Flame-retardant dihydric alcohol, thin-spray support material and preparation method and application thereof

Abstract

The application discloses a kind of flame-retardant dihydric alcohol, thin spray support material and its preparation method and application, flame-retardant dihydric alcohol has rigid five-membered heterocyclic structure, bridged ring structure and DOPO structure, has intrinsic flame-retardant characteristics, gives thin spray support material excellent thermal stability, intrinsic flame-retardant performance, anti-dripping, strong bonding performance and mechanical property, thin spray support material is realized with roadway by hydrogen bond action, π-π conjugation and strong polarity in molecular main chain Strong bonding, prevent cracking and falling, improve the safety level of roadway.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coal mine roadway reinforcement and support, and in particular, relates to a kind of flame-retardant dihydric alcohol, thin spray support material and its preparation method and application. BACKGROUND

[0002] In the process of coal mining, underground mining is the main mining method. In recent years, the total length of new tunneling in China exceeds 12000 km every year, and coal, semi-coal rock roadway accounts for more than 80%. New tunneling and the roadway in operation constitute the largest underground engineering in China. The traditional coal mine roadway surrounding rock generally adopts anchor rod, metal net and tray, steel belt and other anchor net support system for support, but there are problems of surrounding rock weathering and falling and failure of metal anchor net support system; spray concrete support method can also be used, however, the spray concrete support method has problems of large material construction quantity and transportation quantity, slow setting speed and easy cracking and falling.

[0003] Therefore, instead of spray concrete, developing thin spray support material for roadway surface is a new direction of development of coal mine roadway surrounding rock support technology. The difficulty of developing thin spray support material lies in strict requirements for the flame-retardant performance, mechanical properties and adhesive properties of the thin spray support material for roadway. In order to solve the problem of flame retardation, the effect of the traditional additive flame retardant is relatively single, and after adding the additive flame retardant, the mechanical properties and adhesive properties of the thin spray support material are seriously weakened, which is difficult to meet the technical requirements of the thin spray support material for roadway surface. SUMMARY

[0004] The present application is based on the discovery and understanding of the inventors on the following facts and problems: the current coal mine roadway reinforcement and support method has problems of surrounding rock weathering and falling, support system failure, large material construction quantity and transportation quantity, slow setting speed and easy cracking and falling. The thin spray support material has strict requirements for the flame-retardant performance, mechanical properties and adhesive properties of the material, the effect of the traditional additive flame retardant is relatively single, and after adding the additive flame retardant, the mechanical properties and adhesive properties of the thin spray support material are seriously weakened, which is difficult to meet the technical requirements of the thin spray support material for roadway surface.

[0005] The present application aims to at least solve one of the technical problems in the related art to some extent. To this end, the embodiments of the present application propose a kind of flame-retardant dihydric alcohol, thin spray support material and its preparation method and application, the flame-retardant dihydric alcohol has rigid five-membered heterocyclic ring structure, bridge ring structure and DOPO structure, has intrinsic flame-retardant characteristics, gives the thin spray support material excellent thermal stability, intrinsic flame-retardant performance, anti-dripping property, strong adhesive property and mechanical properties, the thin spray support material realizes strong adhesion with the roadway through hydrogen bonding, π-π conjugation and strong polarity in the molecular main chain, prevents cracking and falling, and improves the safety level of the roadway.

[0006] The application provides a kind of flame-retardant diol, the structural formula of the flame-retardant diol is as follows formula (I) or formula (II):

[0007]

[0008] Wherein, R 1 Or R 2 Each independently selected from unsubstituted or alkyl-substituted pyrrolyl, unsubstituted or alkyl-substituted furanyl.

[0009] The flame-retardant diol of the application embodiment brings the advantages and technical effects: in the related art, by introducing an organic phosphorus flame-retardant component containing an aliphatic structure into a polyester polyol to improve the flame-retardant performance of the material, there are problems of significant damage to the mechanical properties of the material and poor anti-dripping performance. The DOPO structure is introduced into the flame-retardant diol of the application, which has intrinsic flame-retardant performance. The furan and / or pyrrole five-membered aromatic heterocyclic structure forms a rigid structure with the bridged ring structure and the DOPO structure, further improving the thermal stability and flame-retardant properties of the material. In addition, the unsubstituted or alkyl-substituted pyrrolyl contains N elements, which can synergistically flame-retardant with the P elements of the DOPO structure, and has more excellent flame-retardant performance. The bridged ester group structure based on 5-norbornene-2,3-dicarboxylic acid and / or propylene pimaric acid can provide an ester group, can improve the bonding strength of the material through hydrogen bonding and strong polar action; also contains a double bond, which can strengthen the π-π conjugation effect and improve the bonding strength of the material; the chemical properties are stable, and the special non-linear molecular structure endows the material with excellent mechanical properties.

[0010] In the application embodiment, when the flame-retardant diol of the application is used in polyurethane, it can endow the polyurethane material with excellent thermal stability, intrinsic flame-retardant properties, anti-dripping performance and mechanical properties, and the molecular main chain functional groups of the flame-retardant diol can produce hydrogen bonding, π-π conjugation and strong polar action with the coal rock base, realize strong bonding effect, prevent cracking and falling, and improve the safety level of the roadway.

[0011] In some embodiments, R 1 Or R 2 Each independently selected from

[0012] The application embodiment provides a preparation method of a flame-retardant diol, comprising the following steps:

[0013] (1) reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a five-membered aromatic heterocyclic derivative to obtain a diol compound; the five-membered aromatic heterocyclic derivative includes at least one of a pyrrole derivative or a furan derivative;

[0014] (2) reacting the diacid with oxalyl chloride, and then adding the diol compound to perform acylation reaction, to obtain the flame-retardant diol; wherein the diacid comprises at least one of 5-norbornene-2,3-dicarboxylic acid or acrylpimaric acid.

