Hollow microsphere modified chopped glass fiber anti-sedimentation polyurethane and preparation method thereof
By modifying chopped glass fibers with hollow microspheres and combining them with a polyurethane matrix, the problem of easy sedimentation of chopped glass fibers in polyurethane was solved, and the stability and uniformity of the material were improved, resulting in excellent comprehensive performance.
Patent Information
- Application Number
- CN202511608034.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-05
- Publication Date
- 2026-01-13
AI Technical Summary
Short-cut glass fibers tend to settle and disperse poorly in polyurethane, affecting the consistency and performance of the material.
Hollow microspheres were used to modify the surface of chopped glass fibers. Hollow microsphere-modified chopped glass fibers were then combined with a polyurethane matrix to prepare hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam.
It significantly improves the dispersion and stability of chopped glass fibers in polyurethane, enhances the uniformity and overall performance of the material, solves the sedimentation problem, and maintains the excellent properties of polyurethane.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of materials technology, specifically to a hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam and its preparation method. Background Technology
[0002] Polyurethane, as an important polymer material, is widely used in automobiles, construction, and cushioning due to its low density, excellent elastic recovery, good energy absorption, and thermal insulation. However, polyurethane matrix has relatively low modulus and strength, and insufficient fracture toughness and tear resistance, which affect fatigue life and dimensional stability.
[0003] To address these mechanical shortcomings, high-modulus chopped glass fibers were introduced into the polyurethane system as a reinforcing phase. Surface treatments such as silane coupling were used to optimize interfacial bonding, achieving effective stress transfer and energy dissipation. However, the density of chopped glass fibers is approximately 2.25 g / cm³. 3 The density of polyether polyol is approximately 1.00 g / cm³. 3 Fibers are difficult to disperse evenly in polyurethane raw materials and are prone to sedimentation in the material vessel, affecting the consistency of the material. Moreover, the material will undergo significant changes in mechanical properties within one hour, limiting the actual performance of the material.
[0004] To address the aforementioned issues, this invention employs hollow microspheres to modify the surface of chopped glass fibers, and then blends the modified fibers with polyurethane raw materials. The introduction of hollow microspheres significantly improves the dispersibility of chopped glass fibers in polyether polyols, enhances the stability and uniformity of the system, and effectively suppresses fiber sedimentation during use.
[0005] A novel polyurethane material with excellent thermal and mechanical properties was prepared by compositing hollow microspheres modified chopped glass fibers with a polyurethane matrix in different proportions. This modification strategy not only solved the problem of easy sedimentation of chopped glass fibers, but also improved the stability and uniformity of the polyurethane system. Summary of the Invention
[0006] The technical problem to be solved by the present invention is to provide a hollow microsphere modified chopped glass fiber anti-settling polyurethane foam and its preparation method, so as to solve the problems of easy settlement and poor dispersibility of chopped glass fiber in polyurethane in the prior art.
[0007] To solve the above-mentioned technical problems, the technical solution of the present invention is as follows:
[0008] Hollow microsphere-modified chopped glass fiber is synthesized using non-chiral organic solvents from hollow microspheres, chopped glass fiber, KH560, catalyst, and hydroxylamine solution.
[0009] Preferably, the hollow microsphere modified chopped glass fiber is synthesized from the following raw materials in parts by weight:
[0010] Hydroxylamine 3 parts by weight, chopped glass fiber 10 parts by weight, hollow microspheres 20 parts by weight, KH560 3 parts by weight, catalyst 0.8 parts by weight.
[0011] Preferably, the length of the chopped glass fibers is 9–13 μm;
[0012] Preferably, the hollow microspheres are expanded hollow microspheres with a particle size of 50 μm.
[0013] Preferably, the catalyst is 2-methylimidazole.
[0014] The method for preparing hollow microspheres modified chopped glass fibers according to the present invention includes the following steps:
[0015] (1) The hollow microspheres were placed in an aqueous solution of hydroxylamine and heated with a heat-collecting magnetic stirrer. After the reaction was completed, the microspheres were rinsed with deionized water and dried to obtain hydroxylamine-modified hollow microspheres.
[0016] (2) The chopped glass fibers were placed in a mixture of ethanol and water, the pH was adjusted to 5 with an appropriate amount of glacial acetic acid, KH560 was added, and the mixture was heated in an oil bath and refluxed under mechanical stirring. The mixture after the reaction was filtered in batches, washed with ethanol and dried to obtain KH560 grafted chopped glass fibers.
