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WO2024093849A1 - Flame retardant, preparation method therefor, and rigid polyurethane foam - Google Patents

Flame retardant, preparation method therefor, and rigid polyurethane foam Download PDF

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Publication number
WO2024093849A1
WO2024093849A1 PCT/CN2023/127324 CN2023127324W WO2024093849A1 WO 2024093849 A1 WO2024093849 A1 WO 2024093849A1 CN 2023127324 W CN2023127324 W CN 2023127324W WO 2024093849 A1 WO2024093849 A1 WO 2024093849A1
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WO
WIPO (PCT)
Prior art keywords
flame retardant
parts
rigid polyurethane
polyurethane foam
phosphate
Prior art date
Application number
PCT/CN2023/127324
Other languages
French (fr)
Chinese (zh)
Inventor
张春玉
李本怀
梁永久
董德文
Original Assignee
中车长春轨道客车股份有限公司
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Publication of WO2024093849A1 publication Critical patent/WO2024093849A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/388—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the present disclosure relates to the technical field of flame retardants, and in particular to a flame retardant and a preparation method thereof, and a rigid polyurethane foam.
  • Rigid polyurethane foam is a high molecular polymer made of isocyanate and polyether as the main raw materials, mixed with special equipment under the action of various additives such as foaming agent and catalyst, and foamed on site by high-pressure spraying. It has the characteristics of light weight, strong chemical resistance, impact energy absorption, good sound insulation and heat insulation, convenient molding and processing, etc. It has a wide range of applications and can be used in many industries such as transportation, construction, packaging, refrigeration, etc. However, rigid polyurethane foam has poor flame retardant properties, is very easy to burn, and the fire spreads very quickly. The large amount of smoke particles released during the combustion process causes great pollution to the environment, and the toxic gases produced can easily cause a large number of casualties in the fire, which limits the application of rigid polyurethane foam.
  • additive flame retardants are mainly used to improve the flame retardant effect of rigid polyurethane foam plastics.
  • traditional flame retardants such as the large amount of smoke produced and the toxicity of smoke produced by halogen-phosphorus flame retardants; excessive addition of inorganic flame retardants will reduce the mechanical properties of the material; and the worm-like carbon layer formed by pyrolysis of intumescent flame retardants is loose, and the interface compatibility between the polymer and the polymer is poor, resulting in a decrease in mechanical properties. Therefore, it is necessary to develop technical research on flame retardants for rigid polyurethane foam that can improve the flame retardant effect without affecting the mechanical properties of rigid polyurethane foam.
  • the first object of the present disclosure is to provide a flame retardant that can improve the flame retardant effect of rigid polyurethane foam without affecting the mechanical properties of the rigid polyurethane foam.
  • the second object of the present disclosure is to provide a method for preparing the flame retardant as described above, which has simple steps.
  • the third object of the present disclosure is to provide a rigid polyurethane foam having both excellent mechanical properties and flame retardant properties.
  • the present disclosure provides a flame retardant, including a composite additive flame retardant and a composite reactive flame retardant;
  • the composite additive flame retardant comprises the following components by weight: 1 to 80 parts of inorganic flame retardant, 1 to 75 parts of phosphorus halogen flame retardant and 5 to 60 parts of organic phosphorus flame retardant;
  • the composite reactive flame retardant comprises the following components by weight: 20 to 100 parts of di(4-hydroxybutyl)phenyl phosphate and 30 to 150 parts of 2-carboxyethylphenyl phosphite glycol ester;
  • the mass ratio of the composite additive flame retardant to the composite reactive flame retardant is 100:60-150.
  • the composite additive flame retardant includes the following components in parts by weight: 25 to 55 parts of inorganic flame retardant, 25 to 50 parts of phosphorus halogen flame retardant and 10 to 40 parts of organic phosphorus flame retardant.
  • the mass ratio of the di(4-hydroxybutyl)phenyl phosphate to the 2-carboxyethylphenyl phosphite glycol ester is 1:0.5-1.5.
  • the inorganic flame retardant includes aluminum hydroxide and montmorillonite.
  • the mass ratio of the aluminum hydroxide to the montmorillonite is 6:4-8.
  • the phosphorus halogen flame retardant includes tris(2-chloroisopropyl) phosphate.
  • the organophosphorus flame retardant includes triethyl phosphate and triphenyl phosphate.
  • the mass ratio of the triethyl phosphate to the triphenyl phosphate is 3:4-9.
  • the present disclosure also provides a method for preparing the flame retardant as described above, comprising the following steps: after uniformly mixing the components, the flame retardant is obtained.
  • the present disclosure also provides a rigid polyurethane foam, comprising the flame retardant as described above.
  • the mass percentage of the flame retardant is 0.5% to 3.5%.
  • the present disclosure provides a flame retardant, which can be used as a flame retardant for rigid polyurethane foam, can greatly improve the flame retardant effect of the rigid polyurethane foam, and does not affect the mechanical properties of the rigid polyurethane foam; adding the flame retardant of the present disclosure to the rigid polyurethane foam can increase the oxygen index of the rigid polyurethane foam from 21 to 23-30 while maintaining the original mechanical properties of the rigid polyurethane foam.
  • a flame retardant and a preparation method thereof and a rigid polyurethane foam according to an embodiment of the present disclosure are described in detail below.
  • a flame retardant including a composite additive flame retardant and a composite reactive flame retardant;
  • the composite additive flame retardant comprises the following components by weight: 1 to 80 parts of inorganic flame retardant, 1 to 75 parts of phosphorus halogen flame retardant and 5 to 60 parts of organic phosphorus flame retardant;
  • the composite reactive flame retardant comprises the following components by weight: 20 to 100 parts of di(4-hydroxybutyl)phenyl phosphate and 30 to 150 parts of 2-carboxyethylphenyl phosphite glycol ester;
  • the mass ratio of the composite additive flame retardant to the composite reactive flame retardant is 100:60-150.
  • the flame retardant provided by the present disclosure has an excellent flame retardant effect, and adding the flame retardant of the present disclosure to the rigid polyurethane foam can significantly improve the flame retardancy of the rigid polyurethane foam and greatly increase the value of the oxygen index without affecting the original mechanical properties of the rigid polyurethane foam.
  • the flame retardant disclosed in the present invention is composed of a composite additive flame retardant and a composite reactive flame retardant.
  • the composite additive mainly decomposes into released water under a high temperature environment of fire, thereby achieving a flame retardant effect.
  • the composite reactive flame retardant mainly releases free radicals in the gas phase during fire to capture the free radicals of the combustion reaction chain growth, thereby achieving a flame retardant effect.
  • the flame retardant raw material disclosed in the present invention has a flame retardant property and has little effect on the surface tension of the product raw material. It can guarantee the integrity of the foam cells (closed-cell foam) during the foaming process of the rigid polyurethane foam to the greatest extent, and ensures the integrity of the blast hole. Under the same raw material ratio, the compression resistance of the rigid polyurethane foam is guaranteed.
  • the weight proportion of the inorganic flame retardant is 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts or 80 parts, etc.
  • the weight proportion of the phosphorus halogen flame retardant is 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts or 75 parts, etc.
  • the weight proportion of the organophosphorus flame retardant is 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts or 60 parts, etc.
  • the weight proportion of di(4-hydroxybutyl)phenyl phosphate is 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts or 100 parts, etc.
  • the weight proportion of 2-carboxyethylphenyl phosphite is 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts or 150 parts, etc.