[0015] In the embodiment, the DOPO reacts with the five-membered aromatic heterocyclic derivative to generate the diol compound, the diol compound reacts with the reaction product of the oxalyl chloride and the diacid to perform acylation reaction, to obtain the flame-retardant diol, the diacid has high reactivity and stable chemical property of the product, the method is simple, the condition is mild, and the method is suitable for mass production.

[0016] In some embodiments, in the step (1), the pyrrole derivative comprises at least one of the following structural formulae:

[0017]

[0018] And / or, the furan derivative comprises at least one of the following structural formulae:

[0019]

[0020] In some embodiments, in the step (1), the molar ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the five-membered aromatic heterocyclic derivative is 1:1;

[0021] And / or, the temperature of the reaction is 80-150 DEG C;

[0022] And / or, the time of the reaction is 2-8 h.

[0023] In some embodiments, in the step (2), the molar ratio of the diacid and the oxalyl chloride is 1:2;

[0024] And / or, the temperature of the reaction is 5-40 DEG C;

[0025] And / or, the time of the reaction is 2-5 h;

[0026] And / or, the molar ratio of the diacid and the diol compound is 1:2;

[0027] And / or, the temperature of the acylation reaction is 5-40 DEG C;

[0028] And / or, the time of the acylation reaction is 2-5 h.

[0029] The embodiment of the present application provides a thin spray supporting material, which comprises a first component and a second component, and the first component comprises, by mass, 50-90 parts of isocyanate, 10-40 parts of first polyhydric alcohol, 0-10 parts of viscosity reducer and 0.01-0.5 parts of polymerization inhibitor.

[0030] The second component comprises, by mass, 60-80 parts of a second polyol, 15-35 parts of a flame-retardant diol, 2-10 parts of an antistatic agent, and 0.2-2 parts of a catalyst; the flame-retardant diol comprises at least one of the flame-retardant diols described in the embodiments of the present application or the flame-retardant diols prepared by the preparation method described in the embodiments of the present application.

[0031] In the embodiments of the present application, the flame-retardant diol of the present application is used in the thin spray support material, which endows the thin spray support material with excellent thermal stability, intrinsic flame-retardant properties, anti-dripping properties, and mechanical properties. Meanwhile, the functional groups of the molecular main chain of the flame-retardant diol can form hydrogen bonds, π-π conjugation, and strong polarity with the coal rock substrate, so as to achieve strong adhesion between the thin spray support material and the coal rock substrate, prevent cracking and falling, and improve the safety level of the roadway. The thin spray support material can be added with a viscosity reducer to reduce the viscosity of the thin spray support material and improve the workability. The thin spray support material can be added with an antistatic agent to reduce the surface resistance and increase the antistatic property. The thin spray support material can also be added with a trace amount of a polymerization inhibitor, which helps to improve the storage period of the thin spray support material. The thin spray support material has a micro-phase separation structure of soft segments and hard segments, the hard segments are beneficial to improving the strength of the thin spray support material, and the soft segments are beneficial to improving the toughness of the thin spray support material. By optimizing the proportions of the components in the thin spray support material, a thin spray support material with excellent strength and toughness can be obtained.

[0032] In some embodiments, the isocyanate in the first component comprises at least one of toluene diisocyanate, diphenylmethane diisocyanate, or polyphenyl polymethylene polyisocyanate;

[0033] And / or, the first polyol comprises at least one of a polyether polyol or a polyester polyol;

[0034] And / or, the first polyol has a hydroxyl value of 30-500 mg KOH / g;

[0035] And / or, the viscosity reducer comprises at least one of dimethyl adipate or diisopropyl adipate;

[0036] And / or, the polymerization inhibitor comprises at least one of orthophosphoric acid, tartaric acid, benzoyl chloride, or benzoic acid.

[0037] In some embodiments, the second component, the second polyol comprises at least one of a polyether polyol or a polyester polyol;

[0038] And / or, the second polyol has a hydroxyl value of 30-500 mg KOH / g;

[0039] And / or, the antistatic agent comprises at least one of DS-8, E6019, or TRG-329;

[0040] And / or, the catalyst comprises at least one of an organic metal catalyst, an amine catalyst; the organic metal catalyst comprises at least one of dibutyltin dilaurate, stannous octoate, lead isooctoate, bismuth isooctoate; the amine catalyst comprises at least one of an aliphatic amine catalyst, a cycloaliphatic amine catalyst, an aromatic amine catalyst, or an alcohol amine catalyst.

[0041] The embodiment of the present application provides a preparation method of a thin spray supporting material, comprising the following steps:

[0042] 1) reacting isocyanate, first polyol, viscosity reducer and polymerization inhibitor to obtain a first component;

[0043] 2) mixing second polyol, flame-retardant diol, antistatic agent and catalyst to obtain a second component.

[0044] In some embodiments, in the step 1), the temperature of the reaction is 50-120 DEG C; and / or, the time of the reaction is 2-3h.

[0045] The embodiment of the present application provides an application of the flame-retardant diol or the thin spray supporting material, which is used for a roadway. In the embodiment of the present application, the flame-retardant diol or the thin spray supporting material has intrinsic flame-retardant characteristics and excellent mechanical properties, can be strongly bonded with the roadway, prevents cracking and falling, and improves the safety level of the roadway.

[0046] In some embodiments, the roadway comprises a coal mine roadway. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 It is a bonding strength testing device of the thin spray supporting material of the present application.

[0048] Figure 2 It is a bonding strength testing diagram of the thin spray supporting material of the embodiment 7 of the present application.

[0049] Figure 3 It is a H NMR spectrum of the diol compound in the embodiment 3. 1 H NMR spectrum.

