Polyurethane composite insulation board and preparation method thereof

Abstract

The invention relates to the technical field of building materials, and provides a polyurethane composite insulation board and a preparation method thereof.The polyurethane composite insulation board is prepared from, by weight, 40-60 parts of polyether polyol, 50-80 parts of isocyanate, 20-40 parts of epoxy resin and 6-10 parts of modified hollow glass beads, and the modified hollow glass beads are hollow glass beads with styrene grafted on the surfaces. The interface performance of the hollow glass beads can be improved through the hollow glass beads grafted with styrene on the surfaces, and the compatibility of the hollow glass beads with polyurethane and epoxy resin is improved, so that the temperature resistance and mechanical properties of the polyurethane composite insulation board can be improved; meanwhile, the mechanical property of the polyurethane composite insulation board is improved by adding the epoxy resin.

Description

Technical Field

[0001] The invention belongs to the technical field of building materials, and particularly relates to a polyurethane composite thermal insulation board and a preparation method thereof. Background Art

[0002] Existing insulation boards for building exterior walls are mainly divided into organic, inorganic and composite materials. Organic insulation boards mainly include extruded polystyrene foam boards, molded polystyrene foam boards, phenolic foam boards, polyurethane foam boards, etc. Organic insulation boards have low thermal conductivity, but poor flame retardancy, and are prone to cause fires when encountering open flames; inorganic insulation boards mainly include rock wool boards, glass wool boards, foamed cement boards, etc. Inorganic insulation boards have good flame retardancy, but their thermal conductivity is high, the thermal insulation effect is average, and they are heavy, making them inconvenient to transport and install.

[0003] Among them, polyurethane insulation boards have the advantages of good thermal insulation, sound insulation and cold resistance, and are widely used in building exterior wall insulation and thermal insulation of building interior and exterior walls and roofs. However, the heat resistance and mechanical properties of polyurethane insulation boards are poor, which affects the use effect and safety of polyurethane insulation boards. Summary of the invention

[0004] In view of the above situation, in order to overcome at least part of the defects of the above-mentioned prior art, the present invention provides a polyurethane composite insulation board and a preparation method thereof.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows: The present invention provides a polyurethane composite thermal insulation board, comprising the following components by weight: 40-60 parts of polyether polyol, 50-80 parts of isocyanate, 20-40 parts of epoxy resin and 6-10 parts of modified hollow glass microspheres. Wherein, the modified hollow glass microspheres are hollow glass microspheres with styrene grafted on the surface.

[0006] In some embodiments, the modified hollow glass microspheres are prepared from the following components: hollow glass microspheres, coupling agent KH570, styrene, and initiator.

[0007] In some embodiments, the hollow glass microspheres have a particle size of 50 μm to 150 μm.

[0008] In some embodiments, the initiator is one of benzoyl peroxide and azobisisobutyronitrile.

[0009] In some embodiments, the isocyanate is one of toluene diisocyanate and 4,4'-diphenylmethane diisocyanate.

[0010] In some embodiments, the polyurethane composite thermal insulation board further includes: a chain extender MOCA.

[0011] The present invention also provides a method for preparing a polyurethane composite thermal insulation board, comprising: Add modified hollow glass microspheres to polyether polyol, stir for 15-30 minutes, add isocyanate and epoxy resin, heat to 80-90°C, add chain extender, stir quickly, place in a mold, vulcanize for 1-2 hours, put in an oven at 80-100°C, heat for 10-15 hours, and obtain a polyurethane composite insulation board.

[0012] In some embodiments, the method for preparing the modified hollow glass microspheres comprises: S1. Take the hollow glass microspheres and add them to anhydrous ethanol, add coupling agent KH570, stir for 30 min-40 min, filter and dry to obtain hollow glass microspheres modified by coupling agent KH570; S2. Add the hollow glass microspheres modified by coupling agent KH570 into acetone, ultrasonically disperse for 40 min-50 min, heat to 50°C-60°C, add styrene and initiator, react for 3h-5h, centrifuge to obtain the precipitate, wash, and dry to obtain the modified hollow glass microspheres.

[0013] In some embodiments, in step S1, the mass ratio of the hollow glass microspheres to the coupling agent KH570 is 1:1-2.

[0014] In some embodiments, in step S2, the mass ratio of the hollow glass microspheres modified with coupling agent KH570, styrene and initiator is 1:(2-3):(0.1-0.2).

[0015] The beneficial effects achieved by the present invention are as follows: The addition of epoxy resin as an organic modifier can increase the degree of cross-linking of polyurethane and form an interpenetrating network structure between polyurethane and epoxy resin. This structure not only utilizes the advantages of each material, but also produces a synergistic effect through interaction, thereby improving the mechanical properties of the polyurethane composite insulation board.

