A resin composition, its preparation method and application

Abstract

The present invention relates to a resin composition, a preparation method thereof and an application thereof. The resin composition comprises a polymer and an organic small molecule. In the present invention, the resin composition is used in combination with an organic small molecule containing a phenolic hydroxyl group through the polymer, and no additional cross-linking agent needs to be added. When it is further formed into a composite material as a resin matrix, the processing process is simple, and it has the characteristics of excellent protective performance and good moldability.

Description

Technical Field

[0001] The present invention relates to the field of material technologies, and particularly to a resin composition, a preparation method thereof, and an application thereof. Background Art

[0002] The development of bulletproof materials has undergone a long historical process, from ordinary steel to alloy steel, from metal materials to fiberglass, and from single materials to composite materials. Each step has significantly improved its performance. Currently, most of the applied bulletproof materials consider convenience and comfort, and use high-performance fiber composite materials to replace traditional steel and ceramics. The main representatives are carbon fiber, aramid fiber, and ultra-high molecular weight polyethylene (UHMWPE) fiber. Among them, UHMWPE fiber has broad application prospects in the fields of personal protection, aviation and navigation, bulletproof armor, etc. due to its high strength, light weight, and excellent weather resistance. High-performance fiber composite materials mainly use fiber fabrics or fiber fabrics impregnated with resin to make bulletproof layers. The infiltrated resin bonds the fibers together to maintain integrity, make the stress distribution more uniform, and play a role in transmitting loads between the fibers.

[0003] In high-performance fiber composite materials, in addition to the properties of the fibers themselves, the properties and content of the resin matrix, especially the properties of the interface layer formed with the fibers, directly affect the final mechanical properties and protection performance of the composite materials.

[0004] The resin matrix generally selects thermoplastic elastomers or rubber-like materials. Their molecular chains contain flexible functional groups, the molecules are flexible, and they have good impact resistance and good energy absorption. In addition, the resin needs to have strong chemical stability and adhesion performance, and obtain better bulletproof performance through synergistic effects with high-strength fibers.

[0005] CN103403489A discloses a bulletproof article comprising a plurality of fiber layers, each layer comprising a fiber network and a matrix material, wherein the fibers have a strength of at least 800 mN / tex (1100 MPa) according to ASTM-D7269-07, and wherein the matrix material comprises a mixture of - at least one self-crosslinking acrylic resin and / or at least one crosslinkable acrylic resin and - at least one tackifier. Compared with an article having the same structure but having a matrix without a tackifier, the disclosed article has higher adhesion between fiber layers in the unaged and aged states and lower water absorption after water immersion, and the article passes the gasoline immersion test. Articles further comprising a plate of metal or ceramic show minimal or even no fiber layer delamination after ballistic impact, while articles having the same structure but having a matrix without a tackifier show internal delamination within the fiber layers. The disclosed resin matrix contains self-crosslinking acrylic resin or crosslinkable acrylic resin, but it is necessary to add a tackifier to improve the structural integrity of the composite material and ultimately enhance the protection effect of the composite material.

[0006] The journal literature "Lv Shenghua, Wang Jieli, Liang Guozheng, He Yang. Synthesis of waterborne polyacrylate microemulsion for bonding coating of ultra-high molecular weight polyethylene fiber [J]. Fine Chemicals, 2004, 21(6): 461-464." reported a polyacrylate emulsion for bonding UHMWPE fibers. A hydroxyethyl acrylate functional unit was introduced into its disclosed molecular structure. Under certain conditions, the polyacrylate emulsion could undergo a self-crosslinking reaction. By controlling the content of the self-crosslinking functional unit, the adhesiveness and strength of the film-forming were improved.

