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CN-121991487-A - Hybrid fiber polyurea composite flexible puncture-resistant material and preparation method thereof

CN121991487ACN 121991487 ACN121991487 ACN 121991487ACN-121991487-A

Abstract

The invention discloses a hybrid fiber polyurea composite flexible puncture-resistant material and a preparation method thereof, wherein a titanium fiber felt and an aramid fiber felt are overlapped to be used as fiber reinforcements, the fiber reinforcements are placed in a vacuum bag film system, and then a polyurea resin system is guided into a curing molding mode through vacuum negative pressure. According to the hybrid fiber polyurea composite flexible puncture-resistant material and the preparation method thereof, the materials with different characteristics are systematically integrated by adopting the polyurea, titanium fiber felt and aramid fiber felt hybrid composite material, so that the multistage and synergistic protection effect is realized. The titanium fiber felt has excellent rigidity, and can be contacted with the puncture tip at the first time on the surface of the protective layer, so that the concentrated stress of the puncture tip is effectively passivated and dispersed, and the puncture of the fiber gap is prevented. When high-speed impact is applied, the polyurea molecular chain generates intense friction and internal consumption, and a large amount of impact kinetic energy is converted into heat energy. When the spike attempts to penetrate, the polyurea layer will wrap around and grip the spike tip like a sticky plasticine.

Inventors

  • ZHANG XUFENG
  • WANG SHUO
  • FENG XIAO
  • ZHANG JIANPING
  • ZHANG XUDONG
  • CHEN YAQIN

Assignees

  • 山东奥卓新材料有限公司

Dates

Publication Date
20260508
Application Date
20260228

Claims (10)

  1. 1. A hybrid fiber polyurea composite flexible puncture-resistant material is characterized in that a titanium fiber felt and an aramid fiber felt are overlapped to be used as fiber reinforcement bodies, the fiber reinforcement bodies are placed in a vacuum bag film system, a polyurea resin system is led into the composite material with the solidification forming density of 2-6kg/m < 2 >, and the mass ratio of the fiber reinforcement bodies to the polyurea resin system is 100:50-100:150: the polyurea resin system is formed by mixing a component A and a component B according to the volume ratio of 100:50-150, wherein: the component A is isocyanate prepolymer, and is prepared by reacting isocyanate with polyol and polyamine, wherein the NCO content of the component A is 12% -18%; the component B is a mixture of amino-terminated polyether, a chain extender, a defoaming agent and pigment, and consists of the following components in parts by weight; 60-100 parts of amino-terminated polyether; 10-20 parts of chain extender; 0.1-1 part of defoaming agent; 0-5 parts of pigment.
  2. 2. The hybrid fiber polyurea composite flexible puncture-resistant material of claim 1, wherein the surface layer of the fiber reinforcement consists of 1-2 layers of titanium fiber mats, and the aramid fiber mats are sequentially stacked, wherein the number of layers is 5-40.
  3. 3. The hybrid fiber polyurea composite flexible puncture-resistant material of claim 2, wherein the titanium fiber mat has an areal density of 100-500g/m2, the aramid fiber needled mat is para-aramid, and the areal density is 10-100g/m2.
  4. 4. The hybrid fiber polyurea composite flexible puncture-resistant material of claim 1, wherein the polyurea resin system has a viscosity of 800-1500 mPa.s at 25 ℃, a tensile strength of not less than 55MPa, an elongation at break of not less than 350% and a Shore hardness of 35-85A.
  5. 5. A hybrid fiber polyurea composite flexible puncture-resistant material according to claim 1, wherein the isocyanate comprises one or more of 4,4' -diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, and 1, 4-phenylene diisocyanate.
  6. 6. The hybrid fiber polyurea composite flexible puncture-resistant material of claim 1, wherein the polyol is one or more of polycaprolactone polyol, polytetrahydrofuran polyether polyol, polyether modified polycarbonate diol, and the polyamine is polyetheramine selected from one or more of polyetheramine D2000, VERSALINK, P2000, VERSALINK, P1000, or VERSALINK, P650, and the mass ratio of the polyol to the polyamine is (0-100) to (100-0).
  7. 7. The hybrid fiber polyurea composite flexible puncture-resistant material according to claim 1, wherein the polyol or polyamine is dehydrated to a water content lower than 0.05%, the polyol or polyamine and isocyanate are accurately weighed according to the mass ratio of (0-100) to (100-0), a catalyst accounting for 0% -1% of the total mass of the raw materials is added into the polyol, and then the mixture is stirred and reacted for 1-5 hours under the condition of nitrogen protection and 70-90 ℃, and the isocyanate prepolymer is obtained after the mixture is qualified by-NCO value test.
  8. 8. The hybrid fiber polyurea composite flexible puncture-resistant material of claim 1, wherein the amine-terminated polyether is one or both of D2000, VERSALINK [ P1000 ], VERSALINK [ P2000 ], VERSALINK [ P650 ], and the chain extender is one of 1, 4-bis-sec-butylaminophenyl Unilink 4100, N' -bis (1, 4-dimethylpentyl) P-phenylenediamine Unilink 7100, ‌ WANALINK [ 6200 ], and the defoamer is UNIQ FOAMP-573.
  9. 9. A method for preparing the hybrid fiber polyurea composite flexible puncture-resistant material of any one of claims 1 to 8, comprising the steps of: S1, preprocessing, namely cutting a titanium fiber felt and a plurality of layers of aramid fiber felts according to the required size, and laying the titanium fiber felts on the surface layer and overlapping the aramid fiber felts in sequence; S2, cleaning a die, coating a release agent, and sequentially paving a titanium fiber felt, an aramid fiber felt lamination, release cloth, a flow guide net, a separation film and a spiral pipe on a die platform; S3, packaging, namely covering the whole paving layer by using a vacuum bag film, sealing the periphery, inserting a rubber injection pipe and a vacuum pipe, and preheating a die to 25-50 ℃; s4, vacuumizing, namely starting a vacuum pump to vacuumize the die cavity, enabling the vacuum degree in the system to be below-0.095 MPa, and keeping stability for 10-30 minutes so as to remove air and volatile matters in the die cavity; S5, vacuum introducing, namely preheating a polyurea resin system which is mixed in proportion in advance and defoamed to 25-60 ℃, introducing the system under vacuum negative pressure through an injection tube, and keeping vacuum to completely impregnate the aramid fiber felt; S6, curing and forming, namely curing for 1-2 hours at room temperature or heating to 30-80 ℃; S7, after-curing, releasing vacuum, removing the vacuum bag material, and curing for 24-36 hours at room temperature or under the condition of heating to 30-80 ℃; and S8, post-treatment, namely demolding and trimming the product to obtain the flexible puncture-resistant material.
  10. 10. The method of preparing a hybrid fiber polyurea composite flexible puncture-resistant material according to claim 9, wherein the pot life of the polyurea resin system in step S5 is longer than the time required for completing the vacuum introduction.