[0016] At the same time, the hollow glass microspheres with styrene grafted on the surface can improve the interface performance of the hollow glass microspheres, and improve the compatibility of the hollow glass microspheres with polyurethane and epoxy resin, thereby improving the heat resistance and mechanical properties of the polyurethane composite insulation board. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a graph showing the test results of the temperature resistance performance of an embodiment of the present invention.

[0018] The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention. DETAILED DESCRIPTION

[0019] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them; based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0020] The disclosure below provides many different embodiments or examples to realize different structures of the present invention. In order to simplify the disclosure of the present invention, the parts and settings of specific examples are described below. Of course, they are only examples, and the purpose is not to limit the present invention. In addition, the examples of various specific processes and materials provided by the present invention, but those of ordinary skill in the art can appreciate the application of other processes and / or the use of other materials.

[0021] The first aspect of the present invention provides a polyurethane composite insulation board, which comprises the following components by weight: 40-60 parts of polyether polyol, 50-80 parts of isocyanate, 20-40 parts of epoxy resin and 6-10 parts of modified hollow glass microspheres. Wherein, the modified hollow glass microspheres are hollow glass microspheres with styrene grafted on the surface.

[0022] The addition of epoxy resin as an organic modifier can increase the degree of cross-linking of polyurethane, so that polyurethane and epoxy resin form an interpenetrating network structure. This structure not only utilizes the advantages of each material, but also produces a synergistic effect through interaction, thereby improving the mechanical properties of the polyurethane composite insulation board.

[0023] Hollow glass microspheres are tiny hollow particles made of glass. Due to their structure and physical and chemical properties, hollow glass microspheres are often used as fillers to improve the performance of composite materials. However, there are large differences in the properties (density, melting point, surface polarity, etc.) between polyurethane and epoxy resin and hollow glass microspheres, and the interface properties of the two are different and the compatibility is poor. Direct mixing will make it difficult to evenly disperse the hollow glass microspheres in the matrix, causing certain properties of the composite material to deteriorate and become brittle. Therefore, the surface of the hollow glass microspheres needs to be modified.

[0024] The hollow glass microspheres grafted with styrene on the surface can improve the interface performance of the hollow glass microspheres, and improve the compatibility of the hollow glass microspheres with polyurethane and epoxy resin, thereby improving the heat resistance and mechanical properties of the polyurethane composite insulation board.

[0025] In some embodiments, the modified hollow glass microspheres are prepared from the following components: hollow glass microspheres, coupling agent KH570, styrene, and initiator.

[0026] The hollow glass microspheres are modified by coupling agent KH570, and carbon-carbon double bonds are introduced on their surface. Under the action of the initiator, styrene is polymerized and connected with the silane coupling agent on the surface of the hollow glass microspheres, thereby improving the compatibility of the hollow glass microspheres with polyurethane and epoxy resin, thereby improving the heat resistance and mechanical properties of the polyurethane composite insulation board.

[0027] In some embodiments, the hollow glass microspheres have a particle size of 50 μm to 150 μm. Hollow glass microspheres with a moderate particle size are advantageous for dispersion in polyurethane and epoxy resin, and can effectively reduce the shrinkage of the polyurethane composite insulation board, and prevent the polyurethane composite insulation board from bending, warping, etc. caused by residual strain, thereby improving the dimensional stability of the polyurethane composite insulation board.

[0028] In some embodiments, the initiator is one of benzoyl peroxide and azobisisobutyronitrile. Under the initiation of the initiator, styrene is polymerized and connected with the silane coupling agent on the surface of the hollow glass microspheres, so that hollow glass microspheres with styrene grafted on the surface can be prepared, wherein benzoyl peroxide has a higher initiation efficiency and azobisisobutyronitrile has fewer side reactions, so the reaction process is purer.

[0029] In some embodiments, the isocyanate is one of toluene diisocyanate and 4,4'-diphenylmethane diisocyanate. Toluene diisocyanate and 4,4'-diphenylmethane diisocyanate have high reactivity and good performance, and can be used to prepare polyurethane with excellent performance, which is beneficial to improving the performance of polyurethane composite insulation board.

[0030] In some embodiments, the polyurethane composite insulation board further comprises: 8-12 parts of chain extender MOCA. Chain extender MOCA can extend the length of the polyurethane molecular chain and increase the molecular weight of the polyurethane, thereby improving the strength, hardness and modulus of the polyurethane material, making it have better physical and mechanical properties.

