosphoric acid ester polyol PO2. Figure 3 is the infrared spectrum of the halogenated polyphosphoric acid ester polyol produced in Example 2. As can be seen from Figure 3, the halogenated polyphosphoric acid ester polyol of Example 2 has an infrared absorption peak of phosphate ester (1250 cm -1 ) and an absorption peak of the benzene ring (1630 cm -1 ). The GPC spectrum of the resulting halogenated polyphosphoric acid ester polyol PO2 is shown in Figure 2. As can be seen from Figure 2, the halogenated polyphosphoric acid ester polyol of Example 2 is a high molecular weight polymer with a unimodal distribution, and the halogenated polyphosphoric acid ester polyol PO2 has a number average molecular weight of 48000 and a hydroxyl value of 2.8 mg KOH / g. From the infrared spectrum and the raw materials and reaction conditions, it was found that the halogenated polyphosphoric acid ester polyol PO2 has the following structural formula. [Chemical formula] (2) Production of Component A Polyoxypropylene ether polyol and halogenated polyphosphoric acid ester polyol were added to a reaction kettle, dehydrated at 100 °C for 1 h, and toluene diisocyanate was added under the condition of 40 °C, reacted at 70 °C for 2 h, stirred uniformly, then the temperature was lowered, dibutyl phthalate was added to obtain prepolymer A2, and it was used as Component A with an NCO% of 13%. The structural units of the resulting prepolymer A2 are as follows. [Chemical formula] The number average molecular weight of the prepolymer A2 is 50,000. Component A: 54% by weight of polyoxypropylene ether polyol (8200), 16% by weight of halogenated polyphosphoric acid ester polyol PO2, 20% by weight of dicyclohexylmethane diisocyanate, 10% by weight of dibutyl phthalate. (3) Production of Component B: An amino-terminated polyether, isophoronediamine, mercaptopropyltrimethoxysilane, magnesium hydroxide, montmorillonite, carbon nanotubes, and other auxiliaries were added to a reaction kettle, heated to 30 °C under nitrogen conditions, and stirred for 60 min, and then taken out as Component B. Formulation of Component B: 31% by weight of amino-terminated polyether (D400), 30% by weight of amino-terminated polyether (T403), 20% by weight of isophoronediamine, 1% by weight of mercaptopropyltrimethoxysilane, 10% by weight of magnesium hydroxide, 2.5% by weight of montmorillonite, 0.5% by weight of carbon nanotubes, 5% by weight of other auxiliaries (specifically, 1% by weight of color paste manufactured by Xin Nuo An Co., 2% by weight of ultraviolet absorber HM, 2% by weight of BYK defoamer). (4) Production of halogenated polyphosphoric acid ester polyurethanelastomer Using a two-component high-pressure spray gun, at a temperature of 75 °C, Component A and Component B were sprayed onto the surface of a polytetrafluoroethylene plate with a thickness of 2 mm so that the isocyanate index was 1.0, and then rapidly cured and molded to obtain a halogenated polyphosphoric acid ester polyurethanelastomer S2. Example 3