[0050] Figure 4 It is a P NMR spectrum of the diol compound in the embodiment 3. 31 P NMR spectrum. DETAILED DESCRIPTION

[0051] The embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings. The embodiments described below by referring to the accompanying drawings are exemplary, and are intended to explain the present application, and cannot be understood as a limitation of the present application.

[0052] The flame-retardant diol of the embodiment of the present application has a structural formula as shown in the following formula (I) or formula (II):

[0053]

[0054] wherein R 1 or R 2 are each independently selected from unsubstituted or alkyl-substituted pyrrolyl, unsubstituted or alkyl-substituted furanyl.

[0055] The flame-retardant diol of the embodiment of the present application: in the related art, the flame-retardant performance of a material is improved by introducing an organic phosphorus flame-retardant component containing an aliphatic structure into a polyester polyol, which has the problems of significantly impairing the mechanical performance of the material and poor anti-dripping performance. The flame-retardant diol of the present application has intrinsic flame-retardant performance by introducing a DOPO structure. The furan and / or pyrrole five-membered aromatic heterocyclic structure and the bridged ring structure and the DOPO structure form a rigid structure, further improving the thermal stability and flame-retardant performance of the material. In addition, the unsubstituted or alkyl-substituted pyrrolyl contains N elements, which can synergistically flame-retardant with the P elements of the DOPO structure, and has more excellent flame-retardant performance. The bridged ring ester group structure based on 5-norbornene-2,3-dicarboxylic acid and / or propylene pimaric acid can provide an ester group, can improve the bonding strength of the material through hydrogen bonding and strong polar action; also contains a double bond, which can strengthen the π-π conjugation effect, improve the bonding strength of the material; and has stable chemical properties, and the special non-linear molecular structure endows the material with excellent mechanical properties.

[0056] In the embodiment of the present application, when the flame-retardant diol of the present application is used in polyurethane, the flame-retardant diol can endow the polyurethane material with excellent thermal stability, intrinsic flame-retardant performance, anti-dripping performance and mechanical properties, and the functional groups of the molecular main chain of the flame-retardant diol can produce hydrogen bonding, π-π conjugation and strong polar action with the coal rock base, realize strong bonding effect, prevent cracking and falling, and improve the safety level of the roadway.

[0057] In some embodiments, R 1 or R 2 are each independently selected from unsubstituted or alkyl-substituted pyrrolyl, unsubstituted or alkyl-substituted furanyl; optionally, the alkyl is selected from methyl, ethyl.

[0058] In some embodiments, R 1 or R 2 are each independently selected from wherein the * refers to a connecting bond (connecting site on the five-membered ring) of R 1 or R 2 in the flame-retardant diol, which does not represent a carbon atom. In the embodiment of the present application, R 1 or R 2The pyrrole group or the furan group is beneficial to further improve the flame-retardant performance, thermal stability, anti-dripping property, bonding property and mechanical property of the flame-retardant diol.

[0059] The method for preparing the flame-retardant diol comprises the following steps:

[0060] (1) reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and a five-membered aromatic heterocycle derivative (HAOH) to obtain a diol compound (DPH), wherein the five-membered aromatic heterocycle derivative comprises at least one of a pyrrole derivative or a furan derivative;

[0061] (2) reacting a diacid with oxalyl chloride, and then adding the diol compound to perform acylation reaction to obtain the flame-retardant diol (DPHE), wherein the diacid comprises at least one of 5-norbornene-2,3-dicarboxylic acid or acrylpimaric acid.

[0062] In the embodiment of the present application, the DOPO and the five-membered aromatic heterocycle derivative are reacted to generate the diol compound, and the diol compound and the reaction product of the diacid and oxalyl chloride are subjected to acylation reaction to obtain the flame-retardant diol. The diacid has high reactivity and the product generated thereby has stable chemical properties. The method is simple, the conditions are mild, and the method is suitable for mass production.

[0063] In some embodiments, in the step (1), the pyrrole derivative comprises at least one of the following structural formulae:

[0064]

[0065] In the embodiment of the present application, the pyrrole derivative has small steric hindrance and high reactivity, and the aldehyde group is reacted with the DOPO.

[0066] In some embodiments, in the step (1), the furan derivative comprises at least one of the following structural formulae:

[0067]

[0068] In the embodiment of the present application, the furan derivative has small steric hindrance and high reactivity, and the aldehyde group is reacted with the DOPO.

[0069] In some embodiments, in the step (1), the molar ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the five-membered aromatic heterocycle derivative is 1:1.

[0070] In some embodiments, in step (1), the temperature of the reaction is 80-150°C, specifically, for example, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C; and / or, the time of the reaction is 2-8h, specifically, for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h.

[0071] In some embodiments, in step (1), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the five-membered aromatic heterocyclic derivative are reacted in a solvent to obtain the diol compound; optionally, the solvent comprises at least one of dioxane or 2-methyltetrahydrofuran.

[0072] In some embodiments, in step (1), after the reaction is completed, the solvent is removed and dried to obtain the diol compound; optionally, the removal of the solvent is performed by distillation under reduced pressure; optionally, before drying, washing is performed, specifically, washing is performed using chloroform.

[0073] In some embodiments, in step (2), the molar ratio of the dibasic acid to oxalyl chloride is 1:2.

[0074] In some embodiments, in step (2), the temperature of the reaction is 5-40°C, specifically, for example, 5°C, 15°C, 20°C, 25°C, 30°C, 40°C; and / or, the time of the reaction is 2-5h, specifically, for example, 2h, 3h, 4h, 5h.