[0031] A second aspect of the present invention provides a method for preparing a polyurethane composite thermal insulation board, comprising: Add modified hollow glass microspheres to polyether polyol, stir for 15-30 minutes, add isocyanate and epoxy resin, heat to 80-90°C, add chain extender, stir quickly, place in a mold, vulcanize for 1-2 hours, put in an oven at 80-100°C, heat for 10-15 hours, and obtain a polyurethane composite insulation board.

[0032] Among them, polyether polyol and isocyanate can react to form polyurethane, epoxy resin can improve the cross-linking degree of polyurethane, and modified hollow glass microspheres added as fillers can improve the heat resistance and mechanical properties of the polyurethane composite insulation board.

[0033] In some embodiments, the method for preparing the modified hollow glass microspheres comprises: S1. Take the hollow glass microspheres and add them to anhydrous ethanol, add coupling agent KH570, stir for 30 min-40 min, filter and dry to obtain hollow glass microspheres modified by coupling agent KH570; S2. Add the hollow glass microspheres modified by coupling agent KH570 into acetone, ultrasonically disperse for 40 min-50 min, heat to 50°C-60°C, add styrene and initiator, react for 3h-5h, centrifuge to obtain the precipitate, wash, and dry to obtain the modified hollow glass microspheres.

[0034] Because the CH of coupling agent KH570 3 O can react with -OH on the surface of the hollow glass microspheres to introduce carbon-carbon double bonds into the hollow glass microspheres, providing conditions for the subsequent grafting of styrene; under the initiation of the initiator, styrene is polymerized and connected to the silane coupling agent on the surface of the hollow glass microspheres, thereby preparing modified hollow glass microspheres.

[0035] In some embodiments, the mass ratio of the hollow glass microspheres to the coupling agent KH570 is 1: 1-2. When the mass ratio of the hollow glass microspheres to the coupling agent KH570 is set within the range of 1: 1 to 1: 2, the problem of incomplete coating due to insufficient coupling agent can be avoided, and the degradation of material properties due to excessive thickness can be avoided, thereby improving the coating effect of the coupling agent on the surface of the hollow glass microspheres.

[0036] In some embodiments, the mass ratio of the hollow glass microspheres modified by the coupling agent KH570, styrene and initiator is 1:(2-3):(0.1-0.2). By setting the mass ratio of the hollow glass microspheres modified by the coupling agent KH570, styrene and initiator to 1:(2-3):(0.1-0.2), styrene can be fully coated on the surface of the hollow glass microspheres modified by the coupling agent to form a uniform polymer layer. At the same time, the amount of the initiator used within this range can ensure that the polymerization reaction proceeds at an appropriate rate, avoiding incomplete reaction or decreased product performance due to too fast or too slow reaction.

[0037] The present invention will be further described below by way of specific embodiments.

[0038] The experimental methods in the following examples are conventional methods unless otherwise specified; the experimental materials used in the following examples are purchased from commercial channels unless otherwise specified.

[0039] Example 1 A polyurethane composite thermal insulation board comprises the following components by weight: 40 parts of polyether polyol, 50 parts of isocyanate, 20 parts of epoxy resin, 6 parts of modified hollow glass microspheres and 8 parts of chain extender.

[0040] Preparation of modified hollow glass microspheres: S1. Take hollow glass microspheres and add them to anhydrous ethanol, add coupling agent KH570, the mass ratio of hollow glass microspheres to coupling agent KH570 is 1:1, stir for 30 minutes, filter and dry to obtain hollow glass microspheres modified by coupling agent KH570; S2. Add the hollow glass microspheres modified by coupling agent KH570 into acetone, ultrasonically disperse for 40 minutes, heat to 50°C, add styrene and initiator, the mass ratio of hollow glass microspheres modified by coupling agent KH570, styrene and initiator is 1:2:0.1, react for 3 hours, centrifuge to obtain the precipitate, wash and dry to obtain modified hollow glass microspheres.

[0041] Preparation of polyurethane composite insulation board: Add modified hollow glass microspheres to polyether polyol, stir for 15 minutes, add isocyanate and epoxy resin, heat to 80°C, add chain extender, stir rapidly, place in a mold, vulcanize for 1 hour, put in an oven at 80°C and heat for 10 hours to obtain a polyurethane composite insulation board.

[0042] Example 2 A polyurethane composite thermal insulation board comprises the following components by weight: 60 parts of polyether polyol, 80 parts of isocyanate, 40 parts of epoxy resin, 10 parts of modified hollow glass microspheres and 12 parts of chain extender.