[0092] In this example, a halogenated polyphosphoric acid ester polyurethanelastomer produced by the method of the present invention will be described. (1) Production of halogenated polyphosphoric acid ester polyol 1) Add 0.1 mol of phosphorus oxychloride, 60 ml of dichloroethane, and 0.1 g of stannous octoate into a three-necked flask. Under the conditions of 0 °C and nitrogen, add 40 ml of a dichloroethane solution of 0.1 mol of p-fluorophenol dropwise at a rate of 1 - 2 drops / second. After reacting for 4 h, suction-dry the reaction solvent to obtain the intermediate product P3. 2) Add 0.28 mol of ethylene glycol dichloromaleate, 100 ml of dichloroethane, and 0.1 mol of triethylamine into a three-necked flask. Under the conditions of 0 °C and nitrogen, add 50 ml of a dichloroethane solution of P3 dropwise at a rate of 1 - 2 drops / second. 3) After the dropping is completed, raise the temperature and reflux for 8 h. Add a 2 mol / L dilute hydrochloric acid solution and a saturated sodium chloride aqueous solution to wash until neutral, dry with anhydrous magnesium sulfate, filter, and suction-filter the solvent to obtain the halogenated polyphosphoric acid ester polyol PO3. Also, Figure 3 is the infrared spectrum of the halogenated polyphosphoric acid ester polyol produced in Example 3. As can be seen from Figure 3, in the infrared spectrum of the halogenated polyphosphoric acid ester polyol produced in Example 3, the halogenated polyphosphoric acid ester polyol of Example 3 has an infrared absorption peak of phosphate ester (1254 cm -1 ), an infrared absorption peak of double bond (1726 cm -1 ), and an absorption peak of benzene ring (1631 cm -1 ). The GPC spectrum of the resulting halogenated polyphosphoric acid ester polyol PO3 is shown in Figure 2. As can be seen from Figure 2, the halogenated polyphosphoric acid ester polyol of Example 3 is a high molecular weight polymer with a unimodal distribution. The halogenated polyphosphoric acid ester polyol PO3 has a number average molecular weight of 1000 and a hydroxyl value of 111 mg KOH / g. From the infrared spectrum, raw materials, and reaction conditions, it was found that the halogenated polyphosphoric acid ester polyol PO3 has the following structural formula.

Chemical formula

Chemical formula

[0093] In this example, the halogenated polyphosphoric acid ester polyurea elastomer produced by the method of the present invention will be described. (1) Production of Halogenated Polyphosphoric Acid Ester Polyol 1) 0.1 mol of phosphorus oxychloride, 60 ml of dichloroethane, and 0.1 g of stannous octoate were added to a three-necked flask. Under the conditions of 0°C and nitrogen, 40 ml of a dichloromethane solution of 0.1 mol of 2,4,6-tribromophenol was added dropwise at a rate of 1-2 drops / second. After reacting for 4 h, the reaction solvent was suction-dried to obtain an intermediate product P5. 2) 0.22 mol of ethylene glycol maleate polyol, 100 ml of dichloroethane, and 0.1 mol of triethylamine were added to a three-necked flask. Under the conditions of 0°C and nitrogen, 50 ml of a dichloroethane solution of P5 was added dropwise at a rate of 1-2 drops / second. 3) After the dropping was completed, the temperature was raised and refluxed for 8 h. A 2 mol / L dilute hydrochloric acid solution and a saturated sodium chloride aqueous solution were added for washing until neutral, dried over anhydrous magnesium sulfate, filtered, and the solvent was suction-filtered to obtain a halogenated polyphosphoric acid ester polyol PO4. As a result, the halogenated polyphosphoric acid ester polyol PO4 had a number average molecular weight of 2000 and a hydroxyl value of 55 mg KOH / g. From the infrared spectrum and the raw materials and reaction conditions, it was found that the halogenated polyphosphoric acid ester polyol PO4 had the following structural formula. [Chemical formula] (2) Production of Component A Add polyoxypropylene ether polyol and halogenated polyphosphate ester polyol to a reaction kettle, dehydrate at 100 °C for 1.0 h, add toluene diisocyanate at 60 °C, react at 90 °C for 1.0 h, stir uniformly, then cool down to obtain prepolymer A4, and use it as component A with an NCO% of 18%. Moreover, the structural units of the obtained prepolymer A4 are as follows. [Chemical formula] The number average molecular weight of the prepolymer A4 is 3000. Component A: 28 wt% of polyoxypropylene ether polyol (1000), 10 wt% of halogenated polyphosphate ester polyol, 62 wt% of xylylene diisocyanate. (3) Production of component B Add amino-terminated polyether, diethyltoluenediamine, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, montmorillonite, calcium carbonate, glass fiber, aluminum hydroxide, and other auxiliaries to a reaction kettle, heat up to 60 °C under nitrogen conditions, stir for 60 min, and take it out as component B. Formulation of component B: 40 wt% of amino-terminated polyether (D2000), 9 wt% of amino-terminated polyether (T5000), 25 wt% of diethyltoluenediamine, 1 wt% of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 2 wt% of montmorillonite, 2 wt% of calcium carbonate, 1 wt% of glass fiber, 10 wt% of aluminum hydroxide, 10 wt% of other auxiliaries (specifically, 1 wt% of color paste manufactured by Xin Nuo An Co., 2 wt% of ultraviolet absorber HM, 2 wt% of BYK defoamer, 5 wt% of diluent propylene carbonate). (4) Production of halogenated polyphosphate ester polyurethanelastomer Using a two-component high-pressure spray gun, spray components A and B onto the surface of a polytetrafluoroethylene plate with a thickness of 2 mm at a temperature of 65 °C so that the isocyanate index is 1.1, and cure rapidly to form a halogenated polyphosphate ester polyurethanelastomer S4. Example 5