[0007] In the prior art, the film-forming performance of resin emulsions was mostly improved by chemical crosslinking. The production and use processes of the resin were relatively complex, the processability of the hot pressing of fiber composites was poor, and the storage and transportation conditions of the resin were relatively harsh. In summary, it is crucial to develop a resin matrix that does not require additional crosslinking agents and the formed composite materials have excellent protective properties and good formability. Summary of the Invention

[0008] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a resin composition, its preparation method and application. The resin composition does not require additional crosslinking agents, and the further formed composite materials have the characteristics of excellent protective properties and good formability.

[0009] To achieve this purpose, the present invention adopts the following technical solutions:

[0010] In the first aspect, the present invention provides a resin composition, which includes a polymer and an organic small molecule;

[0011] The polymer includes M structural units and N structural units. Optionally, it further includes X structural units and / or Y structural units;

[0012] Among them, the M structural unit is with a degree of polymerization of M;

[0013] The N structural unit is with a degree of polymerization of N;

[0014] The X structural unit is with a degree of polymerization of X;

[0015] The Y structural unit is with a degree of polymerization of Y;

[0016] Among them, R1 is selected from hydrogen or C1-C2 alkyl;

[0017] R2 is selected from C3-C8 alkyl;

[0018] R3 and R4 are each independently selected from hydrogen or methyl;

[0019] M + N ≥ 30 (such as 35, 40, 50, 55, etc.), X + Y ≥ 0 (such as 1, 2, 4, 6, 8, 10, 15, etc.);

[0020] The organic small molecule contains a phenolic hydroxyl group.

[0021] In the present invention, the resin composition is used in combination with a polymer having the structure shown in Formula I and an organic small molecule containing a phenolic hydroxyl group. The phenolic hydroxyl group in the organic small molecule can form a hydrogen bond with the carbonyl group in the polymer. Through structural and process control, physical crosslinking points are formed in the resin matrix without adding an additional crosslinking agent. When it is further formed into a composite material as the resin matrix, the processing process is simple, and it has the characteristics of good protective performance and good moldability.

[0022] In the present invention, "C1-C2" means that the number of main chain carbon atoms is 1-2, such as methyl, ethyl, etc.

[0023] "C3-C8" means that the number of main chain carbon atoms is 3-8, such as C4, C6, C7, etc.

[0024] Preferably, there are four structural types:

[0025] Structure 1:

[0026] Preferably, the ratio of M to N is 1:1 - 1:6 (such as 1:2, 1:3, 1:4, 1:5, etc.), and X = Y = 0.

[0027] More preferably, M:N = 1:4 - 1:6 (such as 1:4.5, 1:5, 1:5.5, 1:6, etc.), and X = Y = 0.

[0028] Structure 2:

[0029] Preferably, the ratio of N to X is 2.5:97.5 - 18.5:81.5 (such as 5:95, 10:90, 15:85, etc.), and M = Y = 0.

[0030] More preferably, N:X is 5:95 - 13:87 (such as 10:90, 11:89, 12:88, etc.), and M = Y = 0.

[0031] Structure 3:

[0032] Preferably, the ratio of M to N is 10:90 - 1:99 (such as 8:92, 6:94, 4:96, 2:98, etc.), X = 0, and (M + N):Y = 70:30 - 95:5 (such as 80:20, 90:10, etc.).

[0033] Further preferably, M:N is 10:90 - 5:95 (such as 8:92, 9:91, etc.), X = 0, (M + N):Y is 70:30 - 90:10.

[0034] Structure 4:

[0035] Preferably, the ratio of M to X is 0.5:99.5 - 15:85 (such as 1:99, 5:95, 10:90, etc.), N = Y = 0.

[0036] Further preferably, the ratio of M to X is 3:97 - 10:90 (such as 5:95, 6:94, 8:92, etc.), N = Y = 0.

[0037] Exemplarily, the structure of the polymer is as shown in Formula I:

[0038]

[0039] Formula I is only an exemplary representation, and the polymer is a random copolymer or a block copolymer.

[0040] Preferably, the functionality of the organic small molecule is 3 or 4.

