Heat-preservation, sound-insulation and moisture-proof composite material and preparation method thereof

Abstract

The invention discloses a heat-preservation, sound-insulation and moisture-proof composite material and a preparation method thereof, and belongs to the technical field of high polymer materials. The heat-preservation, sound-insulation and moisture-proof composite material is prepared from the following raw materials in parts by weight: 60 to 65 parts of PVC (Polyvinyl Chloride), 15 to 20 parts of SBS (Styrene Butadiene Styrene), 2 to 5 parts of plasticizer, 8 to 12 parts of modified flexibilizer, 1 to 2 parts of anti-aging agent, 2 to 5 parts of modified coupling agent, 8 to 10 parts of ceramic hollow microbeads, 5 to 8 parts of nano silicon dioxide and 5 to 10 parts of flame retardant. The modified toughening agent is prepared by reacting 1, 4-benzene diboronic acid with polyethylene glycol to generate a hyperbranched product; and then reacting with 4, 4 '-methylene bis (phenyl isocyanate) to obtain the product. The prepared heat-preservation, sound-insulation and moisture-proof composite material has excellent impact resistance and heat-preservation, sound-insulation and moisture-proof performance.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a thermal insulation, sound insulation, and moisture-proof composite material and its preparation method. Background Technology

[0002] Traditional building materials such as concrete, bricks, and ordinary insulation boards are widely used, but they have significant performance shortcomings: In terms of insulation, they have high thermal conductivity and insufficient thermal resistance, leading to increased building energy consumption and hindering energy conservation and emission reduction; their sound wave absorption and reflection capabilities are poor, making them ineffective at blocking urban noise; they are susceptible to moisture penetration, affecting building lifespan and resident health; and their impact resistance is insufficient, making them prone to structural damage or even collapse under wind loads or accidental impacts, threatening personal safety. These defects not only increase construction and maintenance costs but also affect the comfort of people's living environment.

[0003] Chinese invention patent CN103396629A discloses a smoke-suppressing, flame-retardant, and sound-insulating PVC and its preparation method. The smoke-suppressing, flame-retardant, and sound-insulating PVC is composed of the following raw materials: PVC, plasticizer, heat stabilizer, flame retardant, smoke suppressant, iron oxide powder, calcium carbonate, and carbon black. The smoke-suppressing, flame-retardant, and sound-insulating PVC produces low smoke during combustion, and the components work synergistically to greatly increase the various properties of the product. The product is resistant to low temperatures and ultraviolet light, does not produce corrosive gases, and has low moisture absorption, but its thermal insulation and sound insulation performance is relatively poor.

[0004] Therefore, there is an urgent need to develop a multifunctional composite material that combines heat insulation, sound insulation, moisture resistance, and impact resistance. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the purpose of this invention is to provide a thermal insulation, sound insulation, and moisture-proof composite material and its preparation method.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A thermal insulation, sound insulation, and moisture-proof composite material, comprising the following raw materials in parts by weight: PVC: 60-65 parts, SBS: 15-20 parts, plasticizer: 2-5 parts, modified toughening agent: 8-12 parts, antioxidant: 1-2 parts, modified coupling agent: 2-5 parts, ceramic hollow microspheres: 8-10 parts, nano silica: 5-8 parts, flame retardant: 5-10 parts; The modified toughening agent is prepared by the following method: S1: 1,4-Phenylated boric acid reacts with polyethylene glycol to form a hyperbranched product; the reaction equation is shown below: ; Where R is ; S2: The hyperbranched product reacts with 4,4'-methylenebis(phenyl isocyanate) to generate a modified toughening agent; the hydroxyl group (-OH) in the hyperbranched product reacts with the isocyanate group (-NCO) to generate a carbamate group (-NHCOO-).

[0007] In step S1, the molar ratio of 1,4-phenylenediboric acid to polyethylene glycol is 1:(2.2-2.5).

[0008] In step S2, the mass ratio of the hyperbranched product to 4,4'-methylenebis(phenyl isocyanate) is (6-10):1.

