Halogen-free flame-retardant all-water foaming rigid polyurethane foam material and preparation method thereof

Abstract

The invention discloses a halogen-free flame-retardant all-water foaming rigid polyurethane foam material and a preparation method thereof, and belongs to the technical field of polyurethane synthetic materials. The component A is prepared from polyether polyol, a tertiary amine catalyst, an organic tin catalyst, a foam stabilizer, deionized water and a halogen-free flame retardant; and the component B is polymerized MDI. A preparation method of the component A comprises the following steps: adding polyether polyol, a tertiary amine catalyst, an organic tin catalyst and the like into a stirrer, and stirring; starting vacuumizing and stirring, discharging, sealing and storing to obtain the component A; the environment-friendly all-water foaming system and the halogen-free flame retardant are adopted, and the material has excellent flame retardance, mechanical strength and heat preservation and heat insulation performance and is suitable for occasions with strict requirements for light weight and heat stability such as building wall heat preservation, refrigeration equipment heat insulation layers and new energy automobile battery pack packaging. The rigid polyurethane foam material is especially suitable for application scenarios with strict requirements for environmental protection and fireproof safety.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane synthetic materials, and specifically relates to a halogen-free flame-retardant all-water foamed rigid polyurethane foam material and a preparation method thereof. Background Art

[0002] Traditional rigid polyurethane foam materials mostly use physical blowing agents (such as HCFCs), which have problems of ozone layer depletion and greenhouse effect. Although halogen-containing flame retardants (such as brominated flame retardants) can improve flame retardancy, they release toxic gases when burning, which does not meet environmental protection requirements. It is difficult to balance the flame retardancy, mechanical strength and dimensional stability of existing all-water foamed system foams. Most of the existing two-component foamed polyurethanes have unequal proportion ratios, and cannot use market-equivalent proportion equipment. Customized equipment increases the use cost and limits the application of materials.

[0003] The present invention develops a halogen-free flame-retardant all-water foamed rigid polyurethane foam material and a preparation method thereof, which solve the above-mentioned problems. Summary of the Invention

[0004] The purpose of the present invention is to provide a halogen-free flame-retardant all-water foamed rigid polyurethane foam material and a preparation method thereof, which solve the problems of poor safety and environmental protection, improve the mechanical strength of the material, and reduce the cost.

[0005] To achieve the above purpose, the present invention provides the following technical solution: A halogen-free flame-retardant all-water foamed rigid polyurethane foam material, wherein the component A of the halogen-free flame-retardant all-water foamed rigid polyurethane foam material is prepared from polyether polyol 1, polyether polyol 2, polyether polyol 3, tertiary amine catalyst, organotin catalyst, foam stabilizer, deionized water, and halogen-free flame retardant; The component B of the halogen-free flame-retardant all-water foamed rigid polyurethane foam material is polymeric MDI.

[0006] Further, the mass part of the polyether polyol 1 is 10-15; the mass part of the polyether polyol 2 is 65-70; the mass part of the polyether polyol 3 is 15-20; the mass part of the tertiary amine catalyst is 0.5-6; the mass part of the organotin catalyst is 0.2-3; the mass part of the foam stabilizer is 1-3; the mass part of the deionized water is 0.5-2; the mass part of the halogen-free flame retardant is 15-30; The mass part of the polymeric MDI is 110-136.

[0007] Further, the molecular weight of the polyether polyol 1 is 2000 - 4000; the molecular weight of the polyether polyol 2 is 16000 - 20000; the molecular weight of the polyether polyol 3 is 6000 - 10000; the tertiary amine catalyst is triethylenediamine; the organotin catalyst is dibutyltin dilaurate; the foam stabilizer is silicone oil; the halogen-free flame retardant is a halogen-free phosphate flame retardant; the molecular weight of the polymeric MDI is 320 - 400.