  • the mass ratio of the composite additive flame retardant to the composite reactive flame retardant is 100:60, 100:70, 100:80, 100:90, 100:100, 100:110, 100:120, 100:130, 100:140 or 100:150, etc.
  • the composite additive flame retardant includes the following components in parts by weight: 25 to 55 parts of inorganic flame retardant, 25 to 50 parts of phosphorus halogen flame retardant and 10 to 40 parts of organic phosphorus flame retardant.
  • the mass ratio of di(4-hydroxybutyl)phenyl phosphate and 2-carboxyethylphenyl phosphite glycol ester is 1:0.5-1.5; typically but not limiting, for example, the mass ratio of di(4-hydroxybutyl)phenyl phosphate and 2-carboxyethylphenyl phosphite glycol ester is 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5, etc.
  • the flame retardant for rigid polyurethane foam includes a composite additive flame retardant and a composite reactive flame retardant
  • the composite additive flame retardant comprises the following components by weight: 25 to 55 parts of inorganic flame retardant, 25 to 50 parts of phosphorus halogen flame retardant and 10 to 40 parts of organic phosphorus flame retardant;
  • the composite reactive flame retardant comprises the following components by weight: 100 parts of di(4-hydroxybutyl)phenyl phosphate and 50-150 parts of 2-carboxyethylphenyl phosphite glycol ester;
  • the mass ratio of the composite additive flame retardant to the composite reactive flame retardant is 100:60-150.
  • the inorganic flame retardant includes aluminum hydroxide and montmorillonite; further, the mass ratio of aluminum hydroxide to montmorillonite is 6:4-8; typically but not limitatively, for example, the mass ratio of aluminum hydroxide to montmorillonite is 6:4, 6:5, 6:6, 6:7 or 6:8, etc.
  • the phosphorus halogen flame retardant includes tris(2-chloroisopropyl) phosphate.
  • Tris(2-chloroisopropyl) phosphate is cheap and, compared with other phosphorus halogen flame retardants, is easier to release more PO ⁇ and Cl ⁇ free radicals to capture the free radicals of the combustion reaction chain growth, thereby being more cost-effective and more efficient in achieving a flame retardant effect.
  • tris(2-chloroisopropyl) phosphate has a more excellent coordination effect with other components of the system.
  • the organophosphorus flame retardant includes triethyl phosphate and triphenyl phosphate.
  • the mass ratio of triethyl phosphate to triphenyl phosphate is 3:4-9; typically but not limiting, for example, the mass ratio of triethyl phosphate to triphenyl phosphate is 3:4, 3:5, 3:6, 3:7, 3:8 or 3:9, etc.
  • the flame retardant disclosed in the present invention minimizes the influence on the integrity of the rigid polyurethane foam cells by controlling the ratio of each component, which is more conducive to maintaining the compressive strength of the rigid polyurethane foam.
  • a method for preparing the flame retardant as described above comprising the following steps: after mixing the components, a flame retardant is obtained.
  • a method for preparing a flame retardant comprises the following steps: fully stirring and mixing an inorganic flame retardant, a phosphorus halogen flame retardant, an organic phosphorus flame retardant, di(4-hydroxybutyl)phenyl phosphate and 2-carboxyethylphenyl phosphite glycol ester for 0.5 to 2 hours to obtain a flame retardant; further, the stirring temperature is 20 to 30°C.
  • a rigid polyurethane foam comprising the flame retardant.
  • the mass percentage of the flame retardant in the rigid polyurethane foam is 0.5% to 3.5%; typically but not limiting, for example, the mass percentage of the flame retardant in the rigid polyurethane foam is 0.5%, 1%, 1.5%, 2%, 2.5%, 3% or 3.5%, etc.
  • Adding the flame retardant to the rigid polyurethane foam system disclosed herein can significantly improve the flame retardancy without affecting the mechanical properties of the rigid polyurethane foam; and can increase the oxygen index from 21 to 23-30 without affecting the mechanical properties.
  • the flame retardant provided in this embodiment includes a composite additive flame retardant and a composite reactive flame retardant in a mass ratio of 100:100;
  • the composite additive flame retardant includes the following components by weight: 15 parts of aluminum hydroxide, 10 parts of montmorillonite, 35 parts of tri(2-chloroisopropyl) phosphate, 12 parts of triethyl phosphate and 28 parts of triphenyl phosphate;
  • the composite reactive flame retardant comprises the following components in parts by weight: 50 parts of di(4-hydroxybutyl)phenyl phosphate and 50 parts of 2-carboxyethylphenyl phosphite glycol ester.
  • the method for preparing the rigid polyurethane foam comprises adding the flame retardant mentioned above into the rigid polyurethane foaming system (the mass of the flame retardant added accounts for 1.1% of the mass of the rigid polyurethane foam).
  • the specific steps are: after the flame retardant and the polyol are evenly mixed, isocyanate is added and mixed, and the rigid polyurethane foam is obtained after sufficient foaming and molding.
  • the flame retardant provided in this embodiment includes a composite additive flame retardant and a composite reactive flame retardant in a mass ratio of 100:60;
  • the composite additive flame retardant includes the following components by weight: 17 parts of aluminum hydroxide, 23 parts of montmorillonite, 50 parts of tri(2-chloroisopropyl) phosphate, 2.5 parts of triethyl phosphate and 7.5 parts of triphenyl phosphate;
  • the composite reactive flame retardant comprises the following components by weight: 25 parts of di(4-hydroxybutyl)phenyl phosphate and 35 parts of 2-carboxyethylphenyl phosphite glycol ester.
  • the preparation method of the rigid polyurethane foam provided in this embodiment refers to that in Example 1, the difference is that the mass of the added flame retardant accounts for 2.0% of the mass of the rigid polyurethane foam.
  • the flame retardant provided in this embodiment includes a composite additive flame retardant and a composite reactive flame retardant in a mass ratio of 100:150;
  • the composite additive flame retardant includes the following components by weight: 22.5 parts of aluminum hydroxide, 22.5 parts of montmorillonite, 25 parts of tri(2-chloroisopropyl) phosphate, 8 parts of triethyl phosphate and 22 parts of triphenyl phosphate;
  • the composite reactive flame retardant comprises the following components in parts by weight: 75 parts of di(4-hydroxybutyl)phenyl phosphate and 75 parts of 2-carboxyethylphenyl phosphite glycol ester.
  • the preparation method of the rigid polyurethane foam provided in this embodiment refers to that in Embodiment 1, the difference is that the mass of the added flame retardant accounts for 2.5% of the mass of the rigid polyurethane foam.
  • the flame retardant provided in this embodiment includes a composite additive flame retardant and a composite reactive flame retardant in a mass ratio of 100:80;
  • the composite additive flame retardant includes the following components by weight: 30 parts of aluminum hydroxide, 25 parts of montmorillonite, 25 parts of tris(2-chloroisopropyl) phosphate, 6.67 parts of triethyl phosphate and 13.33 parts of triphenyl phosphate;
  • the composite reactive flame retardant comprises the following components by weight: 50 parts of di(4-hydroxybutyl)phenyl phosphate and 30 parts of 2-carboxyethylphenyl phosphite glycol ester.
  • the preparation method of the rigid polyurethane foam provided in this embodiment refers to that in Embodiment 1, the difference is that the mass of the added flame retardant accounts for 3.5% of the mass of the rigid polyurethane foam.
  • the flame retardant provided in this comparative example is an inorganic flame retardant: 3000 mesh aluminum hydroxide particles.