[0017] (3) The modified hollow microspheres obtained in step (1), the grafted short glass fibers obtained in step (2), the catalyst and the solvent are placed in an oil bath and reacted for a period of time to obtain hollow microsphere modified short glass fibers.
[0018] Preferably, in step (1), the heating temperature of the magnetic stirrer is 55°C, the reaction time is 1.5h, the oven temperature is 80°C, and the drying time is 5h.
[0019] Optionally, in step (2), the oil bath temperature is 75℃, the reaction time is 10h, the stirring rate is 400r / min, the drying temperature is 80℃, and the drying time is 8h.
[0020] Optionally, in step (3), the oil bath temperature is 65℃ and the reaction time is 2h; the drying temperature is 90℃ and the drying time is 4h.
[0021] Preferably, the organic solvent is n-butanol;
[0022] Preferably, the concentration of the hydroxylamine aqueous solution in step (1) is 1 mol / L:
[0023] A hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam is synthesized from polyether polyol, hollow microsphere-modified chopped glass fiber, foam stabilizer, isocyanate, and foaming agent. Preferably, the polyurethane is synthesized from the following raw materials in parts by weight:
[0024] 50 parts by weight of polyether polyol, 6 parts by weight of hollow microsphere modified chopped glass fiber, 4 parts by weight of foam stabilizer, 30 parts by weight of isocyanate, and 2 parts by weight of foaming agent.
[0025] Preferably, the polyether polyol is polyoxypropylene triol;
[0026] Preferably, the foam stabilizer is a copolymer of polyethylene oxide and methylsiloxane;
[0027] Preferably, the isocyanate is diphenylmethane diisocyanate;
[0028] Preferably, the foaming agent is nitrogen.
[0029] The present invention provides a method for preparing hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam, comprising the following steps:
[0030] (1) Mix polyether polyol, hollow microsphere modified short glass fiber and foam stabilizer evenly to obtain polyether component;
[0031] (2) The polyether component obtained in step (1) is mixed with isocyanate in a foaming machine and stirred to foam;
[0032] (3) The foaming material obtained in step (2) is coated and heated and cured in a high-temperature oven to obtain hollow microsphere modified short-cut glass fiber anti-settling polyurethane.
[0033] Optionally, in step (1), the mixing temperature is 25°C and the mixing time is 1 hour;
[0034] Optionally, in step (2), the temperature of the foaming machine is 25°C and the stirring speed is 650 r / min;
[0035] Optionally, in step (3), the oven temperature is 150°C, the curing time is 18 min, and the mass ratio of the polyether component to the isocyanate is controlled at 3.42.
[0036] This invention also provides the application of the hollow microsphere modified short-cut glass fiber anti-settling polyurethane in the fields of lightweight, high-strength, and compressive-resistant materials.
[0037] The above-described solution of the present invention has at least the following beneficial effects:
[0038] By introducing hollow microspheres to modify chopped glass fibers, the dispersibility of chopped glass fibers in polyurethane is significantly improved, effectively solving the problem of easy sedimentation of chopped glass fibers. The preparation method of this invention is simple and easy to implement, can be carried out on conventional polyurethane production equipment, and has good industrial application prospects. The obtained hollow microsphere-modified chopped glass fiber anti-settling polyurethane exhibits excellent stability, uniformity, and comprehensive performance, and can be widely used in lightweight, high-strength, and compressive-resistant fields. By controlling the proportions of each component and the preparation process parameters, the performance of the product can be flexibly adjusted to meet the needs of different application scenarios.
[0039] This invention provides a hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam and its preparation method. The hollow microspheres are grafted with amino groups, and the surface of the chopped glass fibers is grafted with epoxy groups. The epoxy groups react with the amino groups to open the ring. Through modification with hollow microspheres, the true density of the chopped glass fibers can be significantly reduced, allowing them to remain stably suspended in polyether polyol mixtures. This solves the problems of easy sedimentation and poor dispersibility of chopped glass fibers in polyurethane in existing technologies. While maintaining the excellent properties of polyurethane, this material exhibits higher stability and uniformity, providing a new approach for developing high-performance, multifunctional polyurethane materials, and has significant theoretical and practical value. Detailed Implementation
[0040] Exemplary embodiments of this disclosure will now be described in more detail. However, it should be understood that this disclosure may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of this disclosure to those skilled in the art.
[0041] Unless otherwise specified in the embodiments of this invention, the conditions shall be performed under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products. The following only provides some of the reagents used in the embodiments of this invention; different manufacturers and models of raw materials do not affect the implementation of the technical solution or the achievement of the technical effect of this invention.