[0008] Further, the parts by mass of the polyether polyol 1 are 10 - 15; the parts by mass of the polyether polyol 2 are 65 - 70; the parts by mass of the polyether polyol 3 are 15 - 20; the parts by mass of the tertiary amine catalyst are 0.6 - 6; the parts by mass of the organotin catalyst are 0.2 - 3; the parts by mass of the foam stabilizer are 2 - 3; the parts by mass of deionized water are 0.8 - 1.2; the parts by mass of the halogen-free flame retardant are 15 - 30; The parts by mass of the polymeric MDI are 126 - 136.

[0009] Further, the parts by mass of the polyether polyol 1 are 15; the parts by mass of the polyether polyol 2 are 65; the parts by mass of the polyether polyol 3 are 20; the parts by mass of the tertiary amine catalyst are 0.6 - 6; the parts by mass of the organotin catalyst are 0.2 - 3; the parts by mass of the foam stabilizer are 2 - 3; the parts by mass of deionized water are 0.8 - 1.2; the parts by mass of the halogen-free flame retardant are 22; The parts by mass of the polymeric MDI are 126 - 136.

[0010] Further, in the preparation of the halogen-free flame-retardant all-water-blown rigid polyurethane foam material using the component A and the component B, the mass ratio of the component A to the component B is 1:1.

[0011] For the preparation method of the halogen-free flame-retardant all-water-blown rigid polyurethane foam material, the preparation method of the component A is specifically as follows: S1: Add the polyether polyol 1, the polyether polyol 2, the polyether polyol 3, the tertiary amine catalyst, the organotin catalyst, the foam stabilizer, the deionized water, and the halogen-free flame retardant into a blender and stir. S2: Turn on the vacuum pump and stir, then discharge and seal for storage to obtain the component A. Mix and stir the component A and the component B and foam to obtain the halogen-free flame-retardant all-water-blown rigid polyurethane foam material.

[0012] Further, in the step S1, the specific conditions for stirring are as follows: in a double-planet vacuum mixer, stir for 10 - 20 minutes at a high-speed dispersion of 500 - 1000 rpm and a low-speed stirring of 50 - 100 rpm; preferably, stir for 20 minutes at a high-speed dispersion of 880 rpm and a low-speed stirring of 52 rpm.

[0013] Further, in the step S2, the specific vacuum degree is -0.08 to -0.1 MPa; preferably, the specific vacuum degree is -0.1 MPa.

[0014] Further, in the step S2, the specific conditions for stirring are as follows: in a double-planet vacuum mixer, stir for 20 - 30 minutes at a high-speed dispersion of 500 - 1000 rpm and a low-speed stirring of 50 - 1100 rpm; preferably, stir for 25 minutes at a high-speed dispersion of 680 rpm and a low-speed stirring of 52 rpm.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. The environmental protection performance is significantly improved. Halogen-free flame retardant: Halogen-free flame retardants are used to avoid the release of toxic gases (such as HBr and dioxins) during combustion by traditional halogen-containing flame retardants (such as bromine-based ones), meeting the requirements of environmental protection regulations such as RoHS and REACH.

[0016] Full water foaming: Deionized water (0.5 - 2%) is used as a chemical foaming agent to replace traditional physical foaming agents (such as HCFCs and HFCs), eliminating the damage to the ozone layer and the greenhouse effect, and meeting the environmental protection requirements of the Montreal Protocol.

[0017] 2. The flame retardant performance is excellent. The added halogen-free phosphate ester flame retardant has high flame retardant performance and excellent anti-yellow core performance. The flame retardant grade reaches V-0, which is better than traditional halogen-containing flame retardant foams (usually V-1 or V-2 grade), and the smoke density during combustion is reduced by more than 50%, reducing the secondary hazards of fire.

[0018] The halogen-free phosphate ester flame retardant has good compatibility with the polyol system, and the flame retardant components are evenly dispersed, avoiding migration failure and having high long-term stability.

[0019] 3. The mechanical and heat insulation performances are optimized. High strength and lightweight coexist: The density (0.060 - 0.300 g / cm³) is lower than that of traditional foams (0.080 - 0.350 g / cm³), but the tensile strength ≥ 5 MPa, and the shear strength (Al - Al) ≥ 4.5 MPa, meeting the requirements of structural support.