  • the preparation method of the rigid polyurethane foam provided in this comparative example refers to Example 1, except that the mass of the added flame retardant accounts for 5% of the mass of the rigid polyurethane foam.
  • the flame retardant provided in this comparative example is a phosphorus-based flame retardant: triethyl phosphate.
  • the preparation method of the rigid polyurethane foam provided in this comparative example refers to Example 1, except that the mass of the added flame retardant accounts for 4% of the mass of the rigid polyurethane foam.
  • the oxygen index of the rigid polyurethane foams prepared in Examples 1 to 4, the rigid polyurethane foams prepared in Comparative Examples 1 to 2, and the original rigid polyurethane foaming system were tested, and the results are shown in Tables 1 and 2.
  • the original rigid polyurethane foaming system is a system without adding a flame retardant, that is, a rigid polyurethane foam product obtained by mixing polyol and isocyanate and fully foaming and molding.
  • the flame retardant of the invention can improve the flame retardant effect of the rigid polyurethane foam without affecting the mechanical properties of the rigid polyurethane foam.
  • the present disclosure provides a flame retardant, a preparation method thereof and a rigid polyurethane foam.
  • the flame retardant disclosed herein includes a composite additive flame retardant and a composite reactive flame retardant; the composite additive flame retardant includes the following components by weight: 1 to 80 parts of inorganic flame retardant, 1 to 75 parts of phosphorus halogen flame retardant and 5 to 60 parts of organic phosphorus flame retardant; the composite reactive flame retardant includes the following components by weight: 20 to 100 parts of di(4-hydroxybutyl)phenyl phosphate and 30 to 150 parts of 2-carboxyethylphenyl phosphite glycol ester; the mass ratio of the composite additive flame retardant to the composite reactive flame retardant is 100:60 to 150.
  • the flame retardant disclosed herein can improve the flame retardant effect of rigid polyurethane foam without affecting the mechanical properties of rigid polyurethane foam.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The present disclosure relates to the technical field of flame retardants, in particular to a flame retardant, a preparation method therefor, and rigid polyurethane foam. The flame retardant of the present invention comprises a composite additive-type flame retardant and a composite reactive-type flame retardant. The composite additive-type flame retardant comprises the following components in parts by weight: 1-80 parts of an inorganic flame retardant, 1-75 parts of a phosphorus halogen flame retardant, and 5-60 parts of an organophosphorus flame retardant. The composite reactive-type flame retardant comprises the following components in parts by weight: 20-100 parts of bis(4-hydroxybutyl)phenyl phosphate and 30-150 parts of 2-carboxyethyl phenyl ethylene glycol hypophosphite. The mass ratio of the composite additive-type flame retardant to the composite reactive-type flame retardant is 100:60 to 100:150. The flame retardant of the present invention can improve the flame-retardant effect of rigid polyurethane foam without affecting the mechanical properties of the rigid polyurethane foam.

Description

一种阻燃剂及其制备方法和硬质聚氨酯泡沫Flame retardant and preparation method thereof and rigid polyurethane foam
相关申请的交叉引用CROSS-REFERENCE TO RELATED APPLICATIONS
本申请要求于2022年11月02日提交中国专利局的申请号为202211360454.0、名称为“一种阻燃剂及其制备方法和硬质聚氨酯泡沫”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims priority to a Chinese patent application with application number 202211360454.0 filed with the Chinese Patent Office on November 2, 2022, and entitled “A flame retardant, a preparation method thereof, and rigid polyurethane foam”, the entire contents of which are incorporated by reference into this application.
技术领域Technical Field
本公开涉及阻燃剂技术领域，尤其是涉及一种阻燃剂及其制备方法和硬质聚氨酯泡沫。The present disclosure relates to the technical field of flame retardants, and in particular to a flame retardant and a preparation method thereof, and a rigid polyurethane foam.
背景技术Background technique
硬质聚氨酯泡沫是以异氰酸酯和聚醚为主要原料，在发泡剂、催化剂等多种助剂的作用下，通过专用设备混合，经高压喷涂现场发泡而成的高分子聚合物，具有重量轻、耐化学药品性能强、冲击吸能性能以及隔音和绝热性能好、成型加工方便等特点，应用范围十分广泛，可用于交通运输、建筑、包装、冷藏等诸多行业。但硬质聚氨酯泡沫的阻燃性能较差，极易燃烧且燃烧火蔓延极为迅速，在燃烧过程中释放的大量烟颗粒对环境造成较大的污染，产生的有毒气体在火灾中极易造成大量人员伤亡，限制了硬质聚氨酯泡沫的应用。Rigid polyurethane foam is a high molecular polymer made of isocyanate and polyether as the main raw materials, mixed with special equipment under the action of various additives such as foaming agent and catalyst, and foamed on site by high-pressure spraying. It has the characteristics of light weight, strong chemical resistance, impact energy absorption, good sound insulation and heat insulation, convenient molding and processing, etc. It has a wide range of applications and can be used in many industries such as transportation, construction, packaging, refrigeration, etc. However, rigid polyurethane foam has poor flame retardant properties, is very easy to burn, and the fire spreads very quickly. The large amount of smoke particles released during the combustion process causes great pollution to the environment, and the toxic gases produced can easily cause a large number of casualties in the fire, which limits the application of rigid polyurethane foam.
目前，在传统应用中，主要依赖添加型阻燃剂提高硬质聚氨酯泡沫塑料的阻燃效果。但传统阻燃剂存在一些问题，如卤磷系阻燃剂存在产烟量大及产烟毒性等环境问题；无机阻燃剂添加量过大会降低材料力学性能等问题；膨胀型阻燃剂存在热解形成的蠕虫状炭层松散，与聚合物之间的界面相容性较差，导致力学性能下降的问题等。因此，开发提高阻燃效果，不影响硬质聚氨酯泡沫力学性能的硬质聚氨酯泡沫用阻燃剂的技术研究十分必要。At present, in traditional applications, additive flame retardants are mainly used to improve the flame retardant effect of rigid polyurethane foam plastics. However, there are some problems with traditional flame retardants, such as the large amount of smoke produced and the toxicity of smoke produced by halogen-phosphorus flame retardants; excessive addition of inorganic flame retardants will reduce the mechanical properties of the material; and the worm-like carbon layer formed by pyrolysis of intumescent flame retardants is loose, and the interface compatibility between the polymer and the polymer is poor, resulting in a decrease in mechanical properties. Therefore, it is necessary to develop technical research on flame retardants for rigid polyurethane foam that can improve the flame retardant effect without affecting the mechanical properties of rigid polyurethane foam.
申请内容Application Contents
本公开的第一目的在于提供一种阻燃剂，能够在不影响硬质聚氨酯泡沫力学性能的基础上提高硬质聚氨酯泡沫的阻燃效果。The first object of the present disclosure is to provide a flame retardant that can improve the flame retardant effect of rigid polyurethane foam without affecting the mechanical properties of the rigid polyurethane foam.
本公开的第二目的在于提供一种如上所述的阻燃剂的制备方法，该方法步骤简单。 The second object of the present disclosure is to provide a method for preparing the flame retardant as described above, which has simple steps.
本公开的第三目的在于提供一种硬质聚氨酯泡沫，其兼具优异的力学性能和阻燃性能。The third object of the present disclosure is to provide a rigid polyurethane foam having both excellent mechanical properties and flame retardant properties.
