WO2023241155A1 - 一种高氧指数聚氨酯阻燃硬质泡沫及其组合物和制备方法 - Google Patents

一种高氧指数聚氨酯阻燃硬质泡沫及其组合物和制备方法 Download PDF

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WO2023241155A1
WO2023241155A1 PCT/CN2023/083425 CN2023083425W WO2023241155A1 WO 2023241155 A1 WO2023241155 A1 WO 2023241155A1 CN 2023083425 W CN2023083425 W CN 2023083425W WO 2023241155 A1 WO2023241155 A1 WO 2023241155A1
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component
flame retardant
polyether
amount
flame
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PCT/CN2023/083425
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English (en)
French (fr)
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冯运成
关志强
麦景恒
梁秋明
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天长市伯士的环保新材料有限公司
中山市伯士的化工科技有限公司
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Publication of WO2023241155A1 publication Critical patent/WO2023241155A1/zh

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    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
    • Y02B30/90—Passive houses; Double facade technology

Definitions

  • Polyurethane foam is made of isocyanate and polyether polyol as the main raw materials, mixed with special equipment and foamed on-site by a high-pressure foaming machine under the action of various additives such as foaming agents, catalysts, and flame retardants.
  • Polymers are divided into two types: polyurethane soft foam materials and polyurethane hard foam materials. Among them, soft foam materials have an open-cell structure, and hard foam materials have a closed-cell structure. Soft foam materials are divided into skinned and non-skinned. Two kinds.
  • Polyurethane rigid foam material is a new synthetic material with thermal insulation and waterproof functions. Its thermal conductivity is very low, which is equivalent to half of that of extruded board. It is the lowest thermal conductivity among all thermal insulation materials currently.
  • Rigid polyurethane foam is mainly used in building exterior wall insulation, integrated roof waterproofing and insulation, cold storage insulation, pipe insulation materials, building panels, home appliances, refrigerated trucks and cold storage insulation materials.
  • the main function of polyurethane soft foam material is cushioning, so it is often used in sofa furniture, pillows, cushions, toys, clothing and soundproof linings.
  • the early patent CN111647190B of the patentee of this disclosure discloses the formula, set and preparation method of polyurethane rigid foam, as well as the polyurethane rigid foam and its preparation method and application.
  • the foam has good thermal conductivity stability and good attenuation, and is suitable for use in low-temperature insulation environments.
  • flame retardant performance there is no study on the improvement of flame retardant performance, whether to add flame retardants and the impact of adding component A or B.
  • the performance of polyurethane rigid foam cannot be predicted after adding flame retardants.
  • the present disclosure provides a composition for high oxygen index polyurethane flame retardant rigid foam, including component A and component B.
  • the component A includes polyether and flame retardant polyether
  • the component B includes isocyanate and Flame retardant, control the pH of the A component to 7.5-10, and the pH of the B component to 4-6.
  • the ratio of the hydroxyl value of the polyether to the hydroxyl value of the flame-retardant polyether is (1.19-1.57):1.
  • the flame retardant polyether has a hydroxyl value of 300-360 mgKOH/g, and the polyether has a hydroxyl value of 430-470 mgKOH/g.
  • the mass m of the flame-retardant polyether and the mass n of the flame retardant satisfy: m/n is (2-6.5):1.
  • the A component also includes a catalyst, silicone oil and foaming agent, and the B component also includes a desiccant and an anti-crystallization agent.
  • the amount of the flame-retardant polyether is 30-42wt%, and the amount of the catalyst is 2.5-4.5wt%, the amount of silicone oil is 3-4.5wt%, the amount of foaming agent is 10-15wt%, and the amount of polyether is 34-54.5wt%.
  • the amount of flame retardant is 10-22wt%
  • the amount of desiccant is 0.15-0.32wt%
  • the amount of anti-crystallization agent is 0.21-0.32wt%
  • the amount of isocyanate is 77-89.64wt%.
  • the catalyst includes cyclohexylamine
  • the foaming agent includes water and cyclopentane, wherein, based on the total amount of component A, the amount of water is 1-4wt%, and the amount of cyclopentane is 6-14wt%;
  • the desiccant includes phosphite and optional phenol.
  • phosphite/phenol is (1.3-1.6):1;
  • the anti-crystallization agent includes perchloric acid and optional trifluoromethanesulfonic acid.
  • perchloric acid/trifluoromethanesulfonic acid is (1.2-1.7):1 in terms of mass.
  • the flame retardant is TCPP and TEP, and in terms of mass, TCPP/TEP is 1: (1.1-1.9).
  • the flame retardant polyether is LY-pb01.
  • the present disclosure provides a high oxygen index polyurethane flame retardant rigid foam prepared from the composition.
  • the oxygen index of the high oxygen index polyurethane flame retardant rigid foam is above 32%; and the performance of the high oxygen index polyurethane flame retardant rigid foam satisfies: after 6 months, the density deviation change rate Less than 10%, the pressure bubble density change rate is less than 12%, the strength is above 140kPa, the dimensional stability shrinkage is less than 1%, and the thermal conductivity does not exceed 0.022W/(m ⁇ K).
  • the present disclosure provides a method for preparing high oxygen index polyurethane flame retardant rigid foam.
  • the composition is used to prepare the high oxygen index polyurethane flame retardant rigid foam, including:
  • the first mixture and the second mixture are mixed and foamed to obtain a high oxygen index polyurethane flame retardant rigid foam.
  • the present disclosure also provides the use of the above composition or the above high oxygen index polyurethane flame retardant rigid foam in thermal insulation materials, waterproof and thermal insulation integrated materials, building boards, and home appliances.
  • hydroxyl value refers to the number of milligrams of potassium hydroxide equivalent to the hydroxyl groups in 1 g of sample.
  • its The miscibility with other components such as isocyanate will become worse as the functionality and hydroxyl value increase; on the other hand, the fluctuation of the hydroxyl value of polyether polyol will destroy isocyanate, polyether polyol and water during the foaming process.
  • the present disclosure specifically adds flame-retardant polyether and flame retardant stored separately, and controls component A containing polyether and flame-retardant polyether to be alkaline, and controls component B containing isocyanate and flame retardant.
  • the component is acidic.
  • the inventor found that by controlling the above components, the chemical stability of the component can be significantly improved, which is conducive to the reaction of isocyanate, polyether polyol and water to reach an appropriate equilibrium state, thereby making the polyurethane flame retardant rigid foam It can have both suitable hardness and high flame retardant effect, and can be stored for a long time and has stable performance.
  • flame retardant is not added to component A, but flame retardant polyether is added.
  • flame retardant polyether is added.
  • This disclosure sets the flame retardant in component B, and in its specific acidic system, the flame retardant will not decompose.
  • the amount of water in component A is 1.5-2.5 wt%; the water content of component B is less than 200 ppm, optionally, no more than 100 ppm.
  • the water content in component A is at a suitably high level, which is more conducive to improving the reactivity with component B during mixing. It can control the reaction between isocyanate, polyether polyol and water to reach an appropriate balance, and has good foaming performance, so that the hardness of the resulting polyurethane rigid foam meets the requirements; at the same time, the moisture content takes into account the moisture content of component A and will not cause storage for more than half a year. delamination and failure.
  • water in component A and the water in component B can be introduced from the raw materials or adjusted and added in other practical ways.
