A polyethylene fiber composite non-woven fabric and its preparation method and application

Abstract

The present invention discloses a polyethylene fiber composite non-woven fabric and its preparation method and application, relating to the technical field of protective bulletproof composite materials. The polyethylene fiber composite non-woven fabric comprises ultra-high molecular weight polyethylene fibers and an adhesive. The adhesive comprises 100 parts of an adhesive premix, 5 - 60 parts of polyvinylidene fluoride, 0 - 5 parts of a catalyst, and 0.01 - 5 parts of a hindered phenol antioxidant. Among them, each part of the adhesive premix comprises 5 - 40 parts of water-soluble polyurethane, 0.05 - 5 parts of an initiator, and 1 - 20 parts of glycidyl methacrylate. The present invention greatly improves the heat resistance, creep resistance, and anti-aging performance of the obtained polyethylene fiber composite non-woven fabric, enhances the impact resistance and service life of the produced bulletproof products, and effectively ensures the safety factor of the bulletproof products.

Description

Technical Field

[0001] The invention relates to the technical field of protective bulletproof composite materials, and in particular to a polyethylene fiber composite non-woven fabric and a preparation method and application thereof. Background Art

[0002] Polyethylene fiber composite non-woven fabric is a non-woven fabric made by arranging polyethylene fibers (mostly ultra-high molecular weight polyethylene fibers) uniformly, parallelly and straightly, coating them with glue and drying them. This non-woven fabric has multiple advantages such as cutting resistance and corrosion resistance. However, the polyethylene fiber composite non-woven fabric made by conventional methods has its own shortcomings as the adhesive as the base, which affects the comprehensive performance of the non-woven fabric, which is specifically reflected in: general heat resistance, severe creep, and poor aging resistance, resulting in general impact resistance of bullet-proof products made from it, limited service life, and reduced safety factor of bullet-proof products.

[0003] The Chinese patent, publication number CN101397757A, discloses an ultra-high molecular weight polyethylene fiber composite non-woven fabric and its manufacturing method and application. The article states that "its composition includes ultra-high molecular weight polyethylene fiber and an adhesive, and the adhesive is a composite material with modified nano-montmorillonite added, wherein the weight percentage of montmorillonite is 0.5 to 10."

[0004] Although the heat resistance and creep resistance of the polyethylene fiber composite non-woven fabric are improved to a certain extent by adding modified nano-montmorillonite to the adhesive in the prior art, since the surface of the ultra-high molecular weight polyethylene fiber itself does not have any active functional groups and the friction coefficient is low, the bonding strength between the adhesive and the ultra-high molecular weight polyethylene fiber in the prior art is limited. Ultimately, the effect of improving the heat resistance and creep resistance of the polyethylene fiber composite non-woven fabric is still limited, and the impact resistance of the bullet-proof product made therefrom is still average. At the same time, the prior art still has the problem that the aging resistance of the polyethylene fiber composite non-woven fabric is average, and the service life of the bullet-proof product made therefrom is affected.

[0005] Therefore, a new technical solution is needed to solve the above technical problems. Summary of the invention

[0006] The object of the present invention is to provide a polyethylene fiber composite non-woven fabric and a preparation method and application thereof, so as to solve the technical problems that the polyethylene fiber composite non-woven fabric at the current stage proposed in the above-mentioned background technology has limited bonding strength between the adhesive used and the ultra-high molecular weight polyethylene fiber when using an adhesive to improve its own heat resistance and creep resistance, and it is impossible to ensure that the adhesive is used to improve the aging resistance, and the impact resistance and service life of the final bullet-proof product are generally poor.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] In the first aspect, the present invention provides a polyethylene fiber composite non-woven fabric, which includes ultra-high molecular weight polyethylene fibers and an adhesive. The adhesive includes 100 parts of an adhesive premix, 5 - 60 parts of polyvinylidene fluoride, 0 - 5 parts of a catalyst, and 0.01 - 5 parts of a hindered phenol antioxidant. Among them, each part of the adhesive premix includes 5 - 40 parts of water-soluble polyurethane, 0.05 - 5 parts of an initiator, and 1 - 20 parts of glycidyl methacrylate. Among them, the molecular weight of the ultra-high molecular weight polyethylene fibers is higher than 1 million. The catalyst is modified triethylenediamine or polyisocyanuric acid ester. The hindered phenol antioxidant is antioxidant 1010 or 2,8 - di-tert-butyl-4-methylphenol. The initiator is one of benzophenone, dicumyl peroxide, azobisisobutyronitrile, bis(2,5-dimethyl-2,5-di(tert-butylperoxy)hexane), and benzoin dimethyl ether.