[0094] In this example, a halogenated polyphosphate ester polyurethane elastomer produced by the method of the present invention will be described. (1) Production of halogenated polyphosphate ester polyol 1) 0.1 mol of phosphorus oxychloride, 60 ml of dichloroethane, and 0.1 g of stannous octoate were added to a three-necked flask. Under the conditions of 0 °C and nitrogen, 40 ml of a dichloroethane solution of 0.1 mol of 3,5-dibromophenol was added dropwise at 1 - 2 drops / second. After reacting for 4 h, the reaction solvent was suction-dried to obtain an intermediate product P4. 2) 0.25 mol of ethylene glycol maleate, 100 ml of dichloroethane, and 0.1 mol of triethylamine were added to a three-necked flask. Under the conditions of 0 °C and nitrogen, 50 ml of a dichloroethane solution of P4 was added dropwise at 1 - 2 drops / second. 3) After the dropping was completed, the temperature was raised and refluxed for 8 h. A 2 mol / L dilute hydrochloric acid solution and a saturated sodium chloride aqueous solution were added and washed until neutral. It was dried over anhydrous magnesium sulfate, filtered, and the solvent was suction-filtered to obtain a halogenated polyphosphate ester polyol PO5. As a result, the halogenated polyphosphate ester polyol PO5 had a number average molecular weight of 1000 and a hydroxyl value of 112 mg KOH / g. From the infrared spectrum and the raw materials and reaction conditions, it was found that the halogenated polyphosphate ester polyol PO5 had the following structural formula. [Chemical formula] (2) Production of Component A Hydroxy-terminated polybutadiene and halogenated polyphosphate ester polyol were added to a reaction kettle and dehydrated at 100 °C for 1 h. Under the conditions of 40 °C, toluene diisocyanate was added and reacted at 80 °C for 2 h. After stirring uniformly, the temperature was lowered to obtain a prepolymer A5, which was used as Component A with an NCO% of 10%. Moreover, the structural units of the obtained prepolymer A5 are as follows. [Chemical formula] The number average molecular weight of the prepolymer A5 is 1600. Component A: 67% by weight of hydroxy-terminated polybutadiene (2000), 5% by weight of halogenated polyphosphate polyol, 28% by weight of toluene diisocyanate. (3) Production of Component B An amino-terminated polyether, N,N-dialkylphenylenediamine, 3-(methacryloyloxy)propyltrimethoxysilane, carbon nanotubes, carbon fibers, aluminum hydroxide, and other auxiliaries were added to a reaction kettle, heated to 60°C under nitrogen conditions, and stirred for 60 minutes, and then taken out as Component B. Component B: 40% by weight of amino-terminated polyether (D2000), 9% by weight of amino-terminated polyether (T3000), 25% by weight of N,N-dialkylphenylenediamine, 1% by weight of 3-(methacryloyloxy)propyltrimethoxysilane, 2% by weight of carbon nanotubes, 3% by weight of carbon fibers, 15% by weight of aluminum hydroxide, 5% by weight of other auxiliaries (specifically, 1% by weight of color paste manufactured by Xin Nuo'an Co., 2% by weight of ultraviolet absorber HM, 2% by weight of BYK defoamer). (4) Production of Halogenated Polyphosphate Polyurea Elastomer Using a two-component high-pressure spray gun, under the condition of a temperature of 65°C, Component A and Component B were sprayed on the surface of a polytetrafluoroethylene plate with a thickness of 2 mm so that the isocyanate index was 1.1, and then rapidly cured and molded to obtain a halogenated polyphosphate polyurea elastomer S5. Example 6