  • the ratio of the hydroxyl value of the polyether to the hydroxyl value of the flame-retardant polyether is (1.19-1.57):1, for example, it can be (1.20-1.55):1, (1.25-1.50):1 or (1.30- 1.45): 1, such as can be any value among 1.19, 1.20, 1.23, 1.28, 1.30, 1.34, 1.40, 1.47, 1.50, 1.57 or any value between adjacent values.
  • the hydroxyl value of the polyether is 430-470mgKOH/g, such as 435-465mgKOH/g, 440-460mgKOH/g or 445-455mgKOH/g, such as 430mgKOH/g, 435mgKOH/g, 440mgKOH/g. g, 445mgKOH/g, 450mgKOH/g, 455mgKOH/g, 460mgKOH/g, 465mgKOH/g, 470mgKOH/g, or an interval value between any two endpoint values.
  • the mass m of the flame retardant polyether and the mass n of the flame retardant satisfy: m/n is (2-6.5):1, for example, it can be (2.5-6.0):1, (3.0- 5.5): 1 or (3.5-5.0): 1, such as 2, 2.5, 3, Any value among 3.5, 4, 4.5, 5, 5.5, 6, 6.5 or any value between adjacent values.
  • the ratio of flame retardant polyether and flame retardant is more conducive to the reasonable distribution of flame retardant components, and is more conducive to giving full play to the synergy, achieving the maximum flame retardant effect at the lowest usage amount, and making Group A Both component and component B are stable and will not affect the use effect when stored for more than half a year; component A does not delaminate, and its hardness and other properties meet the requirements.
  • the flame-retardant polyether can optionally be LY-pb01 or LY-pb02, for example, it can be the flame-retardant polyether LY-pb01 or LY-pb02 commercially available from Jiangsu Luyuan New Materials Co., Ltd.
  • the polyether is optionally polyether 4110, for example, it can be polyether 4110 commercially available from Hebei Yadong Co., Ltd.
  • the amount of flame-retardant polyether is 30-42wt%, such as 32-40wt%, 33-38wt% or 35-36wt%, such as 30wt %, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%; the amount of polyether is 58-70wt%.
  • silicone oil disclosed in this disclosure can be silicone oil commonly used in this field, which will not be described in detail here.
  • the amount of flame-retardant polyether is 30-42wt%, optionally 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt% , 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, optionally 35-42wt%;
  • the amount of catalyst is 2.5-4.5wt%, optionally 2.5wt%, 2.7wt%, 3wt%, 3.2wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 4wt%, 4.2wt%, 4.4wt%, 4.5wt%;
  • the amount of silicone oil is 3-4.5wt%, optional 3wt% , 3.2wt%, 3.5wt%, 3.7wt%, 4wt%, 4.2wt%, 4.4wt%, 4.5wt%;
  • the amount of foam is 3-4.5wt%
  • Component A of the present disclosure through the appropriate ratio of flame retardant polyether and polyether, and the appropriate content of catalyst, silicone oil, and foaming agent, is not affected by the addition of additional flame retardants, anti-crystallization agents, desiccants, etc., and can be adjusted Cell size, so that the polyurethane flame retardant rigid foam can still maintain a high hardness, achieving coordinated adjustment of flame retardant performance and hardness; and the composition has stable performance for more than half a year and is not easy to stratify.
  • the amount of flame retardant is 10-22wt%, such as 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt% or 22wt%; desiccant
  • the amount is 0.15-0.32wt%, such as 0.16wt%, 0.18wt%, 0.20wt%, 0.22wt%, 0.24wt%, 0.26wt%, 0.28wt%, 0.30wt% or 0.31wt%; to prevent crystallization
  • the amount of the agent is 0.21-0.32wt%, optionally 0.23-0.32wt%, such as 0.22wt%, 0.24wt%, 0.26wt%, 0.28wt%, 0.30wt% or 0.31wt%; the amount of isocyanate 77-90wt%, such as 78wt%, 80wt%, 82wt%, 84wt%, 86wt%, 88wt
  • a high content of desiccant is used to control moisture, a high content of anti-crystallization agent, and an appropriate amount of isocyanate can increase the storage temperature range of component B, enabling long-term storage at room temperature for more than half a year without failure, and It reacts well with component A and has excellent performance; optionally, the desiccant content is appropriately high, which can fully absorb the higher moisture in the flame retardant, air moisture and moisture absorbed during storage, which is more conducive to reducing component B.
  • Deterioration phenomena such as increased viscosity; thus it is more conducive to maintaining the original viscosity of component B and the stable storage of component B; moreover, adding a suitable high content of anti-crystallization agent can avoid isocyanate (such as crude MDI) and flame retardant When the agent is mixed, it will absorb moisture in the air and become crystallized, which prevents the near-polymerization reaction of component B to form crystals during low-temperature storage. This allows component B to have a wider storage temperature range and can be stored at room temperature.
  • isocyanate such as crude MDI
  • flame retardant When the agent is mixed, it will absorb moisture in the air and become crystallized, which prevents the near-polymerization reaction of component B to form crystals during low-temperature storage. This allows component B to have a wider storage temperature range and can be stored at room temperature.
  • the foaming agent includes water and cyclopentane, wherein, based on the total amount of component A, the amount of water is 1-4wt%, such as 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt % or 3.5wt%; the amount of cyclopentane is 6-14wt%, such as 6.5wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt% or 13wt%.
  • the amount of water is 1-4wt%, such as 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt % or 3.5wt%
  • the amount of cyclopentane is 6-14wt%, such as 6.5wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt% or 13wt%.
  • the desiccant includes phosphite and optional phenol.
  • phosphite/phenol is (1.3-1.6):1, such as 1.35:1, 1.4:1, 1.45: 1. 1.5:1 or 1.55:1, which is more conducive to synergistic and rapid water absorption.
  • the anti-crystallization agent includes perchloric acid and optional trifluoromethanesulfonic acid.
  • perchloric acid/trifluoromethanesulfonic acid is (1.2-1.7):1 by mass, such as can be 1.3:1, 1.4:1, 1.5:1, 1.6:1, or 1.65:1, which is more conducive to synergistic and rapid prevention of crystallization of component B.
  • the flame retardants are TCPP (i.e., tris(2-chloropropyl)phosphate) and TEP (i.e., triethyl phosphate).
  • TCPP/TEP is 1: ( 1.1-1.9), for example, it can be 1: (1.2-1.8), 1: (1.3-1.7) or 1: (1.4-1.6), such as 1:1.1, 1:1.2, 1:1.3, 1:1.4 , any value among 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 and any value between adjacent point values.
  • This optional solution is more conducive to enhancing the flame retardant effect. It will be appreciated that, generally, flame retardants contain water.
  • the flame retardant TCPP can be, for example, a commercial product from Chun'an Auxiliary Factory, and the flame retardant TEP can be, for example, a commercial product from Chun'an Auxiliary Factory. Of course, it can also be a commercial product from other manufacturers.
  • the isocyanate of the present disclosure can be common crude MDI in the art, optionally diphenylmethane diisocyanate.
  • component A and component B of the present disclosure are stored separately, optionally at room temperature, and when used, can be mixed for reaction under required conditions as needed.
  • component B is mixed and prepared in an air-isolated airtight chamber that is dried at room temperature and filled with nitrogen and maintained at a pressure of 0.05-0.2MPa.
  • the present disclosure provides a high oxygen index polyurethane flame retardant rigid foam, which is prepared from the above composition.