[0020] Low thermal conductivity (0.020 - 0.035 W / m·K), with better heat insulation performance than similar physical foaming products (usually 0.035 - 0.045 W / m·K), suitable for fields such as building insulation and cold chain transportation.

[0021] 4. Process Efficiency and Cost Advantages One-step preparation: Direct foaming after mixing A / B components, simplifying the process and shortening the production cycle by more than 30% compared to traditional multi-step methods.

[0022] High raw material utilization rate: The addition amount of halogen-free flame retardant (15 - 30%) is lower than that of halogen-containing systems (usually 20 - 40%), reducing raw material costs.

[0023] Strong equipment compatibility: Supports manual stirring or mechanized pouring / spraying, adapting to different production scale requirements.

[0024] 5. Application Scenario Expansion Suitable for fields with strict environmental protection and fire prevention requirements, Construction industry: Exterior wall insulation sandwich panels, with a combustion performance grade up to A2 (combined with other flame retardant measures); Transportation: Flame retardant encapsulation material for new energy vehicle battery packs; Cold chain logistics: Insulation layer for refrigerated containers, with long-term resistance to low temperatures (-40°C) without cracking. Description of the Drawings

[0025] Figure 1 Flow chart for preparing halogen-free flame retardant all-water foamed rigid polyurethane foam material; Figure 2 Schematic diagrams of two main forming processes (spraying, pouring) of the present invention; Figure 3 Foaming ratio diagram of the rigid polyurethane foam material in Example 1; Figure 4 Flame retardancy diagram of the cured rigid polyurethane foam material in Example 1; Figure 5 Thermal conductivity measurement diagram of the cured rigid polyurethane foam material in Example 2.

[0026] Figure 6 Natural foaming cross-section diagram of the rigid polyurethane foam material in Example 1; Figure 7 Data analysis diagram of the damp and heat aging resistance test of the rigid polyurethane foam material in Example 1; Figure 8 Application of the rigid polyurethane foam material in Example 1 in the flame retardant encapsulation material for new energy vehicle battery packs; Figure 9The rigid polyurethane foam material of Example 2 is used as a thermal insulation material on the surface of thermal insulation parts. Detailed implementation manners

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Apparently, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention. The experimental methods described in the following embodiments are all conventional methods unless otherwise specified; the reagents and materials are all commercially available unless otherwise specified.

[0028] The purpose of the present invention is to provide a rigid polyurethane foam material that is safe, environmentally friendly, low-density and lightweight, and flame-retardant and heat-insulating for places such as new energy battery packs or subway and high-speed rail doors that require filling and potting. Another purpose of the present invention is to provide a preparation method for the above-mentioned rigid polyurethane foam material.

[0029] The present invention relates to a method for detecting the performance of materials, specifically as follows: 1. Density and viscosity The density detection of the A and B two-component stock solutions is based on GB / T 13354-1992.

[0030] The viscosity detection is carried out by the method of GB / T 10247-2008.

[0031] The determination of the free foam density of the foam is based on GB / T6343-2009.

[0032] 2. Foaming ratio The foaming ratio or expansion ratio refers to the multiple of the volume change of the sample before and after expansion, which is used to measure the expansion of the material before and after foaming. The ratio of the volume before and after foaming is the foaming ratio.

[0033] 3. Tensile strength and elongation at break Both the tensile strength and the elongation at break are detected by the method of "Test Method for Tensile Properties of Rigid Cellular Plastics GB9641-88".

[0034] 4. Hardness The hardness is detected by the method of "Test Method for Indentation Hardness of Vulcanized Rubber or Thermoplastic Rubber GB / T531-2008" (Shore C).

[0035] 5. Shear strength The shear strength (Al-Al) is detected by the method of "Adhesives - Determination of Tensile Shear Strength - Rigid-to-Rigid Adherends GB7124-2008".

[0036] 6. Flame Retardancy Performance The flame retardancy performance is detected by the method of "Determination of flammability of plastics - Horizontal and vertical methods GB / T 2408 - 2008".

[0037] 7. Thermal Conductivity The thermal conductivity is detected by the method of "Test method for thermal conductivity of plastics - Heat flow meter method GB / T 3399 - 1982".