[0043] Preparation of modified hollow glass microspheres: S1. Take hollow glass microspheres and add them to anhydrous ethanol, add coupling agent KH570, the mass ratio of hollow glass microspheres to coupling agent KH570 is 1:2, stir for 40 minutes, filter and dry to obtain hollow glass microspheres modified by coupling agent KH570; S2. Add the hollow glass microspheres modified by coupling agent KH570 into acetone, ultrasonically disperse for 50 minutes, heat to 60°C, add styrene and initiator, the mass ratio of hollow glass microspheres modified by coupling agent KH570, styrene and initiator is 1:3:0.2, react for 5 hours, centrifuge to obtain the precipitate, wash and dry to obtain modified hollow glass microspheres.

[0044] Preparation of polyurethane composite insulation board: Add the modified hollow glass microspheres to the polyether polyol, stir for 30 minutes, add isocyanate and epoxy resin, heat to 90°C, add chain extender, stir rapidly, place in a mold, vulcanize for 2 hours, put in an oven at 100°C and heat for 15 hours to obtain a polyurethane composite insulation board.

[0045] Example 3 A polyurethane composite thermal insulation board comprises the following components by weight: 50 parts of polyether polyol, 70 parts of isocyanate, 30 parts of epoxy resin, 8 parts of modified hollow glass microspheres and 10 parts of chain extender.

[0046] Preparation of modified hollow glass microspheres: S1. Take hollow glass microspheres and add them to anhydrous ethanol, add coupling agent KH570, the mass ratio of hollow glass microspheres to coupling agent KH570 is 1:1, stir for 35 minutes, filter and dry to obtain hollow glass microspheres modified by coupling agent KH570; S2. Add the hollow glass microspheres modified by coupling agent KH570 into acetone, ultrasonically disperse for 45 minutes, heat to 55°C, add styrene and initiator, the mass ratio of hollow glass microspheres modified by coupling agent KH570, styrene and initiator is 1:2.5:0.15, react for 4 hours, centrifuge to obtain the precipitate, wash and dry to obtain modified hollow glass microspheres.

[0047] Preparation of polyurethane composite insulation board: Add modified hollow glass microspheres to polyether polyol, stir for 20 minutes, add isocyanate and epoxy resin, heat to 85°C, add chain extender, stir rapidly, place in a mold, vulcanize for 1.5 hours, put in an oven at 90°C and heat for 13 hours to obtain a polyurethane composite insulation board.

[0048] Example 4 A polyurethane composite thermal insulation board comprises the following components by weight: 40 parts of polyether polyol, 50 parts of isocyanate, 20 parts of epoxy resin, 10 parts of modified hollow glass microspheres and 8 parts of chain extender.

[0049] Preparation of modified hollow glass microspheres: S1. Take hollow glass microspheres and add them to anhydrous ethanol, add coupling agent KH570, the mass ratio of hollow glass microspheres to coupling agent KH570 is 1:1, stir for 30 minutes, filter and dry to obtain hollow glass microspheres modified by coupling agent KH570; S2. Add the hollow glass microspheres modified by coupling agent KH570 into acetone, ultrasonically disperse for 40 minutes, heat to 50°C, add styrene and initiator, the mass ratio of hollow glass microspheres modified by coupling agent KH570, styrene and initiator is 1:2:0.1, react for 3 hours, centrifuge to obtain the precipitate, wash and dry to obtain modified hollow glass microspheres.

[0050] Preparation of polyurethane composite insulation board: Add modified hollow glass microspheres to polyether polyol, stir for 15 minutes, add isocyanate and epoxy resin, heat to 80°C, add chain extender, stir rapidly, place in a mold, vulcanize for 1 hour, put in an oven at 80°C and heat for 10 hours to obtain a polyurethane composite insulation board.

[0051] Example 5 A polyurethane composite thermal insulation board comprises the following components by weight: 60 parts of polyether polyol, 80 parts of isocyanate, 40 parts of epoxy resin, 6 parts of modified hollow glass microspheres and 12 parts of chain extender.

[0052] Preparation of modified hollow glass microspheres: S1. Take hollow glass microspheres and add them to anhydrous ethanol, add coupling agent KH570, the mass ratio of hollow glass microspheres to coupling agent KH570 is 1:2, stir for 40 minutes, filter and dry to obtain hollow glass microspheres modified by coupling agent KH570; S2. Add the hollow glass microspheres modified by coupling agent KH570 into acetone, ultrasonically disperse for 50 minutes, heat to 60°C, add styrene and initiator, the mass ratio of hollow glass microspheres modified by coupling agent KH570, styrene and initiator is 1:3:0.2, react for 5 hours, centrifuge to obtain the precipitate, wash and dry to obtain modified hollow glass microspheres.