  • the oxygen index of the polyurethane flame retardant rigid foam is above 32% (i.e. ⁇ 32%); and, the polyurethane flame retardant rigid foam
  • the performance of the quality foam meets: after 6 months, the density deviation change rate is less than 10%, the pressure bubble density change rate is less than 12%, the strength is above 140kPa (i.e. ⁇ 140kPa), the dimensional stability shrinkage is less than 1%, and the thermal conductivity is not More than 0.022W/(m ⁇ K).
  • the polyurethane flame retardant rigid foam of the present disclosure has fine cells.
  • the calculation method of density deviation change rate in this disclosure is: ((density after half a year - initial density)/initial density) ⁇ 100%. Density here refers to the core density of the foam after peeling. The calculation method of pressure bubble density change rate is the same. The density and pressure bubble density tests disclosed in this disclosure are both industry standard and common drainage methods in this field, and will not be described in detail here.
  • the strength refers to the strength of the polyurethane flame retardant rigid foam in the parallel direction and/or the vertical direction.
  • the testing of the strength and the dimensional stability and shrinkage are all industry standard and common methods in this field, and will not be described in detail here.
  • the present disclosure provides a method for preparing high oxygen index polyurethane flame retardant rigid foam.
  • the above composition is used to prepare high oxygen index polyurethane flame retardant rigid foam, including:
  • each component of component B is mixed in an air-isolated airtight chamber that is dried at room temperature and filled with nitrogen and pressure-maintained. This can avoid an environment in contact with air and prevent the viscosity of component B from changing due to water absorption. A polyurea reaction occurs and crystallization occurs.
  • the nitrogen filling and pressure maintaining described in this disclosure refers to filling in nitrogen to replace the air and maintaining the pressure in the sealed chamber at 0.05-0.2MPa.
  • the time for the mixing reaction described in this disclosure can be selected by those skilled in the art according to needs.
  • the mixing reaction time of component A is 30-100 min
  • the mixing reaction time of component B is 30-100 min.
  • the present disclosure overcomes the shortcomings of the existing polyurethane rigid foam material compositions in the prior art, such as short storage period and unsatisfactory flame retardancy, and provides a high oxygen index polyurethane flame retardant rigid foam, its composition and preparation method.
  • Polyurethane flame-retardant rigid foam has excellent flame-retardant properties while meeting hardness requirements, and can be stored for a long time without stratification and has stable performance.
  • the present disclosure adds flame retardant and flame retardant polyether for synergistic flame retardancy and separation.
  • Open storage can prevent the flame retardant activity from failing and maintain the flame retardant activity even after long-term storage.
  • the addition of flame-retardant polyether can reduce the amount of flame retardant to a certain extent, and can also reduce the amount of flame retardant during mixing. It has a synergistic flame retardant effect.
  • component B and component C Mix component B and component C for storage, with a pH of 5.6, and there will be no stratification after half a year of storage.
  • Component A is: Component A according to Example 1, except that the same amount of 4110H oil ether (manufacturer: Jiahua Chemical Co., Ltd.) is used instead of polyether 4110.
  • the pH of component A is 11; stored for one week It does not stratify when stored, but stratifies when stored for two months.
  • the A component of this example is stored for half a year without stratification.
  • the difference is that the amount of flame-retardant polyether is adjusted so that the mass m of the flame-retardant polyether and the total mass n of the flame retardant satisfy: m/n is 4:1, and the polyether is adjusted.
  • the amount of ether is such that 100% of the total amount of component A is met, and Component A is an alkaline system with a pH of 9.
  • the difference is that the type of polyether is adjusted so that the ratio of the hydroxyl value of the polyether to the hydroxyl value of the flame-retardant polyether is 1:1, and component A is an alkaline system, pH is 10.
  • the A component of this example is stored for half a year without stratification.
  • the A component of this example is stored for half a year without stratification.
  • the B component and the C component in Examples 2 to 6 were mixed and stored respectively, and then mixed with the A component at a mass ratio of 1.3:1 to perform foaming under the same conditions, which were recorded as experiments Q2, Q3, and Q4. , Q5, Q6, and then perform performance testing on them.
  • the results are as follows in Table 3.
  • the 6-month density deviation change rate ((density after half a year - initial density) / initial density) ⁇ 100%
  • the pressure bubble density change rate ((pressure bubble density after half a year - initial pressure bubble density) )/initial pressure bubble density) ⁇ 100%.
  • D initial refers to the data obtained from the immediate performance test of the polyurethane flame-retardant rigid foam obtained in experiment D.
  • D after two months refers to the performance test data of the polyurethane flame retardant rigid foam obtained in experiment D after two months.
  • Other corresponding expressions are the same.
  • the dimensional stability of -3.8% refers to the dimensional shrinkage of 3.8% to evaluate the stability.
  • the foaming time refers to the time of different reactions after mixing and foaming.
  • CT, GT, and TFT are the milky time, drawing time, and viscosity loss time in order.
  • the solution of adding flame retardant to isocyanate has a longer storage time, and a higher amount of flame retardant can be added. It can be stored for more than half a year without stratification and has high strength. , the oxygen index is above 32%, the flame retardant effect is excellent, it can meet B1 requirements, the curing time is short, and the dimensional stability meets the requirements.
  • Example 1 by comparing Example 1 and Examples 5-6, it can be seen that by using the optional polyether combination or the optional flame-retardant polyether and flame retardant appropriately proportioned solution of the present disclosure, the obtained polyurethane is flame retardant.
  • the flame retardancy of rigid foam has been further improved, and other properties such as thermal conductivity and strength have been relatively further improved.
  • the present disclosure provides a high oxygen index polyurethane flame-retardant rigid foam, its composition and preparation method.
  • the composition of the present disclosure can make the polyurethane flame-retardant rigid foam maintain the When the hardness reaches the standard, it has excellent flame retardant effect and long storage time, so it has excellent practical performance.