[0009] In the second aspect, the present invention provides a preparation method of the above polyethylene fiber composite non-woven fabric,

[0010] including the following steps:

[0011] S1. Preparation of the adhesive premix: Mix the formulated amounts of water-soluble polyurethane, initiator, and glycidyl methacrylate evenly by ultrasonic mixing and stirring to obtain the adhesive premix, where the stirring time is 20 - 30 minutes;

[0012] S2. Preparation of the adhesive: Mix 100 parts of the adhesive premix prepared in S1, the formulated amounts of polyvinylidene fluoride, catalyst, and hindered phenol antioxidant evenly by ultrasonic mixing and stirring to obtain the adhesive, where the stirring time is 20 - 35 minutes;

[0013] S3. Preparation of the polyethylene fiber composite non-woven fabric: After applying the adhesive prepared in S2 to the ultra-high molecular weight polyethylene fibers, dry them to obtain the polyethylene fiber composite non-woven fabric, where the drying temperature is 80 - 110 °C and the drying time is 20 - 50 s.

[0014] In the third aspect, the present invention provides the application of the above polyethylene fiber composite non-woven fabric in bulletproof products.

[0015] Compared with the prior art, the beneficial effects of the present invention are:

[0016] 1. The adhesive of the present invention uses water-soluble polyurethane and polyvinylidene fluoride as the main raw materials, and the components of water-soluble polyurethane, polyvinylidene fluoride, glycidyl methacrylate, initiator, catalyst and hindered phenolic antioxidant in the adhesive cooperate with each other to undergo a polymerization reaction, which not only endows the adhesive with good dispersibility, mechanical properties and antioxidant properties, but also enables the adhesive to fully bond with ultra-high molecular weight polyethylene fibers, thereby greatly improving the heat resistance, creep resistance and anti-aging properties of the prepared polyethylene fiber composite non-woven fabric, enhancing the impact resistance and service life of the produced bulletproof products, and effectively ensuring the safety factor of the bulletproof products;

[0017] 2. In the present invention, first, water-soluble polyurethane, initiator and glycidyl methacrylate are ultrasonically mixed and stirred evenly to obtain an adhesive premix, and then the adhesive premix is ultrasonically mixed and stirred evenly with polyvinylidene fluoride, catalyst and hindered phenolic antioxidant to obtain the adhesive. This step-by-step ultrasonic mixing method is beneficial to increasing the mixing uniformity of the adhesive components and promoting the synergistic effect of each component, thereby further improving the heat resistance, creep resistance and anti-aging properties of the polyethylene fiber composite non-woven fabric prepared by compounding the adhesive with ultra-high molecular weight polyethylene fibers. Specific embodiments

[0018] To deepen the understanding of the present invention, the present invention will be further described in detail below in conjunction with embodiments.

[0019] Example 1

[0020] Preparation of polyethylene fiber composite non-woven fabric:

[0021] S1. Preparation of adhesive semi-finished product: 40 parts of water-soluble polyurethane, 5 parts of benzoin dimethyl ether and 20 parts of glycidyl methacrylate are ultrasonically mixed and stirred for 20 - 30 minutes until evenly stirred to obtain an adhesive premix;

[0022] S2. Preparation of adhesive: 100 parts of the adhesive premix prepared in S1, 60 parts of polyvinylidene fluoride, 5 parts of modified triethylenediamine and 5 parts of 2,8 - di-tert-butyl-4-methylphenol are ultrasonically mixed and stirred for 20 - 35 minutes until evenly stirred to obtain the adhesive;

[0023] S3. Preparation of polyethylene fiber composite non-woven fabric: The adhesive prepared in S2 is used to coat ultra-high molecular weight polyethylene fibers with a molecular weight higher than 1 million, and then dried at 80 - 110 °C for 20 - 50 s to obtain the polyethylene fiber composite non-woven fabric.

[0024] Example 2

[0025] Preparation of polyethylene fiber composite non-woven fabric:

[0026] S1. Preparation of adhesive semi-finished product: Mix 20 parts of water-soluble polyurethane, 3 parts of diisopropylbenzene peroxide, and 10 parts of glycidyl methacrylate by ultrasonic stirring for 20 - 30 minutes until evenly mixed to obtain an adhesive premix;

[0027] S2. Preparation of adhesive: Mix 100 parts of the adhesive premix prepared in S1, 30 parts of polyvinylidene fluoride, 3 parts of polyisocyanurate, and 3 parts of antioxidant 1010 by ultrasonic stirring for 20 - 35 minutes until evenly mixed to obtain an adhesive;

[0028] S3. Preparation of polyethylene fiber composite non-woven fabric: Apply the adhesive prepared in S2 to ultra-high molecular weight polyethylene fibers with a molecular weight higher than 1 million, and then dry at 80 - 110°C for 20 - 50 s to obtain a polyethylene fiber composite non-woven fabric.