为了实现本公开的上述目的，特采用以下技术方案：In order to achieve the above-mentioned purpose of the present disclosure, the following technical solutions are specially adopted:
本公开提供了一种阻燃剂，包括复合添加型阻燃剂和复合反应型阻燃剂；The present disclosure provides a flame retardant, including a composite additive flame retardant and a composite reactive flame retardant;
所述复合添加型阻燃剂，包括按重量份数计的如下组分：1～80份无机阻燃剂、1～75份磷卤阻燃剂和5～60份有机磷阻燃剂；The composite additive flame retardant comprises the following components by weight: 1 to 80 parts of inorganic flame retardant, 1 to 75 parts of phosphorus halogen flame retardant and 5 to 60 parts of organic phosphorus flame retardant;
所述复合反应型阻燃剂，包括按重量份数计的如下组分：二(4-羟丁基)苯基磷酸酯20～100份和2-羧乙基苯基次磷酸乙二醇脂30～150份；The composite reactive flame retardant comprises the following components by weight: 20 to 100 parts of di(4-hydroxybutyl)phenyl phosphate and 30 to 150 parts of 2-carboxyethylphenyl phosphite glycol ester;
所述复合添加型阻燃剂和所述复合反应型阻燃剂的质量比为100：60～150。The mass ratio of the composite additive flame retardant to the composite reactive flame retardant is 100:60-150.
进一步地，所述复合添加型阻燃剂，包括按重量份数计的如下组分：25～55份无机阻燃剂、25～50份磷卤阻燃剂和10～40份有机磷阻燃剂。Furthermore, the composite additive flame retardant includes the following components in parts by weight: 25 to 55 parts of inorganic flame retardant, 25 to 50 parts of phosphorus halogen flame retardant and 10 to 40 parts of organic phosphorus flame retardant.
进一步地，所述二(4-羟丁基)苯基磷酸酯和所述2-羧乙基苯基次磷酸乙二醇脂的质量比为1：0.5～1.5。Furthermore, the mass ratio of the di(4-hydroxybutyl)phenyl phosphate to the 2-carboxyethylphenyl phosphite glycol ester is 1:0.5-1.5.
进一步地，所述无机阻燃剂包括氢氧化铝和蒙脱土。Furthermore, the inorganic flame retardant includes aluminum hydroxide and montmorillonite.
进一步地，所述氢氧化铝和所述蒙脱土的质量比为6：4～8。Furthermore, the mass ratio of the aluminum hydroxide to the montmorillonite is 6:4-8.
进一步地，所述磷卤阻燃剂包括磷酸三(2-氯异丙基)酯。Furthermore, the phosphorus halogen flame retardant includes tris(2-chloroisopropyl) phosphate.
进一步地，所述有机磷阻燃剂包括磷酸三乙酯和磷酸三苯酯。Furthermore, the organophosphorus flame retardant includes triethyl phosphate and triphenyl phosphate.
进一步地，所述磷酸三乙酯和所述磷酸三苯酯的质量比3：4～9。Furthermore, the mass ratio of the triethyl phosphate to the triphenyl phosphate is 3:4-9.
本公开还提供了如上所述的阻燃剂的制备方法，包括如下步骤：各组分混匀后，得到所述阻燃剂。The present disclosure also provides a method for preparing the flame retardant as described above, comprising the following steps: after uniformly mixing the components, the flame retardant is obtained.
本公开还提供了一种硬质聚氨酯泡沫，包括如上所述的阻燃剂。The present disclosure also provides a rigid polyurethane foam, comprising the flame retardant as described above.
进一步地，所述硬质聚氨酯泡沫中，所述阻燃剂的质量百分数为0.5％～3.5％。Furthermore, in the rigid polyurethane foam, the mass percentage of the flame retardant is 0.5% to 3.5%.
与现有技术相比，本公开的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
本公开提供了一种阻燃剂，该阻燃剂可作为硬质聚氨酯泡沫用阻燃剂，可以大幅度提高硬质聚氨酯泡沫的阻燃效果，且不影响硬质聚氨酯泡沫力学性能；向硬质聚氨酯泡沫中添加本公开的阻燃剂，可在保持硬质聚氨酯泡沫原有力学性能的基础上，将硬质聚氨酯泡沫的氧指数从21提升至23～30。The present disclosure provides a flame retardant, which can be used as a flame retardant for rigid polyurethane foam, can greatly improve the flame retardant effect of the rigid polyurethane foam, and does not affect the mechanical properties of the rigid polyurethane foam; adding the flame retardant of the present disclosure to the rigid polyurethane foam can increase the oxygen index of the rigid polyurethane foam from 21 to 23-30 while maintaining the original mechanical properties of the rigid polyurethane foam.
具体实施方式Detailed ways
下面对本公开实施例的一种阻燃剂及其制备方法和硬质聚氨酯泡沫进行具体说明。 A flame retardant and a preparation method thereof and a rigid polyurethane foam according to an embodiment of the present disclosure are described in detail below.
在本公开的一些实施方式中提供了一种阻燃剂，包括复合添加型阻燃剂和复合反应型阻燃剂；In some embodiments of the present disclosure, a flame retardant is provided, including a composite additive flame retardant and a composite reactive flame retardant;
复合添加型阻燃剂，包括按重量份数计的如下组分：1～80份无机阻燃剂、1～75份磷卤阻燃剂和5～60份有机磷阻燃剂；The composite additive flame retardant comprises the following components by weight: 1 to 80 parts of inorganic flame retardant, 1 to 75 parts of phosphorus halogen flame retardant and 5 to 60 parts of organic phosphorus flame retardant;
复合反应型阻燃剂，包括按重量份数计的如下组分：二(4-羟丁基)苯基磷酸酯20～100份和2-羧乙基苯基次磷酸乙二醇脂30～150份；The composite reactive flame retardant comprises the following components by weight: 20 to 100 parts of di(4-hydroxybutyl)phenyl phosphate and 30 to 150 parts of 2-carboxyethylphenyl phosphite glycol ester;
复合添加型阻燃剂和复合反应型阻燃剂的质量比为100：60～150。The mass ratio of the composite additive flame retardant to the composite reactive flame retardant is 100:60-150.
本公开提供的阻燃剂，具有优异的阻燃效果，并且，将本公开的阻燃剂添加到硬质聚氨酯泡沫中，能够在不影响硬质聚氨酯泡沫原有的力学性能的基础上，显著提高硬质聚氨酯泡沫的阻燃性，大幅度提高氧指数的数值。The flame retardant provided by the present disclosure has an excellent flame retardant effect, and adding the flame retardant of the present disclosure to the rigid polyurethane foam can significantly improve the flame retardancy of the rigid polyurethane foam and greatly increase the value of the oxygen index without affecting the original mechanical properties of the rigid polyurethane foam.
本公开的阻燃剂由复合添加型阻燃剂和复合反应型阻燃剂两部分组成，复合添加型主要起到在着火高温环境下分解成释放水，从而起到阻燃效果，复合反应型阻燃剂主要起到的是在着火时气相上释放自由基捕获燃烧反应链增长的自由基，从而起到阻燃效果。本公开的阻燃剂原料在具备阻燃性能的同时，对产品原料的表面张力影响很小，可以最大程度的保证在硬质聚氨酯泡沫发泡过程中泡孔的完整性(闭孔泡沫)，保证了炮孔的完整性在相同原料配比的情况下就保证了硬质聚氨酯泡沫抗压性能。The flame retardant disclosed in the present invention is composed of a composite additive flame retardant and a composite reactive flame retardant. The composite additive mainly decomposes into released water under a high temperature environment of fire, thereby achieving a flame retardant effect. The composite reactive flame retardant mainly releases free radicals in the gas phase during fire to capture the free radicals of the combustion reaction chain growth, thereby achieving a flame retardant effect. The flame retardant raw material disclosed in the present invention has a flame retardant property and has little effect on the surface tension of the product raw material. It can guarantee the integrity of the foam cells (closed-cell foam) during the foaming process of the rigid polyurethane foam to the greatest extent, and ensures the integrity of the blast hole. Under the same raw material ratio, the compression resistance of the rigid polyurethane foam is guaranteed.