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Abstract

本公开属于聚氨酯硬质泡沫技术领域，具体涉及一种高氧指数聚氨酯阻燃硬质泡沫及其组合物和制备方法，所述组合物包括A组分和B组分，所述A组分包括聚醚和阻燃聚醚，所述B组分包括异氰酸酯和阻燃剂，控制所述A组分的pH为7.5-10，所述B组分的pH为4-6。本公开的组合物能够在添加较低量的阻燃剂的情况下，使得聚氨酯阻燃硬质泡沫在保持硬度达标的情况下，具有优异的阻燃效果，且储存时间长。

Description

一种高氧指数聚氨酯阻燃硬质泡沫及其组合物和制备方法
相关申请的交叉引用
本公开要求于2022年06月17日提交中国专利局的申请号为CN202210692506.8、名称为“一种高氧指数聚氨酯阻燃硬质泡沫及其组合物和制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开属于聚氨酯硬质泡沫技术领域，具体涉及一种高氧指数聚氨酯阻燃硬质泡沫及其组合物和制备方法。
背景技术
聚氨酯泡沫材料是以异氰酸酯和聚醚多元醇为主要原料，在发泡剂、催化剂、阻燃剂等多种助剂的作用下，通过专用设备混合，经高压发泡机现场发泡而成的高分子聚合物，分为聚氨酯软泡材料和聚氨酯硬泡材料两种，其中，软泡材料为开孔结构，硬泡材料为闭孔结构，而软泡材料又分为结皮和不结皮两种。
聚氨酯硬泡材料是一种具有保温与防水功能的新型合成材料，其导热系数很低，相当于挤塑板的一半，是目前所有保温材料中导热系数最低的。硬质聚氨酯泡沫塑料主要应用在建筑物外墙保温、屋面防水保温一体化、冷库保温隔热、管道保温材料、建筑板材、家电、冷藏车及冷库隔热材等方面。聚氨酯软泡材料的主要功能是缓冲，因此常用于沙发家具、枕头、坐垫、玩具、服装以及隔音内衬。
本公开的专利权人的早期专利CN111647190B公开了制备聚氨酯硬泡的配方、套装及其制备方法以及聚氨酯硬泡及其制备方法与应用。该泡沫导热系数稳定性好，衰减性好，适合应用于低温保温环境中。但是没有涉及阻燃性能提升，是否加入阻燃剂以及在A组分或B组分加入的影响等均未做研究，加入阻燃剂后聚氨酯硬泡性能均无法预估。
CN114395097A公开了一种用于井下巷道加固的双组分阻燃聚氨酯材料及其制备方法。该专利申请的聚氨酯材料具有反应温度低，力学性能高、阻燃效果好的特点，满足煤矿用高分子材料的性能要求。但是该技术通过多种性能差别大的聚醚多元醇复配，聚醚多元醇与阻燃剂复配，且需通过阻燃剂与异氰酸酯反应成为改性异氰酸酯型聚氨酯预聚体后作为B组分，才实现阻燃性能提升，多种成分的复配以及改性，工艺复杂，且阻燃效果不能保证。
然而，目前国际上对聚氨酯硬泡的阻燃性要求越来越高，板材要达到B2甚至B1级阻燃。现有技术中的聚氨酯硬泡的阻燃效果无法达到B2以上，很难达到B1级，特别是氧指数≥32％的指标基本达不到，且若阻燃剂量增多或长时间储存会导致分层；而且，原料制备工艺复杂，组成复杂，同时还存在收缩、存放期短、强度低、活性失效，不能发泡，熟化时间长的缺点。本领域亟需一种高氧指数聚氨酯阻燃硬质泡沫能够在满足硬度要求的情况下，具有优异的阻燃性能，而且可长时间储存，不分层，性能稳定。
发明内容
本公开提供了一种高氧指数聚氨酯阻燃硬质泡沫用组合物，包括A组分和B组分，所述A组分包括聚醚和阻燃聚醚，所述B组分包括异氰酸酯和阻燃剂，控制所述A组分的pH为7.5-10，所述B组分的pH为4-6。
可选地，所述聚醚的羟值与所述阻燃聚醚的羟值的比值为(1.19-1.57)：1。
可选地，所述阻燃聚醚的羟值为300-360mgKOH/g，所述聚醚的羟值为430-470mgKOH/g。
可选地，所述阻燃聚醚的质量m和阻燃剂的质量n满足：m/n为(2-6.5)：1。
可选地，所述A组分还包括催化剂、硅油和发泡剂，所述B组分还包括干燥剂和防结晶剂。
可选地，以A组分总量计，所述阻燃聚醚的量为30-42wt％，催化剂的量为 2.5-4.5wt％，硅油的量为3-4.5wt％，发泡剂的量为10-15wt％，聚醚的量为34-54.5wt％。
可选地，以B组分总量计，所述阻燃剂的量为10-22wt％，干燥剂的量为0.15-0.32wt％，防结晶剂的量为0.21-0.32wt％，异氰酸酯的量为77-89.64wt％。
可选地，所述催化剂包括环己胺；
所述发泡剂包括水和环戊烷，其中，以A组分总量计，水的量为1-4wt％，环戊烷的量为6-14wt％；
所述干燥剂包括亚磷酸酯和任选的苯酚，优选地，以质量计，亚磷酸酯/苯酚为(1.3-1.6):1；
所述防结晶剂包括高氯酸和任选的三氟甲磺酸，可选地，以质量计，高氯酸/三氟甲磺酸为(1.2-1.7):1。
可选地，所述A组分中水的量为1.5-2.5wt％；所述B组分的含水量小于200ppm，更优选不超过100ppm。
可选地，所述阻燃剂为TCPP和TEP，以质量计，TCPP/TEP为1：(1.1-1.9)。
可选地，所述阻燃聚醚为LY-pb01。
可选地，所述A组分中水的量为1.5-2.5wt％；所述B组分的含水量小于200ppm，可选地，所述B组分的含水量不超过100ppm。
本公开提供了一种高氧指数聚氨酯阻燃硬质泡沫，其由所述的组合物制备得到。
可选地，所述高氧指数聚氨酯阻燃硬质泡沫的氧指数在32％以上；且，所述高氧指数聚氨酯阻燃硬质泡沫的性能满足：在6个月之后，密度偏差变化率小于10％，压力泡密度变化率小于12％，强度在140kPa以上，尺寸稳定性收缩小于1％，导热系数不超过0.022W/(m·K)。
本公开提供了一种高氧指数聚氨酯阻燃硬质泡沫的制备方法，采用所述的组合物来制备所述高氧指数聚氨酯阻燃硬质泡沫，包括：
将所述A组分中各成分混合反应，得到第一混料；
将所述B组分中的各成分在常温下干燥、充氮保压的隔绝空气的密闭腔室内混合，得到第二混料，其中充氮保压的压力为0.05-0.2MPa；
将第一混料和第二混料混合发泡，得到高氧指数聚氨酯阻燃硬质泡沫。
本公开还提供上述组合物或上述高氧指数聚氨酯阻燃硬质泡沫用于保温隔热材料、防水保温一体化材料、建筑板材、家电中的用途。
具体实施方式
在文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中公开。
术语定义
如本文所用，术语“羟值”是指1g样品中的羟基所相当的氢氧化钾的毫克数。
本发明人研究发现，对聚氨酯泡沫材料的性能产生影响的因素众多，其中，一方面，聚醚多元醇的官能度越大、羟值越高，则制得的泡沫塑料硬度越大，然而其与异氰酸酯等其他组分的互溶性则会随官能度以及羟值的增大而变差；另一方面，聚醚多元醇羟值的波动会破坏发泡过程中异氰酸酯与聚醚多元醇及水的反应平衡；若聚醚多元醇的羟值高，则异氰酸酯与聚醚多元醇的反应性增强；聚醚多元醇的羟值低，则异氰酸酯与水的反应增强，造成主反应速度跟不上发泡反应速度，易造成塌泡现象，影响硬度。也即，聚氨酯泡沫材料的原料的羟值等参数的波动，会影响异氰酸酯与聚醚多元醇及水的反应达到适宜的平衡状态，从而影响聚氨酯阻燃硬质泡沫的硬度和阻燃效果。基于此，发明人进一步研究，而提出本公开。