[0042]
[0043] Example 1
[0044] The hollow microsphere-modified chopped glass fiber in this embodiment is synthesized from the following raw materials in parts by weight:
[0045] Hydroxylamine 2 parts by weight, chopped glass fiber 10 parts by weight, hollow microspheres 10 parts by weight, KH560 3 parts by weight, catalyst 0.6 parts by weight.
[0046] The hollow microspheres modified chopped glass fibers described in this embodiment specifically include the following steps:
[0047] (1) Hollow microspheres were placed in an aqueous solution of hydroxylamine and heated to 55°C using a heat-collecting magnetic stirrer for 1.5 h. After the reaction was completed, the microspheres were rinsed with deionized water and dried at 80°C for 5 h to obtain hydroxylamine-modified hollow microspheres.
[0048] (2) Short glass fibers were placed in a mixture of ethanol and water, and the pH was adjusted to 5 with an appropriate amount of glacial acetic acid. KH560 was added, and the mixture was heated in an oil bath at 75°C and refluxed for 10 hours with mechanical stirring at 400 r / min. The mixture after the reaction was filtered in batches, washed with ethanol, and dried in an oven at 80°C for 8 hours to obtain KH560-grafted short glass fibers.
[0049] (3) The modified hollow microspheres obtained in step (1), the grafted short-cut glass fibers obtained in step (2), the catalyst and the solvent were placed in an oil bath at 65°C and reacted for 2 hours. After the reaction was completed, they were placed in an oven at 90°C and dried for 4 hours to obtain hollow microsphere modified short-cut glass fibers.
[0050] This embodiment describes a hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam and its preparation method, which is synthesized from the following raw materials in parts by weight:
[0051] 50 parts by weight of polyether polyol, 6 parts by weight of hollow microsphere modified chopped glass fiber, 4 parts by weight of foam stabilizer, 30 parts by weight of isocyanate, and 2 parts by weight of foaming agent.
[0052] The hollow microsphere-modified short-cut glass fiber anti-settling polyurethane and its preparation method described in this embodiment specifically include the following steps:
[0053] (1) Polyether polyol, hollow microsphere modified short glass fiber and foam stabilizer were stirred and mixed at 25°C for 1 h to obtain polyether component;
[0054] (2) The polyether component obtained in step (1) is mixed with isocyanate in a foaming machine and nitrogen is introduced. The mixture is stirred and foamed at a speed of 650 rpm and the temperature of the foaming machine is controlled at 25°C.
[0055] (3) The foaming material obtained in step (2) is coated and placed in a high-temperature oven at 150°C and heated and cured for 18 minutes to obtain hollow microsphere modified short-cut glass fiber anti-settling polyurethane foam.
[0056] Example 2
[0057] The hollow microsphere-modified chopped glass fiber in this embodiment is synthesized from the following raw materials in parts by weight:
[0058] Hydroxylamine 2.5 parts by weight, chopped glass fiber 10 parts by weight, hollow microspheres 15 parts by weight, KH5603 parts by weight, catalyst 0.7 parts by weight.
[0059] This embodiment describes a hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam and its preparation method, which is synthesized from the following raw materials in parts by weight:
[0060] 50 parts by weight of polyether polyol, 6 parts by weight of hollow microsphere modified chopped glass fiber, 4 parts by weight of foam stabilizer, 30 parts by weight of isocyanate, and 2 parts by weight of foaming agent.
[0061] The preparation process is the same as in Example 1.
[0062] Example 3
[0063] The hollow microsphere-modified chopped glass fiber in this embodiment is synthesized from the following raw materials in parts by weight:
[0064] Hydroxylamine 3 parts by weight, chopped glass fiber 10 parts by weight, hollow microspheres 20 parts by weight, KH560 3 parts by weight, catalyst 0.8 parts by weight.
[0065] This embodiment describes a hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam and its preparation method, which is synthesized from the following raw materials in parts by weight:
[0066] 50 parts by weight of polyether polyol, 6 parts by weight of hollow microsphere modified chopped glass fiber, 4 parts by weight of foam stabilizer, 30 parts by weight of isocyanate, and 2 parts by weight of foaming agent.
[0067] The preparation process is the same as in Example 1.
[0068] Example 4
[0069] The hollow microsphere-modified chopped glass fiber in this embodiment is synthesized from the following raw materials in parts by weight:
[0070] Hydroxylamine 3.5 parts by weight, chopped glass fiber 10 parts by weight, hollow microspheres 25 parts by weight, KH5603 parts by weight, catalyst 0.9 parts by weight.