在本公开的一些实施方式中，复合添加型阻燃剂中，典型但非限制性的，例如，无机阻燃剂的重量份数为1份、5份、10份、15份、20份、25份、30份、35份、40份、45份、50份、55份、60份、65份、70份、75份或者80份等等；磷卤阻燃剂的重量份数为1份、5份、10份、15份、20份、25份、30份、35份、40份、45份、50份、55份、60份、65份、70份或者75等等；有机磷阻燃剂的重量份数为5份、10份、15份、20份、25份、30份、35份、40份、45份、50份、55份或者60份等等。In some embodiments of the present disclosure, in the composite additive flame retardant, typically but not limiting, for example, the weight proportion of the inorganic flame retardant is 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts or 80 parts, etc.; the weight proportion of the phosphorus halogen flame retardant is 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts or 75 parts, etc.; the weight proportion of the organophosphorus flame retardant is 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts or 60 parts, etc.
在本公开的一些实施方式中，复合反应型阻燃剂中，典型但非限制性的，例如，二(4-羟丁基)苯基磷酸酯的重量份数为10份、20份、30份、40份、50份、60份、70份、80份、90份或者100份等等；2-羧乙基苯基次磷酸乙二醇脂的重量份数为30份、40份、50份、60份、70份、80份、90份、100份、110份、120份、130份、140份或者150份等等。 In some embodiments of the present disclosure, in the composite reactive flame retardant, typically but not limiting, for example, the weight proportion of di(4-hydroxybutyl)phenyl phosphate is 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts or 100 parts, etc.; the weight proportion of 2-carboxyethylphenyl phosphite is 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts or 150 parts, etc.
在本公开的一些实施方式中，复合添加型阻燃剂和复合反应型阻燃剂的质量比为100：60、100：70、100：80、100：90、100：100、100：110、100：120、100：130、100：140或者100：150等等。In some embodiments of the present disclosure, the mass ratio of the composite additive flame retardant to the composite reactive flame retardant is 100:60, 100:70, 100:80, 100:90, 100:100, 100:110, 100:120, 100:130, 100:140 or 100:150, etc.
在本公开的一些实施方式中，复合添加型阻燃剂，包括按重量份数计的如下组分：25～55份无机阻燃剂、25～50份磷卤阻燃剂和10～40份有机磷阻燃剂。In some embodiments of the present disclosure, the composite additive flame retardant includes the following components in parts by weight: 25 to 55 parts of inorganic flame retardant, 25 to 50 parts of phosphorus halogen flame retardant and 10 to 40 parts of organic phosphorus flame retardant.
在本公开的一些实施方式中，二(4-羟丁基)苯基磷酸酯和2-羧乙基苯基次磷酸乙二醇脂的质量比为1：0.5～1.5；典型但非限制性的，例如，二(4-羟丁基)苯基磷酸酯和2-羧乙基苯基次磷酸乙二醇脂的质量比为1：0.5、1：0.6、1：0.7、1：0.8、1：0.9、1：1、1：1.1、1：1.2、1：1.3、1：1.4或者1：1.5等等。In some embodiments of the present disclosure, the mass ratio of di(4-hydroxybutyl)phenyl phosphate and 2-carboxyethylphenyl phosphite glycol ester is 1:0.5-1.5; typically but not limiting, for example, the mass ratio of di(4-hydroxybutyl)phenyl phosphate and 2-carboxyethylphenyl phosphite glycol ester is 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5, etc.
在本公开的一些实施方式中，硬质聚氨酯泡沫用阻燃剂，包括复合添加型阻燃剂和复合反应型阻燃剂；In some embodiments of the present disclosure, the flame retardant for rigid polyurethane foam includes a composite additive flame retardant and a composite reactive flame retardant;
复合添加型阻燃剂，包括按重量份数计的如下组分：25～55份无机阻燃剂、25～50份磷卤阻燃剂和10～40份有机磷阻燃剂；The composite additive flame retardant comprises the following components by weight: 25 to 55 parts of inorganic flame retardant, 25 to 50 parts of phosphorus halogen flame retardant and 10 to 40 parts of organic phosphorus flame retardant;
复合反应型阻燃剂，包括按重量份数计的如下组分：二(4-羟丁基)苯基磷酸酯100份和2-羧乙基苯基次磷酸乙二醇脂50～150份；The composite reactive flame retardant comprises the following components by weight: 100 parts of di(4-hydroxybutyl)phenyl phosphate and 50-150 parts of 2-carboxyethylphenyl phosphite glycol ester;
复合添加型阻燃剂和复合反应型阻燃剂的质量比为100：60～150。The mass ratio of the composite additive flame retardant to the composite reactive flame retardant is 100:60-150.
在本公开的一些实施方式中，无机阻燃剂包括氢氧化铝和蒙脱土；进一步地，氢氧化铝和蒙脱土的质量比为6：4～8；典型但非限制性的，例如，氢氧化铝和蒙脱土的质量比为6：4、6：5、6：6、6：7或者6：8等等。In some embodiments of the present disclosure, the inorganic flame retardant includes aluminum hydroxide and montmorillonite; further, the mass ratio of aluminum hydroxide to montmorillonite is 6:4-8; typically but not limitatively, for example, the mass ratio of aluminum hydroxide to montmorillonite is 6:4, 6:5, 6:6, 6:7 or 6:8, etc.
在本公开的一些实施方式中，磷卤阻燃剂包括磷酸三(2-氯异丙基)酯。磷酸三(2-氯异丙基)酯在价格便宜的同时，相比其他磷卤阻燃剂更加容易释放出更多的PO·和Cl·自由基捕获燃烧反应链增长的自由基从而更具性价比的并且更高效的起到阻燃效果。相比于其他种类的磷卤阻燃剂，磷酸三(2-氯异丙基)酯与体系的其他组分具有更加优异的配合效果。In some embodiments of the present disclosure, the phosphorus halogen flame retardant includes tris(2-chloroisopropyl) phosphate. Tris(2-chloroisopropyl) phosphate is cheap and, compared with other phosphorus halogen flame retardants, is easier to release more PO· and Cl· free radicals to capture the free radicals of the combustion reaction chain growth, thereby being more cost-effective and more efficient in achieving a flame retardant effect. Compared with other types of phosphorus halogen flame retardants, tris(2-chloroisopropyl) phosphate has a more excellent coordination effect with other components of the system.
在本公开的一些实施方式中，有机磷阻燃剂包括磷酸三乙酯和磷酸三苯酯。In some embodiments of the present disclosure, the organophosphorus flame retardant includes triethyl phosphate and triphenyl phosphate.
在本公开的一些实施方式中，磷酸三乙酯和磷酸三苯酯的质量比3：4～9；典型但非限制性的，例如，磷酸三乙酯和磷酸三苯酯的质量比3：4、3：5、3：6、3：7、3：8或者3：9等等。 In some embodiments of the present disclosure, the mass ratio of triethyl phosphate to triphenyl phosphate is 3:4-9; typically but not limiting, for example, the mass ratio of triethyl phosphate to triphenyl phosphate is 3:4, 3:5, 3:6, 3:7, 3:8 or 3:9, etc.