[0095] A polyurea elastomer was produced in the same manner as in Example 1 except for the following. For the production of Component A in step (2), the usage amounts of the respective components are as follows. 6% by weight of polytetrahydrofuran diol (PTMG-1000), 50% by weight of halogenated polyphosphate polyol PO1, 22% by weight of diphenylmethane-4,4'-diisocyanate, 20% by weight of ethyl carbonate. As a result, a halogenated polyphosphoric acid ester polyurea elastomer S6 was obtained. Example 7

[0096] A polyurea elastomer was produced in the same manner as in Example 1, except for the following. For the production of Component B in Step (3), As raw materials, 5% by weight of amino-terminated polyether (D2000), 80% by weight of diethyltoluenediamine, 0.2% of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 8% by weight of aluminum hydroxide, 1.8% by weight of silica, and 5% by weight of other auxiliaries were charged into a reaction kettle. As a result, a halogenated polyphosphoric acid ester polyurea elastomer S7 was obtained. Comparative Example 1

[0097] A polyurea elastomer was produced in the same manner as in Example 1, except that halogenated polyphosphoric acid ester polyol PO1 was not added. As a result, a polyurea elastomer DS1 was obtained. Comparative Example 2

[0098] A polyurea elastomer was produced in the same manner as in Example 2, except that halogenated polyphosphoric acid ester polyol PO2 was not added. As a result, a polyurea elastomer DS2 was obtained. Comparative Example 3

[0099] A polyurea elastomer was produced in the same manner as in Example 3, except that halogenated polyphosphoric acid ester polyol PO3 was not added. As a result, a polyurea elastomer DS3 was obtained. Comparative Example 4

[0100] A polyurea elastomer was produced in the same manner as in Example 4, except that halogenated polyphosphoric acid ester polyol PO4 was not added. As a result, a polyurea elastomer DS4 was obtained. Comparative Example 5

[0101] A polyurethane elastomer was produced in the same manner as in Example 5, except that halogenated polyphosphoric acid ester polyol PO5 was not added. As a result, a polyurethane elastomer DS5 was obtained. Comparative Example 6

[0102] A polyurethane elastomer was produced in the same manner as in Example 1, except that "halogenated polyphosphoric acid ester polyol" was changed to "tris(chloroisopropyl) phosphate" as a flame retardant additive in the production of Component A. As a result, a polyurethane elastomer DS6 was obtained. Test Example

[0103] Tensile property (tensile strength and elongation at break) test: GB / T528-2009; Oxygen index test: GB / T2406-2009; Precipitate content test: The test sample was placed in an ethanol solution, heated under reflux for 48 h, the sample was taken out and baked, and the change in the mass of the sample was measured. The properties of the polyurethane elastomers produced in Examples 1 to 7 and Comparative Examples 1 to 6 were tested by the above methods. The results are shown in Table 1.

[0104]

Table 1

[0105] As can be seen from the results in Table 1, the halogenated polyphosphoric acid ester polyurethane elastomers produced in Examples 1 to 5 by the production method of the present invention have good mechanical properties and a high oxygen index.