Description

Hybrid fiber polyurea composite flexible puncture-resistant material and preparation method thereof Technical Field The invention relates to the technical field of composite materials, in particular to a hybrid fiber polyurea composite flexible puncture-proof material and a preparation method thereof. Background With the increasing demand for safety, the performance requirements for puncture-resistant materials (e.g., stab resistant vests, cut resistant gloves, etc.) are increasing. The stab-resistant materials on the market at present are mainly divided into two major categories of hard (such as metal plates and ceramic plates) and soft (such as multi-layer high-performance fiber fabrics). The hard material directly resists the puncture tip by virtue of the high hardness and strength of the material, and defends the puncture tip by deforming or passivating and breaking the puncture tip. But the weight is large, the hardness is high, the activity flexibility of a user is severely limited, the flexibility is poor, and the comfort is poor. Soft stab-resistant materials are usually formed by laminating a plurality of layers of fiber fabrics such as aramid fiber, ultra-high molecular weight polyethylene and the like, and although the flexibility is good, the soft stab-resistant materials often need to obtain enough stab-resistant performance through high surface density, so that the materials are thick and heavy. Meanwhile, when the fiber is impacted by a sharp object, the fiber is easy to be pushed away by a sharp tool instead of being cut off, so that the stability of the stab-resistant effect is affected. Polyurea is an elastomeric material with excellent toughness, high impact resistance and wear resistance, which is compounded with high performance fibers, and combines the advantages of both. The traditional coating, lamination and other composite modes are difficult to enable polyurea to fully permeate into the fiber bundles, and poor interface bonding is easily caused. And secondly, the common polyurea material has short pot life and is not easy to process. In the prior art, a technical scheme for compounding polyurea serving as an integral matrix of a continuous phase with metal titanium and aramid fiber materials and specially solving the problem of puncture of a sharp object is lacking. The invention aims to fill the technical gap. Disclosure of Invention (One) solving the technical problems Aiming at the defects of the prior art, the invention provides a hybrid fiber polyurea composite flexible puncture-resistant material and a preparation method thereof, solves the problem that the prior art lacks an integral matrix which takes polyurea as a continuous phase, is compounded with metal titanium and aramid fiber materials, and is specially used for solving the problem of puncture of a sharp object. (II) technical scheme The invention is realized by the following technical scheme that the hybrid fiber polyurea composite flexible puncture-resistant material is prepared by superposing a titanium fiber felt and an aramid fiber felt as fiber reinforcements, placing the fiber reinforcements in a vacuum bag film system, introducing a polyurea resin system into the composite material with the solidification molding density of 2-6kg/m < 2 >, and ensuring that the mass ratio of the fiber reinforcements to the polyurea resin system is 100:50-100:150, wherein the mass ratio range can ensure that the material has enough fibers to bear main loads, and has a proper amount of polyurea matrix to transfer stress, absorb energy and maintain flexibility: the polyurea resin system is formed by mixing a component A and a component B according to the volume ratio of 100:50-150, wherein: the component A is isocyanate prepolymer, and is prepared by reacting isocyanate with polyol and polyamine, wherein the NCO content of the component A is 12% -18%; the component B is a mixture of amino-terminated polyether, a chain extender, a defoaming agent and pigment, and consists of the following components in parts by weight; 60-100 parts of amino-terminated polyether; 10-20 parts of chain extender; 0.1-1 part of defoaming agent; 0-5 parts of pigment. Preferably, the surface layer of the fiber reinforcement consists of 1-2 layers of titanium fiber mats, and aramid fiber mats are sequentially overlapped, wherein the number of layers is 5-40, so that an effective fiber network is formed to resist puncture. Preferably, the surface density of the titanium fiber felt is 100-500g/m < 2 >, the porosity is 40% -90%, the aramid fiber needled felt is para-aramid fiber, and the surface density is 10-100g/m < 2 >. Preferably, the viscosity of the polyurea resin system at 25 ℃ is 800-1500 mPa.s, the tensile strength is more than or equal to 55MPa, the elongation at break is more than or equal to 350%, and the Shore hardness is 35-85A. Preferably, the isocyanate comprises one or more of 4,4' -diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diiso