本公开的阻燃剂，通过控制各组分的配比关系，使其对于硬质聚氨酯泡沫泡孔完整性的影响最小，更有利于硬质聚氨酯泡沫抗压强度的保持。The flame retardant disclosed in the present invention minimizes the influence on the integrity of the rigid polyurethane foam cells by controlling the ratio of each component, which is more conducive to maintaining the compressive strength of the rigid polyurethane foam.
在本公开的一些实施方式中还提供了如上所述的阻燃剂的制备方法，包括如下步骤：各组分混匀后，得到阻燃剂。In some embodiments of the present disclosure, a method for preparing the flame retardant as described above is also provided, comprising the following steps: after mixing the components, a flame retardant is obtained.
在本公开的一些实施方式中，阻燃剂的制备方法，包括如下步骤：将无机阻燃剂、磷卤阻燃剂、有机磷阻燃剂、二(4-羟丁基)苯基磷酸酯和2-羧乙基苯基次磷酸乙二醇脂充分搅拌混合0.5～2h后，得到阻燃剂；进一步地，搅拌的温度为20～30℃。In some embodiments of the present disclosure, a method for preparing a flame retardant comprises the following steps: fully stirring and mixing an inorganic flame retardant, a phosphorus halogen flame retardant, an organic phosphorus flame retardant, di(4-hydroxybutyl)phenyl phosphate and 2-carboxyethylphenyl phosphite glycol ester for 0.5 to 2 hours to obtain a flame retardant; further, the stirring temperature is 20 to 30°C.
在本公开的一些实施方式中还提供了一种硬质聚氨酯泡沫，包括上述阻燃剂。In some embodiments of the present disclosure, a rigid polyurethane foam is also provided, comprising the flame retardant.
在本公开的一些实施方式中，硬质聚氨酯泡沫中，阻燃剂的质量百分数为0.5％～3.5％；典型但非限制性的，例如，硬质聚氨酯泡沫中，阻燃剂的质量百分数为0.5％、1％、1.5％、2％、2.5％、3％或者3.5％等等。In some embodiments of the present disclosure, the mass percentage of the flame retardant in the rigid polyurethane foam is 0.5% to 3.5%; typically but not limiting, for example, the mass percentage of the flame retardant in the rigid polyurethane foam is 0.5%, 1%, 1.5%, 2%, 2.5%, 3% or 3.5%, etc.
本公开的硬质聚氨酯泡沫体系中加入上述阻燃剂，可在不影响硬质聚氨酯泡沫力学性能的条件下，大幅提高阻燃性能；在不影响力学性能的前提下可将氧指数从21提升至23～30。Adding the flame retardant to the rigid polyurethane foam system disclosed herein can significantly improve the flame retardancy without affecting the mechanical properties of the rigid polyurethane foam; and can increase the oxygen index from 21 to 23-30 without affecting the mechanical properties.
实施例1Example 1
本实施例提供的阻燃剂，包括质量比为100：100的复合添加型阻燃剂和复合反应型阻燃剂；The flame retardant provided in this embodiment includes a composite additive flame retardant and a composite reactive flame retardant in a mass ratio of 100:100;
复合添加型阻燃剂包括按重量份数计的如下组分：氢氧化铝15份、蒙脱土10份、磷酸三(2-氯异丙基)酯35份、磷酸三乙酯12份和磷酸三苯酯28份；The composite additive flame retardant includes the following components by weight: 15 parts of aluminum hydroxide, 10 parts of montmorillonite, 35 parts of tri(2-chloroisopropyl) phosphate, 12 parts of triethyl phosphate and 28 parts of triphenyl phosphate;
复合反应型阻燃剂包括按重量份数计的如下组分：二(4-羟丁基)苯基磷酸酯50份和2-羧乙基苯基次磷酸乙二醇脂50份。The composite reactive flame retardant comprises the following components in parts by weight: 50 parts of di(4-hydroxybutyl)phenyl phosphate and 50 parts of 2-carboxyethylphenyl phosphite glycol ester.
本实施例提供的阻燃剂的制备方法，包括以下步骤：The method for preparing the flame retardant provided in this embodiment comprises the following steps:
将氢氧化铝15份、蒙脱土10份、磷酸三(2-氯异丙基)酯35份、磷酸三乙酯12份、磷酸三苯酯28份、二(4-羟丁基)苯基磷酸酯50份和2-羧乙基苯基次磷酸乙二醇脂50份用行星搅拌釜在常温下充分搅拌混合1h后，得到阻燃剂。15 parts of aluminum hydroxide, 10 parts of montmorillonite, 35 parts of tris(2-chloroisopropyl) phosphate, 12 parts of triethyl phosphate, 28 parts of triphenyl phosphate, 50 parts of di(4-hydroxybutyl)phenyl phosphate and 50 parts of 2-carboxyethylphenyl phosphite glycol were fully stirred and mixed in a planetary stirring kettle at room temperature for 1 hour to obtain a flame retardant.
本实施例提供的硬质聚氨酯泡沫的制备方法，包括将上述阻燃剂加入到硬质聚氨酯发泡体系中(阻燃剂添加质量占硬质聚氨酯泡沫质量的1.1％)。具体步骤为：上述阻燃剂与多元醇混合均匀后，再加入异氰酸酯混匀，充分发泡成型后得到的硬质聚氨酯泡沫。 The method for preparing the rigid polyurethane foam provided in this embodiment comprises adding the flame retardant mentioned above into the rigid polyurethane foaming system (the mass of the flame retardant added accounts for 1.1% of the mass of the rigid polyurethane foam). The specific steps are: after the flame retardant and the polyol are evenly mixed, isocyanate is added and mixed, and the rigid polyurethane foam is obtained after sufficient foaming and molding.
实施例2Example 2
本实施例提供的阻燃剂，包括质量比为100：60的复合添加型阻燃剂和复合反应型阻燃剂；The flame retardant provided in this embodiment includes a composite additive flame retardant and a composite reactive flame retardant in a mass ratio of 100:60;
复合添加型阻燃剂包括按重量份数计的如下组分：氢氧化铝17份、蒙脱土23份、磷酸三(2-氯异丙基)酯50份、磷酸三乙酯2.5份和磷酸三苯酯7.5份；The composite additive flame retardant includes the following components by weight: 17 parts of aluminum hydroxide, 23 parts of montmorillonite, 50 parts of tri(2-chloroisopropyl) phosphate, 2.5 parts of triethyl phosphate and 7.5 parts of triphenyl phosphate;
复合反应型阻燃剂包括按重量份数计的如下组分：二(4-羟丁基)苯基磷酸酯25份和2-羧乙基苯基次磷酸乙二醇脂35份。The composite reactive flame retardant comprises the following components by weight: 25 parts of di(4-hydroxybutyl)phenyl phosphate and 35 parts of 2-carboxyethylphenyl phosphite glycol ester.