本公开提供了一种高氧指数聚氨酯阻燃硬质泡沫用组合物，包括A组分和B组分，A组分包括聚醚和阻燃聚醚，B组分包括异氰酸酯和阻燃剂，控制A组分的pH为7.5-10， B组分的pH为4-6。
在上述技术方案中，本公开特别的添加分开储存的阻燃聚醚和阻燃剂，且控制含聚醚和阻燃聚醚的A组分为碱性，控制含异氰酸酯和阻燃剂的B组分为酸性，发明人发现通过上述组分控制，能够显著提高组分的化学稳定性，有利于异氰酸酯与聚醚多元醇及水的反应达到适宜的平衡状态，从而使得聚氨酯阻燃硬质泡沫能够兼具适宜的硬度和高阻燃效果，且可储存时间长，性能稳定。而在相同条件下，若将阻燃聚醚和阻燃剂混合在一起，会导致阻燃剂失效，反应活性下降，反应时间变慢至不能发泡，以及长时间储存分层的问题。而在相同条件下，若A组分不加入阻燃聚醚，无法达到氧指数32以上的阻燃效果，最高只能达到氧指数30；若B组分不加入阻燃剂，只使用阻燃聚醚，其氧指数只能达到28。一般地，现有技术只能达到氧指数30以下。
一般地，本公开中含聚醚的A组分要加水作为发泡剂，B组分中不可避免的会含水，还可以含有其他本领域现有的其他组分或助剂。一般地，含聚醚的A组分的水含量高于含异氰酸酯的B组分中的水含量。
本公开在A组分中不加入阻燃剂，而加入阻燃聚醚，一方面，能够避免A组分中聚醚等组分和阻燃剂混合会相互削弱阻燃效果的情况发生，这是由于在A组分的上述特定pH条件下，阻燃剂会因为聚醚(以及A组分中可能含有的催化剂、硅油等)的碱性基团影响易遭到破坏，含水相对较高，出现易于水解等情况。本公开将阻燃剂设置在B组分中，在其特定的酸性体系中，阻燃剂不会发生分解。另一方面，避免了A组分加阻燃剂容易分层、长时间会失效，这是由于阻燃剂加入后在A组分中溶解度不高，易于分层，长时间储存失效，溶解性差，同时阻燃剂在A组分的较高水量的环境会发生水解，达不到本公开高氧指数的阻燃效果。
本领域技术人员可以适当控制含水量。在本公开可选的一些实施方式中，A组分中水的量为1.5-2.5wt％；B组分的含水量小于200ppm，可选地，不超过100ppm。该可选的方案下，A组分中含水量处于适宜的较高水平，更利于混合时提高与B组分的反应性， 能够控制异氰酸酯与聚醚多元醇及水的反应达到适宜的平衡，发泡性能好，使得所得聚氨酯硬泡的硬度满足要求；同时该含水量兼顾了A组分的含水率不会导致半年以上存储的分层以及失效。
可以理解的是，A组分中水和B组分中的水可以是由原料带入或调整加入等可实施的方式引入。
本发明人进一步发现，限定聚醚的羟值与阻燃聚醚的羟值的比值在适宜范围，更利于聚氨酯阻燃硬质泡沫的硬度和阻燃性能的提高。可选地，聚醚的羟值与阻燃聚醚的羟值的比值为(1.19-1.57)：1，例如可以为(1.20-1.55)：1、(1.25-1.50)：1或(1.30-1.45)：1，诸如可以为1.19、1.20、1.23、1.28、1.30、1.34、1.40、1.47、1.50、1.57中的任一值或相邻值之间的任一值。该可选的方案下，提高A组分综合羟值在适宜水平，减少羟值波动，能够促进尽量高的反应活性及反应速率，避免阻燃剂加入导致A组分羟值变化大造成的阻燃性能及硬化、活性降低等性能劣化的情况发生，从而在提高阻燃性能的同时，还使其能保持足够高的硬度，实现阻燃性能与硬度等性能的协同调节；且组合物半年以上性能稳定，不易分层。
可选地，阻燃聚醚的羟值为300-360mgKOH/g，例如可以为310-350mgKOH/g、315-345mgKOH/g或320-340mgKOH/g，诸如可以为300mgKOH/g、305mgKOH/g、310mgKOH/g、315mgKOH/g、320mgKOH/g、325mgKOH/g、330mgKOH/g、335mgKOH/g、340mgKOH/g、345mgKOH/g、350mgKOH/g、355mgKOH/g、360mgKOH/g，或者任意两个端点值之间的区间值。可选地，聚醚的羟值为430-470mgKOH/g，诸如可以为435-465mgKOH/g、440-460mgKOH/g或445-455mgKOH/g，例如可以为430mgKOH/g、435mgKOH/g、440mgKOH/g、445mgKOH/g、450mgKOH/g、455mgKOH/g、460mgKOH/g、465mgKOH/g、470mgKOH/g，或者任意两个端点值之间的区间值。
根据本公开，可选地，阻燃聚醚的质量m和阻燃剂的质量n满足：m/n为(2-6.5)：1，例如可以为(2.5-6.0)：1、(3.0-5.5)：1或(3.5-5.0)：1，诸如可以为2、2.5、3、 3.5、4、4.5、5、5.5、6、6.5中的任一值或相邻值之间的任一值。该可选的方案下，阻燃聚醚和阻燃剂的比例更利于合理分配阻燃组分，更利于充分发挥协同作用，能在最低使用量下达到最大的阻燃效果，且使A组分、B组分均稳定存放半年以上时不影响使用效果；组分A不分层，同时硬度等性能满足要求。
在一种实施方式中，阻燃聚醚可选地为LY-pb01、LY-pb02，例如可以为江苏绿源新材料有限公司市售的阻燃聚醚LY-pb01、LY-pb02。
在一种实施方式中，聚醚可选地为聚醚4110，例如可以为河北亚东有限公司市售的聚醚4110。
本公开中，可选地，以A组分总量计，阻燃聚醚的量为30-42wt％，例如可以为32-40wt％、33-38wt％或35-36wt％，诸如可以为30wt％、31wt％、32wt％、33wt％、34wt％、35wt％、36wt％、37wt％、38wt％、39wt％、40wt％、41wt％、42wt％；聚醚的量为58-70wt％。
可选地，以B组分总量计，阻燃剂的量为10-22wt％，例如可以为12-20wt％、14-18wt％或16-17wt％，诸如可以为10wt％、11wt％、12wt％、13wt％、14wt％、15wt％、16wt％、17wt％、18wt％、19wt％、20wt％、21wt％、22wt％；异氰酸酯的量为78-90wt％。
本发明人进一步发现，A组分和B组分的组成还会影响其分别储存一定时间后的混合结晶情况，并影响上机实验的设备堵塞情况。对此，可选地，A组分还包括催化剂、硅油和发泡剂，B组分还包括干燥剂和防结晶剂。该可选的方案下，B组分储存长时间后的混合中不会出现结晶或浑浊，且不会堵塞上机设备的枪头，更利于充分发挥阻燃协同效果。而，异氰酸酯以及任选的阻燃剂(不含干燥剂和防结晶剂)储存一定时间后的混合中会出现结晶和浑浊的情况，且会堵塞上机设备的枪头，使发泡不能进行有效混合。
本公开硅油可以采用本领域常用的硅油，在此不再赘述。