[0009] The modified coupling agent is prepared by the following method: N1: The reaction of 4-aminomethylbenzoic acid and pentaerythritol yields a tetraester compound; the reaction equation is shown below: ; N2: The tetraester compound reacts with 3-chloropropyltrimethoxysilane to form a modified coupling agent; the reaction equation is shown below: ; In step N1, the molar ratio of 4-aminomethylbenzoic acid to pentaerythritol is 4.4:1.

[0010] In step N2, the molar ratio of the tetraester compound to 3-chloropropyltrimethoxysilane is 1:4.2.

[0011] The plasticizer is one of dibutyl phthalate and dioctyl phthalate.

[0012] The antioxidant is one of antioxidant 1010 and antioxidant 1076.

[0013] The flame retardant is one of antimony trioxide and zinc borate.

[0014] A method for preparing a thermal insulation, sound insulation, and moisture-proof composite material includes the following steps: (1) Weigh the following by weight: PVC: 60-65 parts, SBS: 15-20 parts, plasticizer: 2-5 parts, modified toughening agent: 8-12 parts, antioxidant: 1-2 parts, modified coupling agent: 2-5 parts, ceramic hollow microspheres: 8-10 parts, nano silica: 5-8 parts, flame retardant: 5-10 parts; (2) Add the above components to a high-speed mixer and mix them. Then, feed the mixture into a twin-screw extruder and extrude it. After air cooling, the heat-insulating, sound-insulating and moisture-proof composite material is obtained.

[0015] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include: The novel modified toughening agent and modified coupling agent prepared by this invention can improve the impact resistance of the material and the dispersibility of the inorganic filler, so that the thermal insulation, sound insulation and moisture-proof composite material prepared by this invention has excellent impact resistance and thermal insulation, sound insulation and moisture-proof functions. Detailed Implementation

[0016] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.

[0017] Example 1: Preparation of modified toughening agent: S1: Add 800 ml toluene, 0.22 mol polyethylene glycol (PEG400), and 0.1 mol 1,4-phenylenediboric acid to a reaction vessel, stir and mix well, heat to reflux, and react for 20 h. During this period, the water produced in the reaction is separated through a water separator. Cool to room temperature and distill under reduced pressure at 65 °C for 3 h to obtain the hyperbranched product; its number average molecular weight is 8037. S2: Under nitrogen protection, 500 ml of DMF, 60 g of hyperbranched product, and 10 g of 4,4'-methylenebis(phenyl isocyanate) were added sequentially to a reaction vessel and stirred until homogeneous. Then, 1.5 g of dibutyltin dilaurate was added, the temperature was raised to 50 °C, and the reaction was carried out for 6 h. 1000 ml of deionized water was added to precipitate the solid, which was then filtered, washed with 400 ml of deionized water, and dried under vacuum at 50 °C for 6 h to obtain the modified toughening agent.

[0018] Example 2: Preparation of modified toughening agent: S1: Add 800 ml toluene, 0.24 mol polyethylene glycol (PEG400), and 0.1 mol 1,4-phenylenediboric acid to a reaction vessel, stir and mix well, heat to reflux, and react for 22 h. During this period, the water produced in the reaction is separated through a water separator. Cool to room temperature and distill under reduced pressure at 65 °C for 3 h to obtain the hyperbranched product; its number average molecular weight is 8315. S2: Under nitrogen protection, 500 ml of DMF, 80 g of hyperbranched product, and 10 g of 4,4'-methylenebis(phenyl isocyanate) were added sequentially to a reaction vessel and stirred until well mixed. Then, 1.5 g of dibutyltin dilaurate was added, the temperature was raised to 60 °C, and the reaction was carried out for 5 h. 1000 ml of deionized water was added to precipitate the solid, which was then filtered, washed with 400 ml of deionized water, and dried under vacuum at 50 °C for 6 h to obtain the modified toughening agent.