本实施例提供的阻燃剂的制备方法，包括以下步骤：The method for preparing the flame retardant provided in this embodiment comprises the following steps:
将氢氧化铝17份、蒙脱土23份、磷酸三(2-氯异丙基)酯50份、磷酸三乙酯2.5份、磷酸三苯酯7.5份、二(4-羟丁基)苯基磷酸酯25份和2-羧乙基苯基次磷酸乙二醇脂35份用行星搅拌釜在常温下充分搅拌混合1.5h后，得到阻燃剂。17 parts of aluminum hydroxide, 23 parts of montmorillonite, 50 parts of tri(2-chloroisopropyl) phosphate, 2.5 parts of triethyl phosphate, 7.5 parts of triphenyl phosphate, 25 parts of di(4-hydroxybutyl)phenyl phosphate and 35 parts of 2-carboxyethylphenyl phosphite glycol were fully stirred and mixed in a planetary stirring kettle at room temperature for 1.5 hours to obtain a flame retardant.
本实施例提供的硬质聚氨酯泡沫的制备方法参考实施例1，不同之处在于：阻燃剂添加质量占硬质聚氨酯泡沫质量的2.0％。The preparation method of the rigid polyurethane foam provided in this embodiment refers to that in Example 1, the difference is that the mass of the added flame retardant accounts for 2.0% of the mass of the rigid polyurethane foam.
实施例3Example 3
本实施例提供的阻燃剂，包括质量比为100：150的复合添加型阻燃剂和复合反应型阻燃剂；The flame retardant provided in this embodiment includes a composite additive flame retardant and a composite reactive flame retardant in a mass ratio of 100:150;
复合添加型阻燃剂包括按重量份数计的如下组分：氢氧化铝22.5份、蒙脱土22.5份、磷酸三(2-氯异丙基)酯25份、磷酸三乙酯8份和磷酸三苯酯22份；The composite additive flame retardant includes the following components by weight: 22.5 parts of aluminum hydroxide, 22.5 parts of montmorillonite, 25 parts of tri(2-chloroisopropyl) phosphate, 8 parts of triethyl phosphate and 22 parts of triphenyl phosphate;
复合反应型阻燃剂包括按重量份数计的如下组分：二(4-羟丁基)苯基磷酸酯75份和2-羧乙基苯基次磷酸乙二醇脂75份。The composite reactive flame retardant comprises the following components in parts by weight: 75 parts of di(4-hydroxybutyl)phenyl phosphate and 75 parts of 2-carboxyethylphenyl phosphite glycol ester.
本实施例提供的阻燃剂的制备方法，包括以下步骤：The method for preparing the flame retardant provided in this embodiment comprises the following steps:
将氢氧化铝22.5份、蒙脱土22.5份、磷酸三(2-氯异丙基)酯25份、磷酸三乙酯8份、磷酸三苯酯22份、二(4-羟丁基)苯基磷酸酯75份和2-羧乙基苯基次磷酸乙二醇脂75份用行星搅拌釜在常温下充分搅拌混合1h后，得到阻燃剂。22.5 parts of aluminum hydroxide, 22.5 parts of montmorillonite, 25 parts of tri(2-chloroisopropyl) phosphate, 8 parts of triethyl phosphate, 22 parts of triphenyl phosphate, 75 parts of di(4-hydroxybutyl)phenyl phosphate and 75 parts of 2-carboxyethylphenyl phosphite glycol were fully stirred and mixed in a planetary stirring kettle at room temperature for 1 hour to obtain a flame retardant.
本实施例提供的硬质聚氨酯泡沫的制备方法参考实施例1，不同之处在于：阻燃剂添加质量占硬质聚氨酯泡沫质量的2.5％。The preparation method of the rigid polyurethane foam provided in this embodiment refers to that in Embodiment 1, the difference is that the mass of the added flame retardant accounts for 2.5% of the mass of the rigid polyurethane foam.
实施例4 Example 4
本实施例提供的阻燃剂，包括质量比为100：80的复合添加型阻燃剂和复合反应型阻燃剂；The flame retardant provided in this embodiment includes a composite additive flame retardant and a composite reactive flame retardant in a mass ratio of 100:80;
复合添加型阻燃剂包括按重量份数计的如下组分：氢氧化铝30份、蒙脱土25份、磷酸三(2-氯异丙基)酯25份、磷酸三乙酯6.67份和磷酸三苯酯13.33份；The composite additive flame retardant includes the following components by weight: 30 parts of aluminum hydroxide, 25 parts of montmorillonite, 25 parts of tris(2-chloroisopropyl) phosphate, 6.67 parts of triethyl phosphate and 13.33 parts of triphenyl phosphate;
复合反应型阻燃剂包括按重量份数计的如下组分：二(4-羟丁基)苯基磷酸酯50份和2-羧乙基苯基次磷酸乙二醇脂30份。The composite reactive flame retardant comprises the following components by weight: 50 parts of di(4-hydroxybutyl)phenyl phosphate and 30 parts of 2-carboxyethylphenyl phosphite glycol ester.
本实施例提供的阻燃剂的制备方法，包括以下步骤：The method for preparing the flame retardant provided in this embodiment comprises the following steps:
将氢氧化铝30份、蒙脱土25份、磷酸三(2-氯异丙基)酯25份、磷酸三乙酯6.67份、磷酸三苯酯13.33份、二(4-羟丁基)苯基磷酸酯50份和2-羧乙基苯基次磷酸乙二醇脂50份用行星搅拌釜在常温下充分搅拌混合1h后，得到阻燃剂。30 parts of aluminum hydroxide, 25 parts of montmorillonite, 25 parts of tri(2-chloroisopropyl) phosphate, 6.67 parts of triethyl phosphate, 13.33 parts of triphenyl phosphate, 50 parts of di(4-hydroxybutyl)phenyl phosphate and 50 parts of 2-carboxyethylphenyl phosphite glycol were fully stirred and mixed in a planetary stirring kettle at room temperature for 1 hour to obtain a flame retardant.
本实施例提供的硬质聚氨酯泡沫的制备方法参考实施例1，不同之处在于：阻燃剂添加质量占硬质聚氨酯泡沫质量的3.5％。The preparation method of the rigid polyurethane foam provided in this embodiment refers to that in Embodiment 1, the difference is that the mass of the added flame retardant accounts for 3.5% of the mass of the rigid polyurethane foam.
对比例1Comparative Example 1
本对比例提供的阻燃剂为无机阻燃剂：3000目的氢氧化铝颗粒。The flame retardant provided in this comparative example is an inorganic flame retardant: 3000 mesh aluminum hydroxide particles.
本对比例提供的硬质聚氨酯泡沫的制备方法参考实施例1，不同之处在于：阻燃剂添加质量占硬质聚氨酯泡沫质量的5％。The preparation method of the rigid polyurethane foam provided in this comparative example refers to Example 1, except that the mass of the added flame retardant accounts for 5% of the mass of the rigid polyurethane foam.
对比例2Comparative Example 2
本对比例提供的阻燃剂为磷系阻燃剂：磷酸三乙酯。The flame retardant provided in this comparative example is a phosphorus-based flame retardant: triethyl phosphate.
本对比例提供的硬质聚氨酯泡沫的制备方法参考实施例1，不同之处在于：阻燃剂添加质量占硬质聚氨酯泡沫质量的4％。The preparation method of the rigid polyurethane foam provided in this comparative example refers to Example 1, except that the mass of the added flame retardant accounts for 4% of the mass of the rigid polyurethane foam.