[0075] In some embodiments, in step (2), the molar ratio of the dibasic acid to the diol compound is 1:2. In the embodiments of the present application, the amount of substance of the diol compound is twice that of the dibasic acid, and the steric hindrance of the two hydroxyl groups of the diol compound is different, and the reactivity is different. The primary hydroxyl group with small steric hindrance reacts preferentially, and the reaction is selective.

[0076] In some embodiments, in step (2), the temperature of the acylation reaction is 5-40°C, specifically, for example, 5°C, 15°C, 20°C, 25°C, 30°C, 40°C; and / or, the time of the acylation reaction is 2-5h, specifically, for example, 2h, 3h, 4h, 5h.

[0077] In some embodiments, in step (2), after the dibasic acid is reacted with oxalyl chloride, the diol compound is slowly added.

[0078] In some embodiments, in step (2), the dibasic acid and oxalyl chloride are reacted in a solvent; optionally, the solvent comprises at least one of dichloromethane, trichloromethane or tetrahydrofuran.

[0079] In some embodiments, after the acylation reaction in step (2), filtration, distillation under reduced pressure, washing, and drying are performed to obtain the flame-retardant diol.

[0080] In some embodiments, step (2) is performed under an inert gas atmosphere; optionally, the inert gas atmosphere comprises nitrogen.

[0081] A thin spray support material according to an embodiment of the present application comprises a first component and a second component, wherein the first component comprises, by mass: 50-90 parts of isocyanate, 10-40 parts of a first polyol, 0-10 parts of a viscosity reducer, and 0.01-0.5 parts of a polymerization inhibitor.

[0082] The second component comprises, by mass: 60-80 parts of a second polyol, 15-35 parts of a flame-retardant diol, 2-10 parts of an antistatic agent, and 0.2-2 parts of a catalyst; the flame-retardant diol comprises at least one of the flame-retardant diols according to the embodiments of the present application or prepared by the preparation method according to the embodiments of the present application.

[0083] In the embodiments of the present application, the flame-retardant diol of the present application is used in the thin spray support material, which endows the thin spray support material with excellent thermal stability, intrinsic flame-retardant properties, anti-dripping properties, and mechanical properties. Meanwhile, the functional groups of the molecular main chain of the flame-retardant diol can form hydrogen bonds, π-π conjugation, and strong polarity with the coal rock substrate, thereby achieving strong adhesion between the thin spray support material and the coal rock substrate, preventing cracking and falling, and improving the safety level of the roadway. The viscosity reducer can be added to the thin spray support material to reduce the viscosity of the thin spray support material and improve the workability. The antistatic agent can be added to the thin spray support material to reduce the surface resistance and increase the antistatic property. A small amount of polymerization inhibitor can also be added to the thin spray support material, which helps to improve the storage period of the thin spray support material. The thin spray support material has a micro-phase separation structure of soft segments and hard segments, the hard segments are beneficial to improving the strength of the thin spray support material, and the soft segments are beneficial to improving the toughness of the thin spray support material. By optimizing the proportions of the components in the thin spray support material, a thin spray support material with excellent strength and toughness can be obtained.

[0084] In some embodiments, the first component comprises: 50 parts, 60 parts, 70 parts, 80 parts, 85 parts, or 90 parts of isocyanate.

[0085] The first polyol can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, or 40 parts.

[0086] The viscosity reducer can be 0 parts, 0.01 parts, 0.5 parts, 1 parts, 2 parts, 5 parts, 7 parts, 8 parts, or 10 parts.

[0087] The polymerization inhibitor can be 0.01 parts, 0.02 parts, 0.05 parts, 0.1 parts, 0.2 parts, 0.4 parts, or 0.5 parts.

[0088] In some embodiments, in the second component: the second polyol can be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts;

[0089] The flame retardant diol can be 15 parts, 20 parts, 25 parts, 30 parts, 35 parts;

[0090] The antistatic agent can be 2 parts, 4 parts, 6 parts, 8 parts, 10 parts;

[0091] The catalyst can be 0.2 parts, 0.5 parts, 1 parts, 1.5 parts, 2 parts.

[0092] In some embodiments, in the first component, the isocyanate comprises at least one of toluene diisocyanate, diphenyl methane diisocyanate, or polyphenyl polyformethylene polyisocyanate.

[0093] In some embodiments, the first polyol comprises at least one of a polyether polyol or a polyester polyol; optionally, the polyether polyol comprises at least one of polytetrahydrofuran polyol, polyether polyol F3135, polyether polyol R4110, polyether polyol R2380; the polyester polyol comprises at least one of polyester polyol PDA-2000, polyester polyol POL-1256, polyester polyol PS-4002, polyester polyol PS-315S.

[0094] In some embodiments, the first polyol has a hydroxyl value of 30-500 mg KOH / g, specifically, for example, 30 mg KOH / g, 50 mg KOH / g, 100 mg KOH / g, 200 mg KOH / g, 300 mg KOH / g, 400 mg KOH / g, 500 mg KOH / g.

[0095] In some embodiments, the viscosity reducer comprises at least one of dimethyl adipate or diisopropyl adipate.

[0096] In some embodiments, the polymerization inhibitor comprises at least one of orthophosphoric acid, tartaric acid, benzoyl chloride, benzoic acid.

[0097] In some embodiments, in the second component, the second polyol comprises at least one of a polyether polyol or a polyester polyol; optionally, the polyether polyol comprises at least one of polytetrahydrofuran polyol, polyether polyol F3135, polyether polyol R4110, polyether polyol R2380; the polyester polyol comprises at least one of polyester polyol PDA-2000, polyester polyol POL-1256, polyester polyol PS-4002, polyester polyol PS-315S.

[0098] In some embodiments, the second polyol has a hydroxyl value of 30-500 mg KOH / g, specifically, for example, 30 mg KOH / g, 50 mg KOH / g, 100 mg KOH / g, 200 mg KOH / g, 300 mg KOH / g, 400 mg KOH / g, 500 mg KOH / g.