[0041] Preferably, the organic small molecule includes any one or a combination of at least two of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)benzoate, or 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. Among them, typical but non-limiting combinations include: the combination of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; the combination of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)benzoate, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; the combination of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)benzoate, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, etc.

[0042] Exemplarily, the organic small molecules have the following structures respectively:

[0043]

[0044] 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene

[0045]

[0046] 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione

[0047]

[0048] pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)benzoate

[0049]

[0050] 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione Preferably, in the resin composition, the mass ratio of the polymer to the organic small molecule is 1000:(3 - 500), where 3 - 500 can be 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, etc., more preferably 1000:(10 - 300), and even more preferably 1000:(10 - 100).

[0051] Preferably, in the resin composition, the polymer includes any one or at least two combinations of the polymers.

[0052] In a second aspect, the present invention provides a method for preparing the resin composition according to the first aspect, and the preparation method includes the following steps:

[0053] Mix the polymer and the organic small molecule to obtain the resin composition.

[0054] Preferably, the preparation method of the polymer includes the following steps:

[0055] Mix the polymerization monomer and the initiator, and polymerize to form the polymer.

[0056] Preferably, the mixing further includes an emulsifier.

[0057] Preferably, the polymerization monomer includes at least two combinations of acrylic acid, methyl acrylate, butyl acrylate, polyethylene wax or isoprene, and typical but non-limiting combinations include the combination of methyl acrylate and butyl acrylate, the combination of acrylic acid and polyethylene wax, the combination of methyl acrylate, butyl acrylate and isoprene, etc.

[0058] Preferably, the initiator includes potassium persulfate (KPS) and / or benzoyl peroxide (BPO).

[0059] Preferably, the emulsifier includes sodium dodecyl sulfate (SDS) and / or OP-10.

[0060] Preferably, the raw materials for the mixing further include a buffer.

[0061] Preferably, when the raw materials for preparing the polymer do not contain an emulsifier, the preparation method of the polymer includes the following steps:

[0062] Mix the polymerization monomer with the initiator and react at 40 - 100 °C (such as 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, etc.) for 0.5 - 10 hours (such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 4 hours, 6 hours, 8 hours, etc.) to obtain the polymer.

[0063] Preferably, when the raw materials for preparing the polymer contain an emulsifier, the method for preparing the polymer comprises the following steps:

[0064] (1) Mix water and the emulsifier for the first time, then mix with the polymerization monomer and part of the initiator for the second time and react;

[0065] (2) Mix part of the initiator with the solution after the reaction in step (1), raise the temperature for reaction, and filter to obtain the polymer;

[0066] Or,

[0067] (1) Mix water and the emulsifier for the first time, then mix with part of the polymerization monomer and part of the initiator for the second time and react;

[0068] (2) Mix part of the polymerization monomer and part of the initiator with the solution after the reaction in step (1), raise the temperature for reaction, and filter to obtain the polymer.

[0069] Preferably, in step (1), the temperature of the first mixing is 10 - 100 °C, such as 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, etc.

[0070] Preferably, the time of the first mixing is 5 - 30 minutes, such as 10 minutes, 15 minutes, 20 minutes, 25 minutes, etc.

[0071] Preferably, the raw materials for the first mixing further include a buffer.

[0072] Preferably, the way of the first mixing includes stirring.

[0073] Preferably, the temperature of the second mixing is 10 - 100 °C, such as 20 °C, 30 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, etc.

[0074] Preferably, the way of the second mixing includes dropwise adding part of the polymerization monomer initiator to the solution after the first mixing.

[0075] Preferably, the time of the second mixing is 5 - 30 minutes, such as 10 minutes, 15 minutes, 20 minutes, 25 minutes, etc.

[0076] Preferably, the temperature of the reaction is 10 - 100 °C, such as 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, etc.

[0077] Preferably, the time of the reaction is 30 - 60 minutes, such as 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, etc.