[0019] Example 3: Preparation of modified toughening agent: S1: Add 800 ml toluene, 0.25 mol polyethylene glycol (PEG400), and 0.1 mol 1,4-phenylenediboric acid to a reaction vessel, stir and mix well, heat to reflux, and react for 24 h. During this period, the water produced in the reaction is separated through a water separator. Cool to room temperature, and distill under reduced pressure at 65 °C for 3 h to obtain the hyperbranched product; its number average molecular weight is 8617. S2: Under nitrogen protection, 500 ml of DMF, 100 g of hyperbranched product, and 10 g of 4,4'-methylenebis(phenyl isocyanate) were added sequentially to a reaction vessel and stirred until well mixed. Then, 1.5 g of dibutyltin dilaurate was added, the temperature was raised to 70 °C, and the reaction was carried out for 4 h. 1000 ml of deionized water was added to precipitate the solid, which was then filtered, washed with 400 ml of deionized water, and dried under vacuum at 50 °C for 6 h to obtain the modified toughening agent.

[0020] Example 4: Preparation of modified coupling agent: N1: 300 ml toluene, 0.1 mol pentaerythritol, 0.44 mol 4-aminomethylbenzoic acid, and 4 g p-toluenesulfonic acid were added to a reaction vessel and stirred until homogeneous. The mixture was reacted at 100 °C for 12 h, during which time the water produced in the reaction was separated using a water separator. The mixture was cooled to room temperature, and the pH was adjusted to 7 using saturated sodium bicarbonate. The mixture was separated into layers and washed three times with deionized water (100 ml each time). The mixture was dried over 20 g of anhydrous magnesium sulfate, filtered, and distilled under reduced pressure at 65 °C for 3 h to obtain the tetraester compound. Its 1H NMR spectrum data are as follows: 1 H NMR (300 MHz, Chloroform- d ) δ 7.97 - 7.91 (m, 8H), 7.40 - 7.33 (m, 8H), 4.54 (s,8H), 4.09 - 4.02 (m, 8H), 4.00 (dt, J = 5.2, 0.8 Hz, 8H); Under nitrogen protection, anhydrous toluene, 0.1 mol of a tetraester compound, 0.42 mol of 3-chloropropyltrimethoxysilane, 0.6 mol of potassium carbonate, and 0.04 mol of potassium iodide were sequentially added to a reaction vessel. The mixture was heated to 80 °C and reacted for 24 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filtrate was distilled under reduced pressure at 60 °C for 3 h and then dried under vacuum at 60 °C for 24 h to obtain the modified coupling agent. Its 1H NMR spectrum data are as follows: 1 H NMR (300 MHz, Chloroform- d ) δ 7.97 - 7.89 (m, 8H), 7.36 - 7.29(m, 8H), 4.54 (s, 8H), 3.91 (dt, J = 5.5, 0.9 Hz, 8H), 3.59 (s, 40H), 2.74(td, J = 6.5, 4.6 Hz, 8H), 1.69 - 1.56 (m, 8H), 0.70 (t, J = 9.1 Hz, 8H).

[0021] Example 5: Preparation of thermal insulation, sound insulation, and moisture-proof composite material: (1) PVC: 600g, SBS: 150g, dibutyl phthalate: 20g, modified toughening agent (prepared in Example 1): 80g, antioxidant 1010: 10g, modified coupling agent (prepared in Example 4): 20g, ceramic hollow microspheres: 80g, nano silica: 50g, flame retardant: 50g; (2) Add the above components to a high-speed mixer and mix them at a mixing temperature of 165°C, a mixing speed of 250 r / min, and a mixing time of 30 min. Then, feed the mixture into a twin-screw extruder and extrude it. The screw speed of the extruder is 20 r / s. The temperature of the conveying section of the twin-screw extruder is 165°C, the temperature of the melting section is 170°C, the temperature of the mixing section is 185°C, and the temperature of the homogenization section is 170°C. After air cooling, the heat-insulating, sound-insulating, and moisture-proof composite material is obtained.