试验例1Test Example 1
对实施例1～4制得的硬质聚氨酯泡沫、对比例1～2制得的硬质聚氨酯泡沫和原始硬质聚氨酯发泡体系的氧指数进行测试，其结果如表1和表2所示。其中，原始硬质聚氨酯发泡体系为未添加阻燃剂的体系，即由多元醇和异氰酸酯混匀，充分发泡成型后得到的硬质聚氨酯泡沫产品。The oxygen index of the rigid polyurethane foams prepared in Examples 1 to 4, the rigid polyurethane foams prepared in Comparative Examples 1 to 2, and the original rigid polyurethane foaming system were tested, and the results are shown in Tables 1 and 2. The original rigid polyurethane foaming system is a system without adding a flame retardant, that is, a rigid polyurethane foam product obtained by mixing polyol and isocyanate and fully foaming and molding.
表1
Table 1
表2
Table 2
对实施例1～4制得的硬质聚氨酯泡沫、对比例1～2制得的硬质聚氨酯泡沫相比于原始硬质聚氨酯发泡体系抗压强度的下降率进行测试，其结果如表3所示。The decrease rate of the compressive strength of the rigid polyurethane foams prepared in Examples 1 to 4 and the rigid polyurethane foams prepared in Comparative Examples 1 to 2 compared with the original rigid polyurethane foaming system was tested, and the results are shown in Table 3.
表3
table 3
从表1、表2和表3可以看出，发明的阻燃剂能够在不影响硬质聚氨酯泡沫力学性能的基础上提高硬质聚氨酯泡沫的阻燃效果。It can be seen from Table 1, Table 2 and Table 3 that the flame retardant of the invention can improve the flame retardant effect of the rigid polyurethane foam without affecting the mechanical properties of the rigid polyurethane foam.
工业实用性Industrial Applicability
本公开提供了一种阻燃剂及其制备方法和硬质聚氨酯泡沫。本公开的阻燃剂，包括复合添加型阻燃剂和复合反应型阻燃剂；所述复合添加型阻燃剂，包括按重量份数计的如下组分：1～80份无机阻燃剂、1～75份磷卤阻燃剂和5～60份有机磷阻燃剂；所述复合反应型阻燃剂，包括按重量份数计的如下组分：二(4-羟丁基)苯基磷酸酯20～100份和2-羧乙基苯基次磷酸乙二醇脂30～150份；所述复合添加型阻燃剂和所述复合反应型阻燃剂的质量比为100：60～150。本公开的阻燃剂能够在不影响硬质聚氨酯泡沫力学性能的基础上提高硬质聚氨酯泡沫的阻燃效果。 The present disclosure provides a flame retardant, a preparation method thereof and a rigid polyurethane foam. The flame retardant disclosed herein includes a composite additive flame retardant and a composite reactive flame retardant; the composite additive flame retardant includes the following components by weight: 1 to 80 parts of inorganic flame retardant, 1 to 75 parts of phosphorus halogen flame retardant and 5 to 60 parts of organic phosphorus flame retardant; the composite reactive flame retardant includes the following components by weight: 20 to 100 parts of di(4-hydroxybutyl)phenyl phosphate and 30 to 150 parts of 2-carboxyethylphenyl phosphite glycol ester; the mass ratio of the composite additive flame retardant to the composite reactive flame retardant is 100:60 to 150. The flame retardant disclosed herein can improve the flame retardant effect of rigid polyurethane foam without affecting the mechanical properties of rigid polyurethane foam.

Claims (11)

  1. 一种阻燃剂，其特征在于，包括复合添加型阻燃剂和复合反应型阻燃剂；A flame retardant, characterized in that it comprises a composite additive flame retardant and a composite reactive flame retardant;
    所述复合添加型阻燃剂，包括按重量份数计的如下组分：1～80份无机阻燃剂、1～75份磷卤阻燃剂和5～60份有机磷阻燃剂；The composite additive flame retardant comprises the following components by weight: 1 to 80 parts of inorganic flame retardant, 1 to 75 parts of phosphorus halogen flame retardant and 5 to 60 parts of organic phosphorus flame retardant;
    所述复合反应型阻燃剂，包括按重量份数计的如下组分：二(4-羟丁基)苯基磷酸酯20～100份和2-羧乙基苯基次磷酸乙二醇脂30～150份；The composite reactive flame retardant comprises the following components by weight: 20 to 100 parts of di(4-hydroxybutyl)phenyl phosphate and 30 to 150 parts of 2-carboxyethylphenyl phosphite glycol ester;
    所述复合添加型阻燃剂和所述复合反应型阻燃剂的质量比为100：60～150。The mass ratio of the composite additive flame retardant to the composite reactive flame retardant is 100:60-150.
  2. 根据权利要求1所述的阻燃剂，其特征在于，所述复合添加型阻燃剂，包括按重量份数计的如下组分：25～55份无机阻燃剂、25～50份磷卤阻燃剂和10～40份有机磷阻燃剂。The flame retardant according to claim 1 is characterized in that the composite additive flame retardant comprises the following components in parts by weight: 25 to 55 parts of inorganic flame retardant, 25 to 50 parts of phosphorus halogen flame retardant and 10 to 40 parts of organic phosphorus flame retardant.
  3. 根据权利要求1所述的阻燃剂，其特征在于，所述二(4-羟丁基)苯基磷酸酯和所述2-羧乙基苯基次磷酸乙二醇脂的质量比为1：0.5～1.5。The flame retardant according to claim 1, characterized in that the mass ratio of the di(4-hydroxybutyl)phenyl phosphate to the 2-carboxyethylphenyl phosphite glycol ester is 1:0.5-1.5.
  4. 根据权利要求1所述的阻燃剂，其特征在于，所述无机阻燃剂包括氢氧化铝和蒙脱土。The flame retardant according to claim 1, characterized in that the inorganic flame retardant comprises aluminum hydroxide and montmorillonite.
  5. 根据权利要求4所述的阻燃剂，其特征在于，所述氢氧化铝和所述蒙脱土的质量比为6：4～8。The flame retardant according to claim 4, characterized in that the mass ratio of the aluminum hydroxide to the montmorillonite is 6:4-8.
  6. 根据权利要求1所述的阻燃剂，其特征在于，所述磷卤阻燃剂包括磷酸三(2-氯异丙基)酯。The flame retardant according to claim 1, characterized in that the phosphorus halogen flame retardant comprises tris(2-chloroisopropyl) phosphate.
  7. 根据权利要求1所述的阻燃剂，其特征在于，所述有机磷阻燃剂包括磷酸三乙酯和磷酸三苯酯。The flame retardant according to claim 1, characterized in that the organophosphorus flame retardant comprises triethyl phosphate and triphenyl phosphate.
  8. 根据权利要求7所述的阻燃剂，其特征在于，所述磷酸三乙酯和所述磷酸三苯酯的质量比3：4～9。The flame retardant according to claim 7, characterized in that the mass ratio of the triethyl phosphate to the triphenyl phosphate is 3:4-9.
  9. 如权利要求1～8任一项所述的阻燃剂的制备方法，其特征在于，包括如下步骤：各组分混匀后，得到所述阻燃剂。The method for preparing a flame retardant according to any one of claims 1 to 8, characterized in that it comprises the following steps: after mixing the components, the flame retardant is obtained.
  10. 一种硬质聚氨酯泡沫，其特征在于，包括权利要求1～8任一项所述的阻燃剂。A rigid polyurethane foam, characterized in that it comprises the flame retardant according to any one of claims 1 to 8.
  11. 根据权利要求10所述的硬质聚氨酯泡沫，其特征在于，所述硬质聚氨酯泡沫中，所述阻燃剂的质量百分数为0.5％～3.5％。 The rigid polyurethane foam according to claim 10, characterized in that, in the rigid polyurethane foam, the mass percentage of the flame retardant is 0.5% to 3.5%.
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