[0071] This embodiment describes a hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam and its preparation method, which is synthesized from the following raw materials in parts by weight:
[0072] 50 parts by weight of polyether polyol, 6 parts by weight of hollow microsphere modified chopped glass fiber, 4 parts by weight of foam stabilizer, 30 parts by weight of isocyanate, and 2 parts by weight of foaming agent.
[0073] The preparation process is the same as in Example 1.
[0074] Example 5
[0075] The hollow microsphere-modified chopped glass fiber in this embodiment is synthesized from the following raw materials in parts by weight:
[0076] Hydroxylamine 4 parts by weight, chopped glass fiber 10 parts by weight, hollow microspheres 30 parts by weight, KH560 3 parts by weight, catalyst 1 part by weight.
[0077] This embodiment describes a hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam and its preparation method, which is synthesized from the following raw materials in parts by weight:
[0078] 50 parts by weight of polyether polyol, 6 parts by weight of hollow microsphere modified chopped glass fiber, 4 parts by weight of foam stabilizer, 30 parts by weight of isocyanate, and 2 parts by weight of foaming agent.
[0079] The preparation process is the same as in Example 1.
[0080] Comparative Example 1
[0081] This comparative example did not use hollow microsphere modification; it directly composited chopped glass fibers with polyurethane raw materials. The formulation is as follows (parts by weight):
[0082] 50 parts by weight of polyether polyol, 6 parts by weight of unmodified chopped glass fiber, 4 parts by weight of foam stabilizer, 30 parts by weight of isocyanate, and 2 parts by weight of foaming agent.
[0083] The preparation process is the same as in Example 1.
[0084] Effect Comparison
[0085] To verify the technical effectiveness of the hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam and its preparation method described in this invention, the following experiments were conducted:
[0086] 1. Comparison of density and suspension performance
[0087] Density tests were conducted on the hollow microsphere-modified chopped glass fibers of the anti-settling polyurethane from Comparative Example 1 and Examples 1-5, the suspension performance of the polyether component was tested, and the density of the prepared polyurethane was also tested.
[0088] The results of the experiment are as follows:
[0089]
[0090] The density of the unmodified chopped glass fibers in Comparative Example 1 was 2.25 g / cm³. 3 It is much higher than that of polyether polyols (approximately 1.00 g / cm³). 3This leads to rapid settling. In Example 3, the amount of hollow microspheres used was most suitable (20 parts), making the density of the modified chopped glass fiber close to that of the polyether polyol, achieving the best suspension effect. In Examples 4-5, the amount of hollow microspheres used was too large (25-30 parts), resulting in excessively low density and floating. The density of the hollow microsphere-modified chopped glass fiber anti-settling polyurethane described in Comparative Example 1 and Examples 1-5 was adjusted to be the same using nitrogen.
[0091] 2. Mechanical properties:
[0092] Compressive strength: According to GB / T 1448-2005 standard, using a universal testing machine.
[0093] Comparison of mechanical properties:
[0094]
[0095] The compressive strength test results showed that the modified sample was significantly improved compared to the comparative example in the initial stage. The compressive strength of Comparative Example 1 was 0.2564 MPa, while that of Example 3 was 0.3158 MPa, an increase of 23%. The addition of hollow microspheres improved dispersion and interface, reduced stress concentration and crack initiation points inside the material, and resulted in more uniform energy dissipation, thereby improving the compressive strength of the material. With the continuous addition of hollow microspheres, the compressive strength of Examples 4 and 5 gradually decreased. Excessive hollow microspheres can cause agglomeration or deterioration of the pore structure, leading to a decrease in compressive strength. Since the foaming material was sampled and coated from the bottom of the material vessel, when Comparative Example 1, Example 1, and Example 2 showed different degrees of sedimentation, the compressive strength after 1-4 hours all first increased and then decreased; when Example 4 and Example 5 showed slight floating, the compressive strength after 1-4 hours all first decreased and then increased; when Example 3 was stably suspended, the compressive strength after 1-4 hours tended to stabilize.
[0096] Based on the comprehensive mechanical property test results, all modified samples showed significant improvement compared to the comparative sample. Example 3 exhibited the most outstanding compressive strength and achieved the best suspension effect, verifying the effectiveness of the hollow microsphere modification and the rationality of the formulation used in Example 3.