[0038] Table 1 shows the relevant information of polyether polyol 1, polyether polyol 2, and polyether polyol 3.

[0039] Table 1 Relevant Information of Polyether Polyols Polyether polyol Molecular mass Hydroxyl value (mg KOH / g) Acid value (mg KOH / g) Water content (%) Viscosity (25°C) (mPa·s) Polyether polyol 1 2000-4000 100-140 ≤0.10 ≤0.10 100-250 Polyether polyol 2 16000-20000 600-660 ≤0.15 ≤0.10 200-500 Polyether polyol 3 6000-10000 300-330 ≤0.10 ≤0.10 500-900 The tertiary amine catalyst is triethylenediamine; the organotin catalyst is dibutyltin dilaurate. The foam stabilizer is silicone oil, that is, organosilicon surfactant, which is a Si - C type non - hydrolyzable silicone copolymer. The halogen - free flame retardant is an additive halogen - free phosphate flame retardant, with high flame retardancy performance and excellent anti - yellow core performance. The polymerized MDI molecular weight is a polymer based on diphenylmethane diisocyanate (MDI), with a molecular weight of 320 - 400. NCO content: 30.7 ± 0.5%, viscosity (25°C): 220 mPa·s.

[0040] Example 1: In component A, the mass part of polyether polyol 1 is 15; the mass part of polyether polyol 2 is 65; the mass part of polyether polyol 3 is 20; the mass part of the tertiary amine catalyst is 0.6; the mass part of the organotin catalyst is 0.2; the mass part of the foam stabilizer is 2; the mass part of deionized water is 0.8; the mass part of the halogen - free flame retardant is 22; The mass part of component B is 125.6.

[0041] Preparation of component A: Polyether polyol 1, polyether polyol 2, polyether polyol 3, tertiary amine catalyst, foam stabilizer, deionized water, and halogen - free flame retardant are accurately added into a planetary mixer with a vacuum - pumping and high - speed dispersion device according to the raw material ratio. Stir at 880 rpm for high - speed dispersion and 52 rpm for low - speed stirring for 20 min, then turn on the vacuum - pumping, with a vacuum degree of - 0.1 MPa, stir at 680 rpm for high - speed dispersion and 52 rpm for low - speed stirring for 25 min, and discharge and seal for storage to obtain component A of rigid polyurethane foam material.

[0042] The two - component is manually stirred and mixed for foaming according to a mass ratio of 1:1 or the casting process is carried out using special equipment to obtain rigid polyurethane foam material.

[0043] The process of preparing the halogen - free flame - retardant all - water - foamed rigid polyurethane foam material is as followsFigure 1 . Figure 2 It is a schematic diagram of two forming processes (spraying, casting) of the present invention.

[0044] The relevant properties of the rigid polyurethane foam material obtained in Example 1 are as follows: (1) The appearance of component A is a transparent liquid, with a viscosity of 469 mPa·s and a density of 1.084 g / cm 3 . The appearance of component B is a brown liquid, with a viscosity of 190 mPa·s and a density of 1.222 g / cm 3 .

[0045] (2) Surface drying time: 6 min. Curing hardness: 78 HA.

[0046] (3) Cream time is 150 s, and the long operation time can meet the use conditions such as casting and sealing of automotive battery packs.

[0047] (4) The density after foaming is 0.297 g / cm³, Figure 6 which is a cross-sectional view of the natural foam of the rigid polyurethane foam material.

[0048] Tensile strength is 6.56 Mpa, and elongation at break is 10.66%.

[0049] Shear strength (using Al-Al, room temperature curing for 1 h) is 0.52 MPa, with adhesive failure; shear strength (room temperature curing for 2 h) is 3.3 MPa, with cohesive failure; shear strength (room temperature curing for 4 h) is 6.2 MPa, with cohesive failure; shear strength (room temperature curing for 6 h) is 6.4 MPa, with cohesive failure.

[0050] Good resistance to damp heat aging (the strength can reach 70 - 80% of the initial strength after 1000 h of double "85" test), as shown in Figure 7 .