[0099] In some embodiments, the antistatic agent comprises at least one of DS-8, E6019, TRG-329.

[0100] In some embodiments, the catalyst comprises at least one of an organometallic catalyst, an amine catalyst; optionally, the organometallic catalyst comprises at least one of dibutyltin dilaurate, stannous octoate, lead isooctoate, bismuth isooctoate; optionally, the amine catalyst comprises at least one of an aliphatic amine catalyst, a cycloaliphatic amine catalyst, an aromatic amine catalyst, or an alcohol amine catalyst; optionally, the amine catalyst comprises at least one of N-methylmorpholine, N,N-dimethylcyclohexylamine.

[0101] In some embodiments, the mass ratio of the first component and the second component is 0.9-1.1:1, specifically, for example, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1.

[0102] In some embodiments, the volume ratio of the first component and the second component is 0.9-1.1:1, specifically, for example, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1.

[0103] A method for preparing a thin spray support material according to an embodiment of the present application comprises the following steps:

[0104] 1) reacting isocyanate, first polyol, viscosity reducer, and polymerization inhibitor to obtain a first component;

[0105] 2) mixing second polyol, flame-retardant diol, antistatic agent, and catalyst to obtain a second component.

[0106] In some embodiments, in step 1), the reaction temperature is 50-120°C, specifically, for example, 50°C, 70°C, 80°C, 100°C, 110°C, 120°C; and / or, the reaction time is 2-3h, specifically, for example, 2h, 2.5h, 3h.

[0107] In some embodiments, in step 1), after the reaction, the temperature is lowered to room temperature, and nitrogen protection is performed, and the first component is obtained.

[0108] In some embodiments, in the step 2), the temperature for mixing is 5-40℃, specifically, for example, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 40℃; and / or, the time for mixing is 2-3h.

[0109] In some embodiments, in the step 2), the mixing mode is stirring.

[0110] In some embodiments, in the step 2), after mixing, the mixture is protected by nitrogen at room temperature or after cooling to room temperature, and then protected by nitrogen, and then discharged to obtain the second component.

[0111] The application of the fire-retardant dihydric alcohol or thin-spraying supporting material in an embodiment of the present application is applied to a roadway. In an embodiment of the present application, the fire-retardant dihydric alcohol or thin-spraying supporting material has intrinsic fire-retardant properties and excellent mechanical properties, can be strongly bonded with the roadway, prevents cracking and falling, and improves the safety level of the roadway.

[0112] In some embodiments, the thin-spraying supporting material is applied to the surface of the surrounding rock of the roadway.

[0113] In some embodiments, the roadway includes a coal mine roadway, which optionally includes a coal rock roadway or a semi-coal rock roadway.

[0114] In some embodiments, the thin-spraying supporting material is sprayed onto the surface of the roadway.

[0115] In some embodiments, the first component and the second component are mixed and sprayed onto the surface of the roadway; optionally, the first component and the second component are added to a spraying device for spraying.

[0116] In some embodiments, the solidification time after spraying is 5-40s, specifically, for example, 5s, 10s, 20s, 30s, 40s.

[0117] In some embodiments, the mass ratio of the first component to the second component is 0.9-1.1:1, specifically, for example, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1.

[0118] In some embodiments, the volume ratio of the first component to the second component is 0.9-1.1:1, specifically, for example, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1.

[0119] In some embodiments, the thickness of the thin-spraying supporting material on the surface of the roadway is 5-10mm, specifically, for example, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm.

[0120] The present application will be described below with reference to specific examples, which are intended to be illustrative only and not limiting of the present application in any way.

[0121] Example 1

[0122] A method for preparing a flame-retardant diol, comprising the steps of:

[0123] (1) reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a five-membered aromatic heterocyclic derivative in 2-methyltetrahydrofuran at 100°C for 5 hours at a molar ratio of 1:1, washing with chloroform and drying to obtain a diol compound (6-(hydroxy(5-(hydroxymethyl)-1-methyl-1H-pyrrol-2-yl)methyl)dibenzo[c,e][1,2]oxaphosphorin-6-oxide);

[0124] (2) after reacting 5-norbornene-2,3-dicarboxylic acid with oxalyl chloride at 40°C for 2 hours at a molar ratio of 1:2, slowly adding the diol compound, and reacting 5-norbornene-2,3-dicarboxylic acid with the diol compound at a molar ratio of 1:2 at 30°C for 3 hours, after the reaction is completed, performing suction filtration, distillation under reduced pressure, washing, and drying to obtain a flame-retardant diol (bis(5-(hydroxy(6-oxidodibenzo[c,e][1,2]oxaphosphorin-6-yl)methyl)-1-methyl-1H-pyrrol-2-yl)methyl(1R,2R,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, DPHE1).

[0125]

[0126] Example 2

[0127] The same as the preparation method of Example 1, except that the five-membered aromatic heterocyclic derivative in the step (1) is replaced with to finally obtain a flame-retardant diol (bis(1-ethyl-5-(hydroxy(6-oxidodibenzo[c,e][1,2]oxaphosphorin-6-yl)methyl)-1H-pyrrol-2-yl)methyl(1R,2R,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, DPHE2).

[0128]

[0129] Example 3

[0130] The same as the preparation method of Example 1, except that the five-membered aromatic heterocyclic derivative in the step (1) is replaced with to obtain a diol compound (1H NMR spectrum as shown in Figure 3 , and a phosphorus spectrum as shown in Figure 4The final product is the flame-retardant diol (bis(5-(hydroxy(6-oxidodi benzo[c,e][1,2]oxaphosphor-6-yl)methyl)furan-2-yl)methyl(1R,2R,4S)-bicyclo[2.2.1]heptan-5-ene-2,3-dicarboxylate, DPHE3).