[0106] Further, FIG. 5 is a schematic diagram of the tensile performance curves of the halogenated polyphosphoric acid ester polyurethane elastomers produced in Examples 1 to 3. As can be seen from FIG. 5, the tensile strength of the materials in Examples 1 to 3 is all 25 MPa or more.

[0107] Figure 6 is a schematic diagram of the combustion comparison between the halogenated polyphosphoric acid ester polyurethane elastomer manufactured in Example 1 of the present invention and the polyurethane elastomer manufactured in Comparative Example 1. As can be seen from Figure 6, the halogenated polyphosphoric acid ester polyurethane elastomer S1 manufactured in Example 1 of the present invention does not burn and has flame retardancy. On the other hand, the polyurethane elastomer DS1 manufactured in Comparative Example 1 was shown to be burning and not have flame retardancy.

[0108] As described above, the preferred embodiments of the present invention have been described in detail, but the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including combining each technical feature in other appropriate ways. These simple modifications and combinations should also be regarded as the disclosed content of the present invention and all belong to the protection scope of the present invention. [Explanation of symbols]

[0109] 1-Example 1, 2-Example 2, 3-Example 3 S1-Halogenated polyphosphoric acid ester polyurethane elastomer manufactured in Example 1 of the present invention DS1-Polyurethane elastomer manufactured in Comparative Example 1 of the present invention [Brief description of the drawings]

[0110]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Claims

1. A halogenated polyphosphoric acid ester polyol, characterized by containing one of the structural units represented by formula (6) and formula (7). 【Chemical 1】 (Here, X １ , X ２ , X ３ , X ４ and X ５ are the same or different and are each H and / or halogen and are not H at the same time, X and X' are the same or different, each being H and / or a halogen atom, and not being H at the same time.

2. The polyol according to claim 1, wherein X and X' are each a bromine, chlorine, iodine, or fluorine atom.

3. The polyol according to claim 1, containing one of the structural units represented by formula (8)-(12). 【Chemical 2】

4.

5. The polyol according to claim 1, having a number average molecular weight of 1000-50000 and a hydroxyl value of 2.5-115 mg KOH / g.

6.

7. A prepolymer, characterized by containing a structural unit derived from the halogenated polyphosphoric acid ester polyol according to any one of claims 1-4.

8.

9. The prepolymer according to claim 5, having a number average molecular weight of 1500-50000, and a NCO content of 10-20% by weight.

10.

11. A method for producing a prepolymer, comprising: step (D-1) of contacting the halogenated polyphosphoric acid ester polyol according to any one of claims 1-4 with a polyether polyol and subjecting them to a dehydration reaction to obtain an intermediate product; step (D-2) of contacting the intermediate product with an isocyanate and subjecting them to prepolymerization to obtain a prepolymer.

12.

13. The conditions for the dehydration reaction include a temperature of 60-120°C and a time of 0.5-1.5 h, and / or the conditions for the prepolymerization include a temperature of 40-90°C and a time of 1-3 h, according to the method of claim 11.

14. Based on the total weight of the prepolymer, the amount of the isocyanate used is 20-70% by weight, the amount of the polyether polyol used is 20-70% by weight, and the amount of the halogenated polyphosphoric acid ester polyol used is 5-20% by weight, according to the method of claim 13.

15.

16. A halogenated polyphosphoric acid ester polyureurea elastomer composition containing component A and component B, wherein component A is the prepolymer according to claim 5, and component B contains an amino-terminated polyether, an organosilane, and a chain extender.

17. The polyurea elastomer composition according to claim 10, wherein the ratio of the component A to the component B is (1 to 1.2):1 in terms of the isocyanate index.

12. The polyurea elastomer composition according to claim 10, wherein the content of the amino-terminated polyether is 18 to 80% by weight, the content of the organosilane is 0.2 to 2% by weight, and the content of the chain extender is 20 to 35% by weight based on the total weight of the component B.

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