[0053] Preparation of polyurethane composite insulation board: Add the modified hollow glass microspheres to the polyether polyol, stir for 30 minutes, add isocyanate and epoxy resin, heat to 90°C, add chain extender, stir rapidly, place in a mold, vulcanize for 2 hours, put in an oven at 100°C and heat for 15 hours to obtain a polyurethane composite insulation board.

[0054] Comparative Example 1 A polyurethane composite thermal insulation board, which differs from Example 1 in that hollow glass microspheres are used instead of modified hollow glass microspheres.

[0055] Comparative Example 2 A polyurethane composite thermal insulation board, which differs from Example 1 in that epoxy resin is not added.

[0056] Temperature resistance test: Referring to the standard GB / T17657-2013 “Test methods for physical and chemical properties of wood-based panels and veneer wood-based panels”, the heat resistance of the polyurethane composite insulation board was tested. The sample size was 30×30×30mm. The samples were placed in 0℃, 30℃, 60℃, 90℃, 120℃ and 150℃ environments for 2h, and the debonding or cracking size was recorded, and the peeling percentage was calculated.

[0057] Figure 1 It is a graph of the test results of the temperature resistance. As shown in the figure, the temperature resistance of Example 1 is greatly improved compared with that of Comparative Example 1 and Comparative Example 2. It can be seen that the addition of modified hollow glass microspheres and epoxy resin can improve the temperature resistance of the polyurethane composite insulation board.

[0058] Mechanical properties test: The compressive strength of the polyurethane composite insulation board was tested by using a QT-6201S universal tensile testing machine. The sample size was 50×50×30mm, the compression speed was 2mm / min, 5 samples were grouped together, and the results were taken as the average value.

[0059] Table 1

[0060] Table 1 shows the compressive strength test results. The compressive strength of Example 1 is increased by 36.1% and 75% compared with Comparative Example 1 and Comparative Example 2, respectively. It can be seen that the addition of modified hollow glass microspheres and epoxy resin can improve the compressive strength of the polyurethane composite insulation board to varying degrees.

[0061] The above is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A polyurethane composite insulation board, characterized in that: The invention comprises the following components by weight: 40-60 parts of polyether polyol, 50-80 parts of isocyanate, 20-40 parts of epoxy resin and 6-10 parts of modified hollow glass microspheres, wherein the modified hollow glass microspheres are hollow glass microspheres with styrene grafted on the surface.

2. The polyurethane composite thermal insulation board according to claim 1, characterized in that: The modified hollow glass microspheres are prepared from the following components: hollow glass microspheres, coupling agent KH570, styrene and initiator.

3. The polyurethane composite thermal insulation board according to claim 2, characterized in that: The particle size of the hollow glass microspheres is 50 μm-150 μm.

4. The polyurethane composite thermal insulation board according to claim 2, characterized in that: The initiator is one of benzoyl peroxide and azobisisobutyronitrile.

5. The polyurethane composite thermal insulation board according to claim 1, characterized in that: The isocyanate is one of toluene diisocyanate and 4,4'-diphenylmethane diisocyanate.

6. The polyurethane composite thermal insulation board according to claim 1, characterized in that: The polyurethane composite thermal insulation board also includes: a chain extender MOCA.

7. The method for preparing the polyurethane composite thermal insulation board according to any one of claims 1 to 6, characterized in that: include: Add modified hollow glass microspheres to polyether polyol, stir for 15-30 minutes, add isocyanate and epoxy resin, heat to 80-90°C, add chain extender, stir quickly, place in a mold, vulcanize for 1-2 hours, put in an oven at 80-100°C, heat for 10-15 hours, and obtain a polyurethane composite insulation board.

8. The preparation method according to claim 7, characterized in that: The preparation method of the modified hollow glass microspheres comprises: S1. Take the hollow glass microspheres and add them to anhydrous ethanol, add coupling agent KH570, stir for 30 min-40 min, filter and dry to obtain hollow glass microspheres modified by coupling agent KH570; S2. Add the hollow glass microspheres modified by coupling agent KH570 into acetone, ultrasonically disperse for 40 min-50 min, heat to 50°C-60°C, add styrene and initiator, react for 3h-5h, centrifuge to obtain the precipitate, wash, and dry to obtain the modified hollow glass microspheres.

9. The preparation method according to claim 8, characterized in that: In step S1, the mass ratio of the hollow glass microspheres to the coupling agent KH570 is 1:1-2.

10. The preparation method according to claim 8, characterized in that: In step S2, the mass ratio of the hollow glass microspheres modified by coupling agent KH570, styrene and initiator is 1:(2-3):(0.1-0.2).

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