[0131] Example 4

[0132] The preparation method is the same as that of Example 1, except that the five-membered aromatic heterocyclic derivative in step (1) is replaced by The 5-norbornene-2,3-dicarboxylic acid in step (2) is replaced by propenymaronic acid, and the final product is DPHE4.

[0133] Example 5

[0134] The preparation method is the same as that of Example 1, except that the five-membered aromatic heterocyclic derivative in step (1) is replaced by The 5-norbornene-2,3-dicarboxylic acid in step (2) is replaced by propenymaronic acid, and the final product is DPHE5.

[0135] Example 6

[0136] A thin spray support material, comprising a first component and a second component, the first component comprising: 63 parts by weight of toluene diisocyanate; 20 parts by weight of polytetrahydrofuran polyol (hydroxyl value 112 mg KOH / g), 12 parts by weight of polyether polyol F3135 (hydroxyl value 33 mg KOH / g); 4.95 parts by weight of a viscosity reducer dimethyl adipate; 0.05 parts by weight of a polymerization inhibitor orthophosphoric acid;

[0137] The second component comprises: 65 parts by weight of polyether polyol R4110 (hydroxyl value 460 mg KOH / g); 29.5 parts by weight of DPHE1 diol; 3 parts by weight of antistatic agent DS-8, 2 parts by weight of E6019; 0.5 parts by weight of catalyst dibutyl tin dilaurate;

[0138] A method for preparing a thin spray support material, comprising the following steps:

[0139] 1) The isocyanate, the first polyol, the viscosity reducer and the polymerization inhibitor are reacted at 70°C for 3h, and then cooled to room temperature and protected by nitrogen, and the first component is obtained by discharging;

[0140] 2) The second polyol, the flame-retardant diol, the antistatic agent and the catalyst are stirred and mixed uniformly at room temperature, and then protected by nitrogen at room temperature after mixing, and the second component is obtained by discharging.

[0141] Example 7

[0142] The preparation method is the same as that of Example 6, except that the thin-spray support material comprises a first component and a second component, the first component comprises: toluene diisocyanate 50 parts by weight, polyphenyl polymethylene polyisocyanate 22 parts by weight; polytetrahydrofuran polyol 10 parts by weight (hydroxyl value 56 mg KOH / g), polyester polyol PDA-2000 (hydroxyl value 52 mg KOH / g) 10 parts by weight; viscosity reducer diisopropyl adipate 7.95 parts by weight; polymerization inhibitor tartaric acid 0.05 parts by weight;

[0143] The second component comprises: polyether polyol R2380 (hydroxyl value 380 mg KOH / g) 65 parts by weight; DPHE1 diol 29.5 parts by weight; antistatic agent E6019 5 parts by weight; catalyst bismuth octoate 0.5 parts by weight.

[0144] Example 8

[0145] The preparation method is the same as that of Example 6, except that the thin-spray support material comprises a first component and a second component, the first component comprises: polyphenyl polymethylene polyisocyanate 59 parts by weight; polyester polyol POL-1256 (hydroxyl value 52 mg KOH / g) 35 parts by weight; viscosity reducer diisopropyl adipate 5.95 parts by weight; polymerization inhibitor benzoyl chloride 0.05 parts by weight;

[0146] The second component comprises: polytetrahydrofuran polyol (hydroxyl value 448 mg KOH / g) 30 parts by weight, polyether polyol R2380 (hydroxyl value 380 mg KOH / g) 45 parts by weight; DPHE1 diol 16.9 parts by weight; antistatic agent TRG-329 7 parts by weight; catalyst dibutyl tin dilaurate 0.5 parts by weight, N-methyl morpholine 0.6 parts by weight.

[0147] Example 9

[0148] The preparation method is the same as that of Example 6, except that in the second component, DPHE1 diol is replaced by DPHE3 diol.

[0149] Example 10

[0150] The preparation method is the same as that of Example 6, except that the thin-spray support material comprises a first component and a second component, the first component comprises: toluene diisocyanate 50 parts by weight, polyphenyl polymethylene polyisocyanate 22 parts by weight; polytetrahydrofuran polyol 10 parts by weight (hydroxyl value 56 mg KOH / g), polyester polyol PDA-2000 (hydroxyl value 52 mg KOH / g) 10 parts by weight; viscosity reducer diisopropyl adipate 7.95 parts by weight; polymerization inhibitor tartaric acid 0.05 parts by weight;

[0151] The second component comprises: polytetrahydrofuran polyol (hydroxyl value 448 mg KOH / g) 35 parts by weight, polyester polyol PS-4002 (hydroxyl value 408 mg KOH / g) 35 parts by weight; DPHE2 diol 19.4 parts by weight; antistatic agent TRG-329 9 parts by weight; catalyst dibutyl tin dilaurate 0.8 parts by weight, N,N-dimethylcyclohexylamine 0.8 parts by weight.

[0152] Example 11

[0153] The preparation method is the same as that of Example 6, except that the thin spray support material comprises a first component and a second component, and the first component comprises: polyphenyl polymethylene polyisocyanate 20 parts by weight, diphenylmethane diisocyanate 60 parts by weight; polyether polyol F3135 (hydroxyl value 33 mg KOH / g) 17 parts by weight; viscosity reducer dimethyl adipate 2.95 parts by weight; polymerization inhibitor benzoyl chloride 0.05 parts by weight;

[0154] The second component comprises: polytetrahydrofuran polyol (hydroxyl value 448 mg KOH / g) 35 parts by weight, polyester polyol PS-315S (hydroxyl value 310 mg KOH / g) 35 parts by weight; DPHE4 diol 19.4 parts by weight; antistatic agent E6019 9 parts by weight; catalyst dibutyl tin dilaurate 0.5 parts by weight, N,N-dimethylcyclohexylamine 1.1 parts by weight.