可选地，以A组分总量计，阻燃聚醚的量为30-42wt％，可选为30wt％、31wt％、32wt％、33wt％、34wt％、35wt％、36wt％、37wt％、38wt％、39wt％、40wt％、41wt％、42wt％，可选地为35-42wt％；催化剂的量为2.5-4.5wt％，可选为2.5wt％、2.7wt％、3wt％、 3.2wt％、3.4wt％、3.5wt％、3.6wt％、3.7wt％、4wt％、4.2wt％、4.4wt％、4.5wt％；硅油的量为3-4.5wt％，可选为3wt％、3.2wt％、3.5wt％、3.7wt％、4wt％、4.2wt％、4.4wt％、4.5wt％；发泡剂的量为10-15wt％，可选为10wt％、11wt％、12wt％、13wt％、14wt％、15wt％；聚醚的量为34-54.5wt％，可选为34wt％、35wt％、37wt％、40wt％、41wt％、42wt％、45wt％、48wt％、50wt％、52wt％、53wt％、54.5wt％，可选地为41-53.5wt％。本公开的A组分，通过阻燃聚醚、聚醚的合适比例，配合合适含量的催化剂、硅油、发泡剂，不受额外添加阻燃剂、防结晶剂、干燥剂等影响，能够调节泡孔尺寸，从而聚氨酯阻燃硬质泡沫仍能保持较高的硬度，实现阻燃性能与硬度等性能的协同调节；且组合物半年以上性能稳定，不易分层。
进一步可选地，以B组分总量计，阻燃剂的量为10-22wt％，诸如可以为10wt％、12wt％、14wt％、16wt％、18wt％、20wt％或22wt％；干燥剂的量为0.15-0.32wt％，诸如可以为0.16wt％、0.18wt％、0.20wt％、0.22wt％、0.24wt％、0.26wt％、0.28wt％、0.30wt％或0.31wt％；防结晶剂的量为0.21-0.32wt％，可选地为0.23-0.32wt％，诸如可以为0.22wt％、0.24wt％、0.26wt％、0.28wt％、0.30wt％或0.31wt％；异氰酸酯的量为77-90wt％，诸如可以为78wt％、80wt％、82wt％、84wt％、86wt％、88wt％或89wt％。该可选的方案下，通过高含量干燥剂来调控水分，高含量防结晶剂，配合适宜量的异氰酸酯，能够增加B组分的可存储温度范围，实现常温半年以上长久存储，不失效，且与A组分反应效果好，性能优异；可选地，干燥剂含量适宜高，能够充分的吸收阻燃剂中较高的水分、空气水分以及储存过程中吸收的水分，更利于减少B组分粘度变大等劣化现象；从而更利于B组分保持原有的粘度，更利于B组分的稳定储存；而且，加入适宜高含量的防结晶剂，能够避免异氰酸酯(如粗MDI)与阻燃剂混合时会吸空气中的水分而变成结晶，避免B组分低温储存发生近聚反应形成结晶，从而使得B组分的储存温度范围更宽，可常温储存。
可选地，催化剂包括环己胺。
可选地，发泡剂包括水和环戊烷，其中，以A组分总量计，水的量为1-4wt％，诸如可以为1.5wt％、2.0wt％、2.5wt％、3.0wt％或3.5wt％；环戊烷的量为6-14wt％，诸如可以为6.5wt％、7wt％、8wt％、9wt％、10wt％、11wt％、12wt％或13wt％。
可选地，干燥剂包括亚磷酸酯和任选的苯酚，优选地，以质量计，亚磷酸酯/苯酚为(1.3-1.6):1，诸如可以为1.35:1、1.4:1、1.45:1、1.5:1或1.55:1，其更利于协同快速吸收水分。
可选地，防结晶剂包括高氯酸和任选的三氟甲磺酸，可选地，以质量计，高氯酸/三氟甲磺酸为(1.2-1.7):1，诸如可以为1.3:1、1.4:1、1.5:1、1.6:1、或1.65:1、，其更利于协同快速防止B组分结晶。
在本公开可选的一些实施方式中，阻燃剂为TCPP(即磷酸三(2-氯丙基)酯)和TEP(即磷酸三乙酯)，以质量计，TCPP/TEP为1：(1.1-1.9)，例如可以为1：(1.2-1.8)、1：(1.3-1.7)或1：(1.4-1.6)，诸如可以为1：1.1、1：1.2、1：1.3、1：1.4、1：1.5、1：1.6、1：1.7、1：1.8、1：1.9中的任一值以及相邻点值之间的任一值。该可选的方案，更利于增强阻燃效果。可以理解的是，一般地，阻燃剂中含水。
阻燃剂TCPP例如可以为淳安助剂厂市售品，阻燃剂TEP例如可以为淳安助剂厂市售品，当然，也可以为其他厂商的市售品。
本公开异氰酸酯可以采用本领域的常见的粗MDI，可选地为二苯甲烷二异氰酸酯。
可以理解的是，本公开的A组分和B组分是分开储存的，可选地，在室温下储存，在使用时，可以按需在所需条件下混合反应。可选地，B组分在常温下干燥、充氮保压的隔绝空气的密闭腔室内混合制备，充氮保压的压力为0.05-0.2MPa。
本公开提供了一种高氧指数聚氨酯阻燃硬质泡沫，其由上述组合物制备得到，聚氨酯阻燃硬质泡沫的氧指数在32％以上(即≥32％)；且，聚氨酯阻燃硬质泡沫的性能满足：在6个月之后，密度偏差变化率小于10％，压力泡密度变化率小于12％，强度在140kPa以上(即≥140kPa)，尺寸稳定性收缩小于1％，导热系数不超过0.022W/(m·K)。
可选地，本公开聚氨酯阻燃硬质泡沫的泡孔细密。
本公开密度偏差变化率的计算方法为：((半年后的密度-初始密度)/初始密度)×100％。此处密度是指泡沫去皮后的芯密度。压力泡密度变化率的计算方法同理。本公开密度和压力泡密度的测试均为本领域行业标准通用的排水法，在此不再赘述。
所述强度是指聚氨酯阻燃硬质泡沫的平行方向和/或垂直方向上的强度。所述强度、所述尺寸稳定性收缩的测试均为本领域行业标准通用的方法，在此不再赘述。
本公开提供了一种高氧指数聚氨酯阻燃硬质泡沫的制备方法，采用上述组合物来制备高氧指数聚氨酯阻燃硬质泡沫，包括：
将A组分中各成分混合反应，得到第一混料；
将B组分中的各成分在常温下干燥、充氨保压的隔绝空气的密闭腔室内混合反应，得到第二混料；
将第一混料和第二混料混合发泡，得到高氧指数聚氨酯阻燃硬质泡沫。
在上述制备方法中，将B组分中的各成分在常温下干燥、充氮保压的隔绝空气的密闭腔室内混合，能避免与空气接触的环境，防止吸水而导致B组分粘度变化、产生聚脲反应，出现结晶。
本公开所述充氮保压是指，充入氮气置换出空气，并保持密闭腔室内的压力为0.05-0.2MPa。
本公开所述混合反应的时间，本领域技术人员可以根据需求选择。可选地，A组分的混合反应时间为30-100min，B组分的混合反应时间为30-100min。
本公开克服了现有技术存在的聚氨酯硬泡材料用组合物存放期短且阻燃性无法满足要求的缺陷，提供一种高氧指数聚氨酯阻燃硬质泡沫及其组合物和制备方法，该聚氨酯阻燃硬质泡沫能够在满足硬度要求的情况下，具有优异的阻燃性能，而且可长时间储存，不分层，性能稳定。
本公开通过上述技术方案，一方面，添加阻燃剂和阻燃聚醚用于协同阻燃且进行分 开储存，能够防止阻燃剂活性失效，即便在长时间储存后也能保持阻燃剂活性，且阻燃聚醚的加入能在一定程度上减少阻燃剂的加入量，还能够在混合时具有协同阻燃的效果，具体的，阻燃聚醚参与反应，形成了利于阻燃的泡沫结构，为泡沫结构性阻燃；阻燃剂不参与反应，为物理性阻燃，从而协同作用使得聚氨酯阻燃硬质泡沫具有高氧指数，氧指数达32％以上，具有优异的阻燃效果；另一方面，控制含聚醚和阻燃聚醚的A组分为碱性体系，既有利于阻燃聚醚在A组分中的均匀分散，又能保证A组分长期储存期间不发生沉降，从而保持阻燃聚醚的活性，从而提高A组分的化学稳定性，有利于聚醚、阻燃聚醚等组分的稳定存储，储存半年以上性能稳定，不易分层；控制含异氰酸酯和阻燃剂的B组分为酸性体系，能够有利于阻燃剂等B组分的稳定存储，储存半年以上性能稳定，不易分层。