[0029] Example 3

[0030] Preparation of polyethylene fiber composite non-woven fabric:

[0031] S1. Preparation of adhesive semi-finished product: Mix 5 parts of water-soluble polyurethane, 0.05 part of benzophenone, and 1 part of glycidyl methacrylate by ultrasonic stirring for 20 - 30 minutes until evenly mixed to obtain an adhesive premix;

[0032] S2. Preparation of adhesive: Mix 100 parts of the adhesive premix prepared in S1, 5 parts of polyvinylidene fluoride, and 0.01 part of 2,8 - di-tert-butyl-4-methylphenol by ultrasonic stirring for 20 - 35 minutes until evenly mixed to obtain an adhesive;

[0033] S3. Preparation of polyethylene fiber composite non-woven fabric: Apply the adhesive prepared in S2 to ultra-high molecular weight polyethylene fibers with a molecular weight higher than 1 million, and then dry at 80 - 110°C for 20 - 50 s to obtain a polyethylene fiber composite non-woven fabric.

[0034] Prepare specimens of (40*40) cm from the polyethylene fiber composite non-woven fabrics prepared in Examples 1 - 3 and commercially available polyethylene fiber composite non-woven fabrics respectively for bulletproof performance testing. The testing method is as follows: Fix the specimen (at a high temperature of 55°C ± 2°C, keep warm for 4 h) on the test target frame, and shoot a 1956 model 7.62 mm ordinary bullet (steel core) with a 1956 model 7.62 mm semi-automatic rifle. The effective number of shooting rounds is 3. The bullet speed requirement is: 750 m / s ± 10 m / s, the shooting distance is 15 meters, and the muzzle direction is perpendicular to the front of the test sample.

[0035] The test results are as follows: The specimens of the polyethylene fiber composite non-woven fabrics prepared in Examples 1 - 3 were not penetrated, while one specimen of the commercially available polyethylene fiber composite non-woven fabric was penetrated.

[0036] Therefore, in summary, the bulletproof product made of the polyethylene fiber composite non-woven fabric of the present invention can have excellent impact resistance and a relatively high safety factor.

Claims

1. A polyethylene fiber composite non-woven fabric, comprising ultra-high molecular weight polyethylene fibers and an adhesive, characterized in that, The adhesive comprises 100 parts of adhesive premix, 5 - 60 parts of polyvinylidene fluoride, 0 - 5 parts of catalyst, and 0.01 - 5 parts of hindered phenol antioxidant. Among them, each part of the adhesive premix comprises 5 - 40 parts of water-soluble polyurethane, 0.05 - 5 parts of initiator, and 1 - 20 parts of glycidyl methacrylate; The specific preparation steps of the polyethylene fiber composite non-woven fabric are as follows: S1. Preparation of the adhesive premix: Mix the formula amount of water-soluble polyurethane, initiator, and glycidyl methacrylate evenly by ultrasonic mixing and stirring to obtain the adhesive premix, where the stirring time is 20 - 30 minutes; S2. Preparation of the adhesive: Mix 100 parts of the adhesive premix prepared in S1, the formula amount of polyvinylidene fluoride, catalyst, and hindered phenol antioxidant evenly by ultrasonic mixing and stirring to obtain the adhesive, where the stirring time is 20 - 35 minutes; S3. Preparation of the polyethylene fiber composite non-woven fabric: After coating the ultra-high molecular weight polyethylene fiber with the adhesive prepared in S2, dry it to obtain the polyethylene fiber composite non-woven fabric, where the drying temperature is 80 - 110 °C and the drying time is 20 - 50 s.

2. The polyethylene fiber composite non-woven fabric according to claim 1, characterized in that, The catalyst is modified triethylenediamine or polyisocyanuric acid ester.

3. The polyethylene fiber composite non-woven fabric according to claim 1, characterized in that, The hindered phenol antioxidant is antioxidant 1010 or 2,8 - di-tert-butyl-4-methylphenol.

4. The polyethylene fiber composite non-woven fabric according to claim 1, characterized in that, The initiator is one of benzophenone, dicumyl peroxide, azobisisobutyronitrile, bis(2,5-dimethyl-2,5-di(tert-butylperoxy)hexane), benzoin dimethyl ether.

5. The polyethylene fiber composite non-woven fabric according to claim 1, characterized in that, The molecular weight of the ultra-high molecular weight polyethylene fiber is higher than 1 million.

6. Application of the polyethylene fiber composite non-woven fabric according to any one of claims 1-5 in bulletproof products.