[0155] Example 12

[0156] The preparation method is the same as that of Example 11, except that in the second component, DPHE4 diol is replaced by DPHE5 diol.

[0157] Comparative Example 1

[0158] The preparation method is the same as that of Example 6, except that in the second component, polyether polyol R4110 (hydroxyl value 460 mg KOH / g) 29.5 parts by weight is replaced by DPHE1 diol 29.5 parts by weight.

[0159] Comparative Example 2

[0160] The preparation method is the same as that of Example 6, except that in the second component, polyether polyol R4110 (hydroxyl value 460 mg KOH / g) 65 parts by weight is adjusted to 55 parts by weight; DPHE1 diol 29.5 parts by weight is adjusted to 39.5 parts by weight.

[0161] Comparative Example 3

[0162] The preparation method of Example 6 was the same, except that in the second component, the polyether polyol DPHE1 (hydroxyl value 460 mg KOH / g) 65 parts by weight was adjusted to 85.5 parts by weight; DPHE1 diol 29.5 parts by weight was adjusted to 9 parts by weight.

[0163] Comparative Example 4

[0164] The preparation method of Example 6 was the same, except that in the second component, the DPHE1 diol 29.5 parts by weight was replaced by the polyether polyol R4110 (hydroxyl value 460 mg KOH / g) 29.5 parts by weight, and 14.9 parts by weight of DOPO was added, and in the step 2), the second polyol, DOPO, antistatic agent and catalyst were stirred and mixed uniformly at room temperature to obtain the second component.

[0165] Comparative Example 5

[0166] The preparation method of Example 6 was the same, except that in the second component, the antistatic agent DS-8 was omitted.

[0167] The thin spray support material in Examples 6-12 and Comparative Examples 1-5, the volume ratio of the first component and the second component was 1:1, according to the "Roadway Surface Thin Spray Support Material Safety Technical Requirements (Trial)", and the standard AQ1088-2011 was tested for curing time, tensile strength, elongation at break, bonding strength and surface resistance, GB / T 2406.2-2009 standard was tested for oxygen index, and the results are shown in Table 1.

[0168] Table 1

[0169]

[0170] As can be seen from Table 1, the thin spray support material of the present application has an oxygen index of not less than 28%, has intrinsic flame retardant properties, has excellent mechanical properties, and the thin spray support material realizes strong adhesion with coal and rock roadways through hydrogen bonding, π-π conjugation and strong polarity in the molecular main chain.

[0171] As can be seen from Comparative Example 6 and Example 9, the thin spray support material of Example 6 has more excellent intrinsic flame retardant properties, adhesion properties, etc., because the pyrrole derivative in Example 6 contains N element, which can synergistically flame retard with P element in DOPO structure, and has more excellent flame retardant properties than the furan derivative in Example 9.

[0172] Comparative Example 6 and Comparative Example 1, it can be seen that Comparative Example 1 does not add the flame-retardant dihydric alcohol, the oxygen index is 23.3%, which does not reach the requirement of the safety regulation that the oxygen index is not less than 28%, and does not have the intrinsic flame-retardant property. The tensile strength and the elongation at break of the thin-spraying supporting material in Comparative Example 1 are both lower than those of Example 6, the mechanical property is poor, and the bonding strength of the thin-spraying supporting material in Comparative Example 1 is only 1.9 MPa, the bonding property is poor, and cracking and falling are prone to occur when used in the roadway. The surface resistance of the thin-spraying supporting material in Comparative Example 1 is 3.2 x 10 8 Ω, which does not reach the requirement of the safety regulation that the surface resistance is not higher than 3.0 x 10 8 Ω, and the surface resistance is high in Comparative Example 1 due to the absence of the flame-retardant dihydric alcohol.

[0173] Comparative Example 6 and Comparative Example 2, it can be seen that the amount of the flame-retardant dihydric alcohol is too high in Comparative Example 2, the toughness of the thin-spraying supporting material is reduced, and the elongation at break is decreased.

[0174] Comparative Example 6 and Comparative Example 3, it can be seen that the oxygen index is significantly reduced to only 27.5% when the amount of the flame-retardant dihydric alcohol is low in Comparative Example 3, which does not reach the requirement of the safety regulation that the oxygen index is not less than 28%, and the flame-retardant property is poor. In addition, the mechanical property and the bonding property are also reduced, and the surface resistance is increased when the amount of the flame-retardant dihydric alcohol is low in Comparative Example 3.

[0175] Comparative Example 6 and Comparative Example 4, it can be seen that the flame retardant DOPO is physically added in Comparative Example 4, and since the DOPO is only physically mixed in the thin-spraying supporting material, the covalent bond connection cannot be achieved, the dispersion at the molecular level is not realized, the internal components of the material are not uniformly dispersed, the mechanical properties such as the tensile strength and the elongation at break are all decreased, the flame-retardant elements are not uniformly distributed due to the physical doping, the flammable components are aggregated, the oxygen index is also significantly affected, and the mechanical property, the bonding property and the flame-retardant property of the thin-spraying supporting material are all seriously weakened, and it is difficult to reach the technical requirements of the thin-spraying supporting material on the surface of the roadway.

[0176] The antistatic agent is not used in Comparative Example 5, and the surface resistance does not reach the requirement of the safety regulation that the surface resistance of the thin-spraying supporting material on the surface of the roadway is not higher than 3.0 x 10 8 Ω.