总之，本公开的组合物能够在添加较低量的阻燃剂的情况下，使得聚氨酯阻燃硬质泡沫在保持硬度达标的情况下，具有优异的阻燃效果，且储存时间长。
实施例
下面结合实施例对本公开进行详细阐述。其中，原料含量均以质量计。
实施例1
组分配比：
A组分：聚醚4110(羟值450mgKOH/g)48％；阻燃聚醚LY-Pb01(羟值330mgKOH/g)30％；催化剂环己胺3％；硅油4％；发泡剂环戊烷13％，水含量2％；A组分的pH为8；聚醚的羟值与阻燃聚醚的羟值的比值为1.36：1。
B组分：粗MDI 80.51％；
C组分：阻燃剂TCPP 9％；阻燃剂TEP 10％；干燥剂亚磷酸酯0.25％；防结晶剂高氯酸0.24％。其中，B组分+C组分的总含水量小于100ppm。
将A组分单独储存，其储存半年后不分层。
关于B组分和C组分的储存实验：将B组分与C组分进行混合储存，pH为5.6，其储存半年后不分层。
储存后的混合结晶试验：
试验1、将B组分与上述C组分(含干燥剂和防结晶剂)进行混合储存作为G组分，将G组分和A组分分别单独储存一定时间后，以质量比1.3:1进行混合发泡，其中阻燃聚醚的质量m和阻燃剂的质量n满足：m/n为2.05:1。观察其结晶实验和上机发泡实验。结果如下表1所示。
试验2、将B组分与上述C组分中的除干燥剂和防结晶剂以外的组成(不含干燥剂和防结晶剂)进行混合储存作为F组分，将F组分和A组分分别单独储存一定时间后，以质量比1.3:1进行混合，观察其结晶实验和上机发泡实验。结果如下表1所示。
表1
对比例1
按照实施例1的组分配比，进行如下储存实验：
将A组分与质量比为1:1.4的TCPP和TEP(TCPP和TEP的总量同实施例1)进行混合储存，pH为8；存放一周时分层。且加入TCPP和TEP的总量越多，pH值越小，越容易分层。
将A组分与质量比为1:0.875的TCPP和TEP(TCPP和TEP的总量同实施例1)进行混合储存，pH为8.3；存放一周时不分层，存放2个月分层。
将A组分与质量比为1:1.8的TCPP和TEP(TCPP和TEP的总量同实施例1)进行混合储存，pH为7.6；存放一周时分层。
A组分为：按照实施例1的A组分，不同的是，采用相同用量的4110H油醚(厂家：佳化化学股份有限公司)代替聚醚4110，A组分的pH为11；存放一周时不分层，存放两个月时分层。
B组分为：异氰酸酯50％和TCPP 25％、TEP 25％，B组分的pH为6.3；存放一周时分层。
对比例2
按照实施例1的组分配比，将B组分(MDI)和A组分分别单独储存一定时间后，以质量比1.3:1进行混合，观察其结晶实验和上机发泡实验的枪头堵塞情况。结果如表1所示。
由上述表1可以看出，由于粗MDI会吸收空气中的水分进行聚脲反应出现浑浊、结晶，而当MDI与阻燃剂的组合进行储存一定时间后混合时，能够降低结晶发生的可能，降低枪头堵塞情况；进一步额外添加干燥剂和防结晶剂的MDI组合，效果最优，无浑浊结晶，无枪头堵塞。
实施例2
按照实施例1的组分配比，不同的是，调节聚醚的种类，使得聚醚的羟值与阻燃聚醚的羟值的比值为1.5：1，且A组分为碱性体系，pH为9。
本实施例的A组分储存半年，不分层。
并按照实施例1中试验1的方法进行储存后的混合结晶试验，结果与实施例1中试验1的结果相同。
实施例3
按照实施例1的组分配比，不同的是，调节阻燃聚醚的量，使得阻燃聚醚的质量m和阻燃剂的总质量n满足：m/n为4：1，并调整聚醚的量以满足A组分100％总量，且 A组分为碱性体系，pH为9。
本实施例的A组分储存半年，不分层。
并按照实施例1中试验1的方法进行储存后的混合结晶试验，结果与实施例1中试验1的结果相同。
实施例4
按照实施例1的组分配比，不同的是，C组分中的干燥剂和防结晶剂的组成不同，所述干燥剂包括亚磷酸酯和苯酚，以质量计，亚磷酸酯/苯酚为1.4:1；所述防结晶剂包括高氯酸和三氟甲磺酸，以质量计，高氯酸/三氟甲磺酸为1.5:1。
B组分和C组分的混合体系为酸性体系，pH为5.5。
本实施例的B组分和C组分的混合体系储存半年，不分层。
并按照实施例1中试验1的方法进行储存后的混合结晶试验，结果与实施例1中试验1的结果相同。
实施例5
按照实施例1的组分配比，不同的是，调节聚醚的种类，使得聚醚的羟值与阻燃聚醚的羟值的比值为1：1，且A组分为碱性体系，pH为10。
本实施例的A组分储存半年，不分层。
并按照实施例1中试验1的方法进行储存后的混合结晶试验，结果与实施例1中试验1的结果相同。
实施例6
按照实施例1的组分配比，不同的是，调节阻燃聚醚的量，使得阻燃聚醚的质量m和阻燃剂的总质量n满足：m/n为1：1，并调整聚醚的量以满足A组分100％总量，且A组分为碱性体系，pH为9.5。
本实施例的A组分储存半年，不分层。
并按照实施例1中试验1的方法进行储存后的混合结晶试验，结果与实施例1中试 验1的结果相同。
测试例
按照实施例1的最优组分配比，不同的是：
将A组分与TCPP 5％和TEP 7％进行混合反应，得到第一混料记为I组分，按照I组分/B组分质量比＝1.3，与B组分进行混合发泡，记为实验D。
将B组分与C组分在常温下干燥、充氮保压的隔绝空气的密闭腔室内混合，得到第二混料，其中充氮保压的压力为0.1MPa，记为G组分，按照G组分/A组分质量比＝1.3，与A组分混合发泡，记为实验Q1，其中混合发泡时控制原料料温为25℃。
上述发泡后，进行脱模，得到聚氨酯阻燃硬质泡沫。然后对其进行性能测试，结果如下表2。
并将对比例2中混合得到的物料进行相同条件的发泡，记为实验E，然后对其进行性能测试，结果如下表2。
并分别将实施例2-实施例6中B组分和C组分混合存储，之后与A组分以质量比1.3:1混合，进行相同条件的发泡，依次记为实验Q2、Q3、Q4、Q5、Q6，然后对其进行性能测试，结果如下表3。其中，6个月密度偏差变化率＝((半年后的密度-初始的密度)/初始的密度)×100％，压力泡密度变化率＝((半年后的压力泡密度-初始的压力泡密度)/初始的压力泡密度)×100％。
表2

注：D初始，是指实验D得到的聚氨酯阻燃硬质泡沫立即进行性能测试的数据。D两个月后是指，实验D得到的聚氨酯阻燃硬质泡沫在两个月后进行性能测试的数据。其他相应表达同理。其中，尺寸稳定性为-3.8％是指尺寸收缩3.8％，以评价稳定性。其中，发泡时间(CT/GT/TFT)是指混合发泡后的不同反应的时间，CT、GT、TFT依次为乳白时间、拉丝时间、失粘时间。
表3

由上可以看出，相对于异氰酸酯不加阻燃剂的方案，异氰酸酯中加入阻燃剂的方案的存放时间长，且可加入较高量的阻燃剂，储存半年以上无分层，强度高，氧指数在32％以上，阻燃效果优，能达到B1要求，熟化时间短，尺寸稳定性能达到要求。
进一步的，通过对比实施例1和实施例5-6，可以看出，采用本公开可选的聚醚组合或可选的阻燃聚醚和阻燃剂适宜配比的方案，所得聚氨酯阻燃硬质泡沫的阻燃性进一步提高，且导热、强度等其他性能得到相对的进一步的提升。
以上详细描述了本公开可选的实施方式，但是，本公开并不限于此。在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本公开所公开的内容，均属于本公开的保护范围。