[0097] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam, characterized in that... Modified glass fibers were synthesized from hollow microspheres, hydroxylamine solution, chopped glass fibers, silane coupling agent KH560, and catalyst, and then polyurethane foam was prepared. The modification of hollow microspheres can significantly reduce the actual density of chopped glass fibers, making them stably suspended in polyether polyol mixtures, thereby effectively solving the problem of rapid sedimentation of chopped glass fibers in the production process of polyurethane foam.
2. The hollow microsphere-modified chopped glass fiber according to claim 1, characterized in that, It is synthesized from the following raw materials in parts by weight: 5-15 parts chopped glass fiber, 2-6 parts hydroxylamine, 10-40 parts hollow microspheres, 2-5 parts KH560, and 0.5-1.5 parts catalyst, using a non-chiral organic solvent.
3. The hollow microsphere modified chopped glass fiber according to claim 1, characterized in that, The hollow microspheres are organic hollow microspheres; optionally, the catalyst is 2-methylimidazole; optionally, the concentration of the hydroxylamine solution is 1 mol / L; optionally, the non-chiral solvent is at least one of chloroform, dimethyl sulfoxide, ethanol, n-butanol, and glacial acetic acid.
4. A method for preparing hollow microsphere-modified chopped glass fibers as described in claims 1-3, characterized in that, Includes the following steps: (1) Add hollow microspheres to an aqueous solution of hydroxylamine, heat it with a heat-collecting magnetic stirrer, react for a period of time, rinse with deionized water and dry after the reaction is complete to obtain hydroxylamine-modified hollow microspheres; (2) Place the short glass fiber in a mixture of ethanol and water, adjust the pH to 5 with an appropriate amount of glacial acetic acid, add KH560, heat in an oil bath, reflux under mechanical stirring, filter the mixture in batches after the reaction, wash with ethanol and dry to obtain KH560 grafted short glass fiber. (3) The grafted short glass fibers, modified hollow microspheres, solvent and catalyst are placed in an oil bath and reacted for a period of time to obtain hollow microsphere modified short glass fibers.
5. The method for preparing hollow microsphere-modified chopped glass fibers according to claim 4, characterized in that, Step (1) The reaction temperature is 40-60℃ and the reaction time is 1-2h; the drying temperature is 70-90℃ and the drying time is 4-6h; Step (2) The reaction temperature is 70-80℃ and the reaction time is 8-10h, the stirring rate is 300-400r / min; the drying temperature is 80-90℃ and the drying time is 8-10h; Step (3) The reaction temperature is 50-80℃ and the reaction time is 1-3h; the drying temperature is 80-120℃ and the drying time is 2-5h.
6. A hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam, characterized in that, Short-cut glass fibers modified with hollow microspheres as described in any one of claims 1-3.
7. The hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam according to claim 6 is characterized in that it is synthesized from the following raw materials in parts by weight: 20-70 parts by weight of polyether polyol, 5-15 parts by weight of hollow microsphere modified chopped glass fiber, 2-6 parts by weight of foam stabilizer, 10-40 parts by weight of isocyanate, and 0.5-5 parts by weight of foaming agent; Optionally, the polyether polyol is one or more of a difunctional polyether, a trifunctional polyether, or a multifunctional polyether; Optionally, the foam stabilizer is a copolymer of polyethylene oxide methylsiloxane or one or more of silicone oils; Optionally, the foaming agent is nitrogen.
8. A hollow microsphere-modified chopped glass fiber anti-settling polyurethane foam according to any one of claims 6-7 and its preparation method, characterized in that, Includes the following steps: (1) Mix polyether polyol, hollow microsphere modified short glass fiber, foam stabilizer evenly to obtain polyether component; (2) The polyether component obtained in step (1) is added to the foaming machine in a predetermined ratio with isocyanate and foaming agent, and mixed evenly under high-speed stirring to obtain foamed material. (3) The foaming material obtained in step (2) is coated and heated and cured in a high-temperature oven to obtain hollow microsphere modified short-cut glass fiber anti-settling polyurethane foam.
9. The method for preparing hollow microsphere-modified chopped glass fibers according to claim 8, characterized in that... Optionally, in step (1), the mixing temperature is 20-30℃ and the mixing time is 0.5-1h; optionally, in step (2), the foaming machine temperature is 15-30℃ and the stirring speed is 300-800r / min; optionally, in step (3), the oven temperature is 100-200℃, the curing time is 10-20min, and the mass ratio of polyether component to isocyanate is controlled at 3.21-3.
58.
10. The application of hollow microsphere modified chopped glass fiber anti-settling polyurethane foam as described in any one of claims 8-9 in the field of lightweight, high-strength, and compressive-resistant materials.