[0022] Example 6: Preparation of thermal insulation, sound insulation, and moisture-proof composite material: Weigh out: PVC: 620g, SBS: 180g, dioctyl phthalate: 30g, modified toughening agent (prepared in Example 2): 100g, antioxidant 1076: 15g, modified coupling agent (prepared in Example 4): 40g, ceramic hollow microspheres: 90g, nano silica: 70g, zinc borate: 80g; (2) Add the above components to a high-speed mixer and mix them at a mixing temperature of 165°C, a mixing speed of 250 r / min, and a mixing time of 30 min. Then, feed the mixture into a twin-screw extruder and extrude it. The screw speed of the extruder is 20 r / s. The temperature of the conveying section of the twin-screw extruder is 165°C, the temperature of the melting section is 170°C, the temperature of the mixing section is 185°C, and the temperature of the homogenization section is 170°C. After air cooling, the heat-insulating, sound-insulating, and moisture-proof composite material is obtained.

[0023] Example 7: Preparation of thermal insulation, sound insulation, and moisture-proof composite material: (1) Weigh out: PVC: 650g, SBS: 200g, dioctyl phthalate: 50g, modified toughening agent (prepared in Example 3): 120g, antioxidant 1076: 20g, modified coupling agent (prepared in Example 4): 50g, ceramic hollow microspheres: 100g, nano silica: 80g, zinc borate: 100g; (2) Add the above components to a high-speed mixer and mix them at a mixing temperature of 165°C, a mixing speed of 250 r / min, and a mixing time of 30 min. Then, feed the mixture into a twin-screw extruder and extrude it. The screw speed of the extruder is 20 r / s. The temperature of the conveying section of the twin-screw extruder is 165°C, the temperature of the melting section is 170°C, the temperature of the mixing section is 185°C, and the temperature of the homogenization section is 170°C. After air cooling, the heat-insulating, sound-insulating, and moisture-proof composite material is obtained.

[0024] Comparative Example 1 The raw material composition and preparation method of the thermal insulation, sound insulation, and moisture-proof composite material are basically the same as those in Example 6, except that the modified toughening agent (prepared in Example 2) is replaced with an equal weight of the modified toughening agent prepared by the following method: The preparation method of the modified toughening agent is basically the same as that in Example 2, except that 1,4-phenylenediboric acid in step S1 is replaced with an equimolar amount of phenylboric acid.

[0025] Comparative Example 2 The raw material composition and preparation method of the thermal insulation, sound insulation, and moisture-proof composite material are basically the same as those in Example 6, except that the modified toughening agent (prepared in Example 2) is replaced with an equal weight of the modified toughening agent prepared by the following method: The preparation method of the modified toughening agent is basically the same as that in Example 2, except that the polyethylene glycol (PEG400) in step S1 is replaced with an equal weight of polyethylene glycol (PEG800).

[0026] Comparative Example 3 The raw material composition and preparation method of the thermal insulation, sound insulation, and moisture-proof composite material are basically the same as those in Example 6, except that the modified toughening agent (prepared in Example 2) is replaced with an equal weight of the modified toughening agent prepared by the following method: The preparation method of the modified toughening agent is basically the same as that in Example 2, except that the polyethylene glycol (PEG400) in step S1 is replaced with an equal weight of polyethylene glycol (PEG200).

[0027] Comparative Example 4 The raw material composition and preparation method of the thermal insulation, sound insulation, and moisture-proof composite material are basically the same as those in Example 6, except that the modified toughening agent (prepared in Example 2) is replaced with an equal weight of the modified toughening agent prepared by the following method: The preparation method of the modified toughening agent is basically the same as that in Example 2, except that 4,4'-methylene bis(phenyl isocyanate) in step S2 is replaced with an equimolar amount of bis(4-phenyl isocyanate) oxide.

[0028] Comparative Example 5 The raw material composition and preparation method of the thermal insulation, sound insulation, and moisture-proof composite material are basically the same as those in Example 6, except that the modified toughening agent (prepared in Example 2) is replaced with an equal weight of the modified toughening agent prepared by the following method: The preparation method of the modified toughening agent is basically the same as that in Example 2, except that 4,4'-methylenebis(phenyl isocyanate) in step S2 is replaced with an equimolar amount of toluene 2,6-diisocyanate.