[0177] Figure 1 is the bonding strength testing device of the thin-spraying supporting material of the present application. Figure 2 is the bonding strength testing diagram of the thin-spraying supporting material of Example 7 of the present application. From Figure 2It can be seen that the bonding strength test substrate of the thin spray support material of embodiment 7 is damaged, because the polar atoms in the molecular structure of the thin spray support material can form hydrogen bonds with the hydroxyl groups in the sand and mudstone, thereby improving the bonding strength of the thin spray support material and the rock interface, and through the firm covalent bond connection, improving its dispersibility, and the experimental results show that the tensile failure occurs in the cement block matrix, and the thin spray support material spray layer is not damaged, which indicates that the bonding strength of the thin spray support material and the rock interface substrate is greater than the strength of the test substrate itself (about 2.9 MPa), and the higher delocalized π electrons in the thin spray support material can interact with the benzene ring structure rich in coal through π-π conjugation effect, thereby realizing strong bonding with the surrounding rock of the roadway, and playing a mechanical role under the small displacement of the surrounding rock of the roadway, thereby realizing timely intervention on the early deformation of the surrounding rock of the roadway, and realizing the disaster prevention and control of the surrounding rock.

[0178] In the present application, the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. mean that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, different embodiments or examples described in the present specification and the features of different embodiments or examples can be combined and combined by those skilled in the art without contradiction.

[0179] Although the above embodiments have been shown and described, it can be understood that the above embodiments are exemplary and cannot be understood as limiting the present application, and the changes, modifications, replacements and variations of the above embodiments made by those skilled in the art are within the protection scope of the present application.

Claims

1. A flame-retardant diol, characterized in that, The structural formula of the flame-retardant diol is shown in the following formula (I) or formula (II): wherein R 1 or R 2 each independently is selected from unsubstituted or alkyl-substituted pyrrolyl, unsubstituted or alkyl-substituted furanyl.

2. The flame retardant diol according to claim 1, characterized in that, R 1 or R 2 each independently is selected from 3. A process for the preparation of a flame-retardant diol according to claim 1 or 2, characterized in that, The method comprises the following steps: (1) reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a five-membered aromatic heterocyclic derivative to obtain a diol compound; the five-membered aromatic heterocyclic derivative comprises at least one of a pyrrole derivative or a furan derivative; (2) reacting a diacid with oxalyl chloride, and then adding the diol compound to perform acylation reaction to obtain the flame-retardant diol; wherein the diacid comprises at least one of 5-norbornene-2,3-dicarboxylic acid or acrylpimaric acid.

4. The method of preparing a flame retardant diol according to claim 3, wherein In the step (1), the pyrrole derivative comprises at least one of the following structural formulae: And / or, the furan derivative comprises at least one of the following structural formulae:

5. The method for preparing the flame-retardant diol according to claim 3, characterized in that, In the step (1), the molar ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the five-membered aromatic heterocyclic derivative is 1:1; And / or, the reaction temperature is 80-150°C; And / or, the reaction time is 2-8h.

6. The method for preparing the flame-retardant diol according to claim 3, characterized in that, In the step (2), the molar ratio of the diacid and the oxalyl chloride is 1:2; And / or, the reaction temperature is 5-40°C; And / or, the reaction time is 2-5h; And / or, the molar ratio of the diacid and the diol compound is 1:2; And / or, the acylation reaction temperature is 5-40°C; And / or, the acylation reaction time is 2-5h.

7. A thin spray-on support material, characterized in that The first component comprises, by mass, 50-90 parts of isocyanate, 10-40 parts of first polyol, 0-10 parts of viscosity reducer and 0.01-0.5 parts of polymerization inhibitor; The second component comprises, by mass, 60-80 parts of second polyol, 15-35 parts of flame-retardant diol, 2-10 parts of antistatic agent and 0.2-2 parts of catalyst; the flame-retardant diol comprises at least one of the flame-retardant diol in claim 1 or 2 or the flame-retardant diol prepared by the method in any one of claims 3-6.

8. The thin spray-on support material of claim 7, wherein, In the first component, the isocyanate comprises at least one of toluene diisocyanate, diphenylmethane diisocyanate or polyphenyl polymethylene polyisocyanate; And / or, the first polyol comprises at least one of polyether polyol or polyester polyol; And / or, the hydroxyl value of the first polyol is 30-500 mg KOH / g; And / or, the viscosity reducer comprises at least one of dimethyl adipate or diisopropyl adipate; And / or, the polymerization inhibitor comprises at least one of orthophosphoric acid, tartaric acid, benzoyl chloride, benzoic acid.

9. The thin spray-on support material of claim 7, wherein, In the second component, the second polyol comprises at least one of polyether polyol or polyester polyol; And / or, the hydroxyl value of the second polyol is 30-500 mg KOH / g; And / or, the antistatic agent comprises at least one of DS-8, E6019, TRG-329. And / or, the catalyst comprises at least one of an organic metal catalyst, an amine catalyst; the organic metal catalyst comprises at least one of dibutyltin dilaurate, stannous octoate, lead isooctoate, bismuth isooctoate; the amine catalyst comprises at least one of an aliphatic amine catalyst, a cycloaliphatic amine catalyst, an aromatic amine catalyst, or an alcohol amine catalyst.

10. A method of producing a thin spray support material according to any one of claims 7-9, characterized in that, Comprising the following steps: 1) reacting isocyanate, first polyol, viscosity reducer, and polymerization inhibitor to obtain a first component; 2) mixing second polyol, flame-retardant diol, antistatic agent, and catalyst to obtain a second component.

11. The method of claim 10, wherein the thin spray-on support material is prepared by, In the step 1), the temperature of the reaction is 50-120°C; and / or, the time of the reaction is 2-3h.

12. Use of a flame-retardant diol according to claim 1 or 2 or a thin spray support material according to any one of claims 7 to 9, characterized in that For a tunnel.

13. Use according to claim 12, characterized in that, The tunnel comprises a coal mine tunnel.

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