工业实用性
本公开提供一种高氧指数聚氨酯阻燃硬质泡沫及其组合物和制备方法，本公开的组合物能够在添加较低量的阻燃剂的情况下，使得聚氨酯阻燃硬质泡沫在保持硬度达标的情况下，具有优异的阻燃效果，且储存时间长，因此具有优异的实用性能。

Claims (12)

  1. 一种高氧指数聚氨酯阻燃硬质泡沫用组合物，包括A组分和B组分，其特征在于，所述A组分包括聚醚和阻燃聚醚，所述B组分包括异氰酸酯和阻燃剂，控制所述A组分的pH为7.5-10，所述B组分的pH为4-6。
  2. 根据权利要求1所述的组合物，其特征在于，所述聚醚的羟值与所述阻燃聚醚的羟值的比值为(1.19-1.57)：1。
  3. 根据权利要求1或2所述的组合物，其特征在于，所述阻燃聚醚的羟值为300-360mgKOH/g，所述聚醚的羟值为430-470mgKOH/g。
  4. 根据权利要求1所述的组合物，其特征在于，所述阻燃聚醚的质量m和阻燃剂的质量n满足：m/n为(2-6.5)：1。
  5. 根据权利要求1所述的组合物，其特征在于，所述A组分还包括催化剂、硅油和发泡剂，所述B组分还包括干燥剂和防结晶剂。
  6. 根据权利要求5所述的组合物，其特征在于，
    以A组分总量计，所述阻燃聚醚的量为30-42wt％，催化剂的量为2.5-4.5wt％，硅油的量为3-4.5wt％，发泡剂的量为10-15wt％，聚醚的量为34-54.5wt％；
    以B组分总量计，所述阻燃剂的量为10-22wt％，干燥剂的量为0.15-0.32wt％，防结晶剂的量为0.21-0.32wt％，异氰酸酯的量为77-89.64wt％。
  7. 根据权利要求6所述的组合物，其特征在于，
    所述催化剂包括环己胺；
    所述发泡剂包括水和环戊烷，其中，以A组分总量计，水的量为1-4wt％，环戊烷的量为6-14wt％；
    所述干燥剂包括亚磷酸酯和任选的苯酚，优选地，以质量计，亚磷酸酯/苯酚为(1.3-1.6):1；
    所述防结晶剂包括高氯酸和任选的三氟甲磺酸，优选地，以质量计，高氯酸/三氟 甲磺酸为(1.2-1.7):1。
  8. 根据权利要求1所述的组合物，其特征在于，
    所述A组分中水的量为1.5-2.5wt％；所述B组分的含水量小于200ppm，优选不超过100ppm；
    和/或，所述阻燃剂为TCPP和TEP，以质量计，TCPP/TEP为1：(1.1-1.9)；
    和/或，所述阻燃聚醚选自LY-pb01、LY-pb02。
  9. 根据权利要求1所述的组合物，其特征在于，
    所述A组分中水的量为1.5-2.5wt％；所述B组分的含水量小于200ppm，可选地，所述B组分的含水量不超过100ppm。
  10. 一种高氧指数聚氨酯阻燃硬质泡沫，其特征在于，其由权利要求1-9中任一项所述的组合物制备得到；
    优选地，所述高氧指数聚氨酯阻燃硬质泡沫的氧指数在32％以上；且，所述高氧指数聚氨酯阻燃硬质泡沫的性能满足：在6个月之后，密度偏差变化率小于10％，压力泡密度变化率小于12％，强度在140kPa以上，尺寸稳定性收缩小于1％，导热系数不超过0.022W/(m·K)。
  11. 一种高氧指数聚氨酯阻燃硬质泡沫的制备方法，其特征在于，采用如权利要求1-9任一项所述的组合物来制备所述高氧指数聚氨酯阻燃硬质泡沫，包括：
    将所述A组分中各成分混合反应，得到第一混料；
    将所述B组分中的各成分在常温下干燥、充氮保压的隔绝空气的密闭腔室内混合，得到第二混料，其中充氮保压的压力为0.05-0.2MPa；
    将第一混料和第二混料混合发泡，得到高氧指数聚氨酯阻燃硬质泡沫。
  12. 权利要求1-9中任一项所述的组合物或者权利要求10所述高氧指数聚氨酯阻燃硬质泡沫用于保温隔热材料、防水保温一体化材料、建筑板材、家电中的用途。
PCT/CN2023/083425 2022-06-17 2023-03-23 一种高氧指数聚氨酯阻燃硬质泡沫及其组合物和制备方法 WO2023241155A1 (zh)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101768250A (zh) * 2009-12-25 2010-07-07 山东东大一诺威聚氨酯有限公司 一种高阻燃聚氨酯组合物及其制备方法
CN103183806A (zh) * 2013-04-17 2013-07-03 北京东方雨虹防水技术股份有限公司 一种高阻燃硬质聚氨酯泡沫材料及其制备方法
CN105131226A (zh) * 2015-09-29 2015-12-09 上海应用技术学院 一种难燃b1级聚氨酯硬质泡沫及其制备方法
CN115028794A (zh) * 2022-06-17 2022-09-09 天长市伯士的环保新材料有限公司 一种高氧指数聚氨酯阻燃硬质泡沫及其组合物和制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL361365A1 (en) * 2003-07-21 2004-01-12 ORION Sp.z o.o. Prepolymer compound for producing polyurethane foam in earosol container, featuring low content of isocyanate monomer
CN104592470A (zh) * 2014-12-24 2015-05-06 上海华峰材料科技研究院（有限合伙） 一种阻燃聚异氰脲酸酯硬质泡沫及其制备方法
CN107459616A (zh) * 2017-08-17 2017-12-12 四川金和成科技有限公司 一种高阻燃聚氨酯泡沫的制备方法
CN111647190B (zh) * 2020-06-16 2022-05-20 中山市伯士的化工科技有限公司 制备聚氨酯硬泡的配方、套装及其制备方法以及聚氨酯硬泡及其制备方法与应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101768250A (zh) * 2009-12-25 2010-07-07 山东东大一诺威聚氨酯有限公司 一种高阻燃聚氨酯组合物及其制备方法
CN103183806A (zh) * 2013-04-17 2013-07-03 北京东方雨虹防水技术股份有限公司 一种高阻燃硬质聚氨酯泡沫材料及其制备方法
CN105131226A (zh) * 2015-09-29 2015-12-09 上海应用技术学院 一种难燃b1级聚氨酯硬质泡沫及其制备方法
CN115028794A (zh) * 2022-06-17 2022-09-09 天长市伯士的环保新材料有限公司 一种高氧指数聚氨酯阻燃硬质泡沫及其组合物和制备方法

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