[0029] Comparative Example 6 The raw material composition and preparation method of the thermal insulation, sound insulation and moisture-proof composite material are basically the same as those in Example 6, except that the modified coupling agent (prepared in Example 4) is replaced with an equal weight of the modified coupling agent prepared by the following method: The preparation method of the modified coupling agent is basically the same as that in Example 4, except that pentaerythritol in step N1 is replaced with an equimolar amount of 1,4-butanediol.

[0030] Comparative Example 7 The raw material composition and preparation method of the thermal insulation, sound insulation and moisture-proof composite material are basically the same as those in Example 6, except that the modified coupling agent (prepared in Example 4) is replaced with an equal weight of the modified coupling agent prepared by the following method: The preparation method of the modified coupling agent is basically the same as that in Example 4, except that 4-aminomethylbenzoic acid in step N1 is replaced with an equimolar amount of glycine.

[0031] Comparative Example 8 The raw material composition and preparation method of the thermal insulation, sound insulation and moisture-proof composite material are basically the same as those in Example 6. The difference is that the modified coupling agent (prepared in Example 4) is replaced with an equal weight of 3-chloropropyltrimethoxysilane.

[0032] The PVC used in this application is grade SG-5; the SBS is grade YH-792E from Baling Petrochemical; the ceramic hollow microspheres are model E-SPHERES (with a particle size uniformly distributed between 80-110 micrometers) and are produced by Dalian Yibang Technology Co., Ltd.; the nano silica is grade T7 and is produced by Fujian Yuanxiang New Materials Co., Ltd.

[0033] The cantilever beam notched impact strength was tested according to GB / T 1843-2008. Samples were cut to a type B notch shape according to the test requirements, and the test temperature was 23℃. The sample (50mm diameter, 2mm thickness) was tested using the transient hot wire method in GB / T 42919.1-2023 with a Hot Disk 2500S thermal conductivity meter. The sample (100mm diameter, 3mm thickness) was tested for sound transmission loss using an SW-422 impedance tube acoustic testing system, referring to GB / Z27764-2011 "Measurement of Sound Transmission Loss in Acoustic Impedance Tubes - Transfer Matrix Method," and the sound transmission loss at 800Hz was recorded. The water absorption rate of the sample (50mm×50mm×1mm) was tested in water at 23℃ according to Method 1 of 6.3 in GB / T 1034-2008. The test results are shown in Table 1.

[0034] Sample preparation: Place the mold of the sample to be prepared on the flat plate hot tooth machine, add the heat insulation, sound insulation and moisture-proof composite material, set the mold temperature to 185℃, set the heating time to 300s, vent twice, hold the pressure at 5MPa for 20s, and let it cool naturally to room temperature to obtain the sample.

[0035] Table 1 Performance Test Data

[0036] As can be seen from Examples 5, 6 and 7 in Table 1, the thermal insulation, sound insulation and moisture-proof composite material prepared by the present invention has good impact resistance, thermal insulation, sound insulation and moisture-proof performance.

[0037] The hyperbranched polymer synthesized in step S1 of this application constitutes the main framework of the toughening agent. Its highly branched three-dimensional structure effectively absorbs and disperses impact energy under impact stress, preventing crack propagation. Furthermore, its internal cavities provide additional deformation space, allowing for significant conformational adjustments to the molecular chains. Secondly, the rigid benzene ring structure in MDI is connected to the ends of the hyperbranched molecules via urethane bonds (-NHCOO-), significantly enhancing the rigidity of the molecular chains and the interfacial interactions (hydrogen bonding or polar interactions) with the PVC / SBS matrix, thereby improving the overall impact resistance of the material. Simultaneously, the methylene (-CH2-) and PEG400 segments bridged by MDI provide necessary flexibility, ensuring good ductility and toughness under stress, and improving the composite material's resistance to brittle fracture caused by stress concentration at notches. Furthermore, the dynamic reversibility of the borate bonds in the modified toughening agent endows the material with energy dissipation capabilities under impact loads; that is, bond breakage and recombination under external force can effectively absorb impact energy, further enhancing impact resistance.