[0051] (5) Flame retardant grade V-0, as shown in Figure 4 . Specifically, the flame goes out within 10 seconds, and no particles fall off, meeting the UL94-V0 flame retardant grade.

[0052] (6) The foaming ratio of the rigid polyurethane foam material is 6.5, as shown in Figure 3 .

[0053] (7) Thermal conductivity is 0.030 W / m·K.

[0054] Example 2: In Component A, the mass part of polyether polyol 1 is 15; the mass part of polyether polyol 2 is 65; the mass part of polyether polyol 3 is 20; the mass part of the tertiary amine catalyst is 6; the mass part of the organotin catalyst is 3; the mass part of the foam stabilizer is 3; the mass part of deionized water is 1.2; the mass part of the halogen-free flame retardant is 22; The mass part of Component B is 135.2.

[0055] Preparation of Component A: Accurately add polyether polyol 1, polyether polyol 2, polyether polyol 3, tertiary amine catalyst, foam stabilizer, deionized water, halogen-free flame retardant, etc. according to the raw material ratio into a planetary mixer equipped with a vacuum pumping and high-speed dispersion device. Stir at 880 rpm for high-speed dispersion and 52 rpm for low-speed stirring for 20 min, then turn on the vacuum pumping. Under a vacuum degree of -0.1 MPa, stir at 680 rpm for high-speed dispersion and 52 rpm for low-speed stirring for 25 min, and then discharge and store it sealed to obtain Component A of rigid polyurethane foam material.

[0056] The two components are manually stirred and foamed in a mass ratio of 1:1 or sprayed using special equipment to obtain rigid polyurethane foam material.

[0057] The relevant properties of the rigid polyurethane foam material obtained in Example 2 are as follows: (1) The appearance of Component A is a transparent liquid, with a viscosity of 452 mPa·s and a density of 1.045 g / cm 3 . The appearance of Component B is a brown liquid, with a viscosity of 193 mPa·s and a density of 1.257 g / cm 3 .

[0058] (2) Surface drying time: 30 s. Curing hardness: 81 HA.

[0059] (3) Cream time is 6 - 8 s. The two components foam rapidly after mixing and stirring, which can meet the spraying use conditions.

[0060] (4) The density after foaming is 0.080 g / cm³, with strong adhesion and good high and low temperature resistance.

[0061] Tensile strength and shear strength were not tested because the foaming time of this material is short and it is impossible to test.

[0062] It has good resistance to damp heat aging.

[0063] (5) Flame retardant grade is V - 0. Specifically, the flame goes out within 10 seconds and there are no particles dropping, meeting the UL94 - V0 flame retardant grade.

[0064] (6) The foaming ratio of the rigid polyurethane foam material is 6.8.

[0065] (7) The thermal conductivity is 0.033 W / m·K, which can provide good heat insulation for automotive thermal management parts. Figure 5 It is the measurement diagram of the thermal conductivity of the cured rigid polyurethane foam material in Example 2.

[0066] The material prepared in the above Example 1 is suitable for the flame retardant encapsulation material of new energy vehicle battery packs, as shown in Figure 8 . The material prepared in Example 2 is suitable for the surface heat insulation material of heat insulation parts, as shown in Figure 9 . The material prepared in Example 2 is also suitable for the external wall thermal insulation sandwich panels in the construction industry.

[0067] The materials prepared by the present invention have the advantages of environmental friendliness, excellent flame retardant performance, long product storage time and stable performance, optimized mechanical and heat insulation performance, simple process, and low production cost.

[0068] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A halogen-free flame-retardant all-water foamed rigid polyurethane foam material, characterized in that: The component A of the halogen-free flame-retardant all-water foamed rigid polyurethane foam material is prepared from polyether polyol 1, polyether polyol 2, polyether polyol 3, tertiary amine catalyst, organotin catalyst, foam stabilizer, deionized water, and halogen-free flame retardant; The component B of the halogen-free flame-retardant all-water foamed rigid polyurethane foam material is polymeric MDI.