[0038] When PEG400 is replaced with PEG200, the branching degree is insufficient due to the short chain segments, while PEG800 has a reduced branching efficiency and loose structure due to the excessively long flexible chains. The above structural defects are further amplified in the crosslinking reaction with isocyanate in step S2: the PEG200 product forms brittle, highly crosslinked microregions, while the PEG800 product generates a loose network with low crosslinking density. Both of them weaken the stress dissipation ability of the toughening agent body, thereby causing a decrease in impact strength.

[0039] The modified coupling agent prepared in this invention has a silanol group that can form Si-O-Si covalent bonds with the hydroxyl groups on the surface of inorganic fillers (ceramic hollow microspheres and silica), improving the compatibility between the inorganic fillers and the PVC matrix and reducing the risk of agglomeration. Its rigid benzene ring structure can improve the impact resistance of the material and can also improve the interfacial bonding strength and compatibility of the material by π-π stacking with the SBS matrix. The steric hindrance of the four-arm structure can effectively improve the dispersibility of the inorganic fillers, and improve the thermal insulation and sound insulation performance and impact resistance of the composite material.

[0040] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. A thermal insulation, sound insulation, and moisture-proof composite material, characterized in that, The ingredients include the following parts by weight: PVC: 60-65 parts, SBS: 15-20 parts, plasticizer: 2-5 parts, modified toughening agent: 8-12 parts, antioxidant: 1-2 parts, modified coupling agent: 2-5 parts, ceramic hollow microspheres: 8-10 parts, nano silica: 5-8 parts, flame retardant: 5-10 parts; The modified toughening agent is prepared by the following method: S1: 1,4-Phenylated boric acid reacts with polyethylene glycol to form hyperbranched products; S2: The hyperbranched product reacts with 4,4'-methylenebis(phenyl isocyanate) to generate a modified toughening agent.

2. The thermal insulation, sound insulation, and moisture-proof composite material according to claim 1, characterized in that, In step S1, the molar ratio of 1,4-phenylenediboric acid to polyethylene glycol is 1:(2.2-2.5).

3. The thermal insulation, sound insulation, and moisture-proof composite material according to claim 2, characterized in that, In step S2, the mass ratio of the hyperbranched product to 4,4'-methylenebis(phenyl isocyanate) is (6-10):

1.

4. The thermal insulation, sound insulation, and moisture-proof composite material according to claim 1, characterized in that, The modified coupling agent is prepared by the following method: N1: 4-Aminomethylbenzoic acid reacts with pentaerythritol to give a tetraester compound; N2: Tetraester compounds react with 3-chloropropyltrimethoxysilane to generate modified coupling agents.

5. The thermal insulation, sound insulation, and moisture-proof composite material according to claim 4, characterized in that, In step N1, the molar ratio of 4-aminomethylbenzoic acid to pentaerythritol is 4.4:

1.

6. The thermal insulation, sound insulation, and moisture-proof composite material according to claim 4, characterized in that, In step N2, the molar ratio of the tetraester compound to 3-chloropropyltrimethoxysilane is 1:4.

2.

7. The thermal insulation, sound insulation, and moisture-proof composite material according to claim 1, characterized in that, The plasticizer is one of dibutyl phthalate and dioctyl phthalate.

8. The thermal insulation, sound insulation, and moisture-proof composite material according to claim 1, characterized in that, The antioxidant is one of antioxidant 1010 and antioxidant 1076.

9. The thermal insulation, sound insulation, and moisture-proof composite material according to claim 1, characterized in that, The flame retardant is one of antimony trioxide and zinc borate.

10. A method for preparing a thermal insulation, sound insulation, and moisture-proof composite material according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Weigh the following by weight: PVC: 60-65 parts, SBS: 15-20 parts, plasticizer: 2-5 parts, modified toughening agent: 8-12 parts, antioxidant: 1-2 parts, modified coupling agent: 2-5 parts, ceramic hollow microspheres: 8-10 parts, nano silica: 5-8 parts, flame retardant: 5-10 parts; (2) Add the above components to a high-speed mixer and mix them. Then, feed the mixture into a twin-screw extruder and extrude it. After air cooling, the heat-insulating, sound-insulating and moisture-proof composite material is obtained.

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