2. The halogen-free flame-retardant all-water foamed rigid polyurethane foam material according to claim 1, characterized in that: The mass parts of the polyether polyol 1 are 10 - 15; the mass parts of the polyether polyol 2 are 65 - 70; the mass parts of the polyether polyol 3 are 15 - 20; the mass parts of the tertiary amine catalyst are 0.5 - 6; the mass parts of the organotin catalyst are 0.2 - 3; the mass parts of the foam stabilizer are 1 - 3; the mass parts of the deionized water are 0.5 - 2; the mass parts of the halogen-free flame retardant are 15 - 30; The mass parts of the polymeric MDI are 110 - 136.

3. The halogen-free flame-retardant all-water foamed rigid polyurethane foam material according to claim 1, characterized in that: The molecular weight of the polyether polyol 1 is 2000 - 4000; the molecular weight of the polyether polyol 2 is 16000 - 20000; the molecular weight of the polyether polyol 3 is 6000 - 10000; the tertiary amine catalyst is triethylenediamine; the organotin catalyst is dibutyltin dilaurate; the foam stabilizer is silicone oil; the halogen-free flame retardant is a halogen-free phosphate flame retardant; the molecular weight of the polymeric MDI is 320 - 400.

4. The halogen-free flame-retardant all-water foamed rigid polyurethane foam material according to claim 1, characterized in that: The mass parts of the polyether polyol 1 are 10 - 15; the mass parts of the polyether polyol 2 are 65 - 70; the mass parts of the polyether polyol 3 are 15 - 20; the mass parts of the tertiary amine catalyst are 0.6 - 6; the mass parts of the organotin catalyst are 0.2 - 3; the mass parts of the foam stabilizer are 2 - 3; the mass parts of the deionized water are 0.8 - 1.2; the mass parts of the halogen-free flame retardant are 15 - 30; The mass parts of the polymeric MDI are 126 - 136.

5. A halogen-free flame-retardant all-water foamed rigid polyurethane foam material according to claim 1, characterized in that: The mass parts of the polyether polyol 1 are 15; the mass parts of the polyether polyol 2 are 65; the mass parts of the polyether polyol 3 are 20; the mass parts of the tertiary amine catalyst are 0.6 - 6; the mass parts of the organotin catalyst are 0.2 - 3; the mass parts of the foam stabilizer are 2 - 3; the mass parts of the deionized water are 0.8 - 1.2; the mass parts of the halogen-free flame retardant are 22; The mass parts of the polymeric MDI are 126 - 136.

6. The halogen-free flame-retardant all-water foamed rigid polyurethane foam material according to claim 2, characterized in that: When preparing the halogen-free flame-retardant all-water foamed rigid polyurethane foam material using the component A and the component B, the mass ratio of the component A to the component B is 1:

1.

7. A preparation method of a halogen-free flame-retardant all-water foamed rigid polyurethane foam material according to any one of claims 1 - 6, characterized in that: The specific preparation method of the component A is as follows: S1: Add the polyether polyol 1, the polyether polyol 2, the polyether polyol 3, the tertiary amine catalyst, the organotin catalyst, the foam stabilizer, the deionized water, and the halogen-free flame retardant into a blender and stir; S2: Turn on the vacuum and stir, then discharge and seal for storage to obtain the component A; Mix and stir the component A and the component B and foam them to obtain the halogen-free flame-retardant all-water foamed rigid polyurethane foam material.

8. The preparation method of a halogen-free flame-retardant all-water foamed rigid polyurethane foam material according to claim 7, characterized in that: In the step S1, the specific conditions for the stirring are to stir in a double-planet vacuum mixer at a high speed of 500 - 1000 rpm and a low speed of 50 - 100 rpm for 10 - 20 minutes.

9. The preparation method of a halogen-free flame-retardant all-water foamed rigid polyurethane foam material according to claim 7, characterized in that: In the step S2, the specific vacuum degree is -0.08 to -0.1 MPa.

10. The preparation method of a halogen-free flame-retardant all-water foamed rigid polyurethane foam material according to claim 7, characterized in that: In the step S2, the specific conditions for the stirring are to stir in a double-planet vacuum mixer at a high speed of 500 - 1000 rpm and a low speed of 50 - 1100 rpm for 20 - 30 minutes.

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