[0078] Preferably, in step (2), the mixing method includes dropping the remaining polymerization monomer and initiator into the solution after the reaction in step (1).

[0079] Preferably, the temperature of the mixing is 10 - 100 °C, such as 40 °C, 50 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, etc.

[0080] Preferably, the time of the mixing is < 3 h, such as 2.5 h, 2 h, 1 h, etc.

[0081] Preferably, the temperature of the temperature-rising reaction is 30 - 100 °C, such as 40 °C, 50 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, etc.

[0082] Preferably, the time of the temperature-rising reaction is 0.5 - 10 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 4 hours, 6 hours, 8 hours, etc.

[0083] Preferably, after the temperature-rising reaction, it further includes cooling and adjusting the pH.

[0084] Preferably, the temperature is cooled to 10 - 40 °C, such as 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, etc.

[0085] Preferably, the pH is adjusted to 6 - 7, such as 6.2, 6.4, 6.6, 6.8, etc.

[0086] Preferably, in steps (1) and (2), the mass ratio of the initiator is 1:(0.1 - 10), where 0.1 - 10 can be 2, 4, 6, 8, etc.

[0087] Preferably, when the polymerization monomer is added in two parts to steps (1) and (2), the mass ratio of the polymerization monomer is 1:(0.1 - 100), where 0.1 - 100 can be 2, 4, 6, 8, 10, 20, 40, 60, 80, etc.

[0088] As a preferred technical solution, the polymer is prepared by the following method, and the preparation method includes the following steps:

[0089] (1) Mix water, an emulsifier, and a buffer, and while stirring, heat up to 10 - 100 °C and dissolve for 5 - 30 minutes to form a mixed solution.

[0090] Then, drop part of the mixed monomers and the initiator solution into the above - mentioned mixed solution within 5 - 30 minutes, and continue the reaction at 10 - 100 °C for 30 - 60 minutes.

[0091] (2) Drop the remaining mixed monomers and the initiator solution evenly into the reaction solution of step (1) within 3 hours at a temperature of 10 - 100 °C, then react at 30 - 100 °C for 0.5 - 10 hours, stop the reaction, cool down to room temperature, adjust the pH value to 6 - 7, and then pour out and filter the emulsion to obtain the polymer emulsion.

[0092] Preferably, the preparation method of the polymer may further include the following steps:

[0093] Mix a commercial prepolymer, a solvent, and an emulsifier, and emulsify to form the polymer.

[0094] In the third aspect, the present invention provides a resin composition dispersion, and the resin composition dispersion includes the resin composition described in the first aspect and a solvent.

[0095] Preferably, the solvent includes any one or at least two combinations of water, n - hexane, petroleum ether, tetrahydrofuran, acetone, N,N - dimethylformamide, 1,4 - dioxane, dichloromethane, chloroform, toluene, or xylene. Among them, typical but non - restrictive combinations include: the combination of water, n - hexane, and petroleum ether; the combination of petroleum ether, tetrahydrofuran, acetone, and N,N - dimethylformamide; the combination of N,N - dimethylformamide, 1,4 - dioxane, dichloromethane, chloroform, toluene, and xylene, etc.

[0096] Exemplarily, the resin composition dispersion is prepared by the following method, and the preparation method includes the following steps:

[0097] First step: Form a polymer emulsion from the polymer.

[0098] Second step: Dissolve an organic small molecule in xylene, stir well to dissolve, then add an emulsifier and stir well to dissolve, and finally add deionized water while stirring at high speed to obtain a uniformly dispersed emulsion.

[0099] Third step: Slowly add the emulsion prepared in the second step to the emulsion prepared in the first step under the condition of high - speed stirring to obtain the resin dispersion for use.

[0100] Fourth aspect, the present invention provides a composite material, which comprises polyethylene fibers and the resin composition described in the first aspect.

[0101] Preferably, the polyethylene fibers comprise ultra-high molecular weight polyethylene fibers.

[0102] Fifth aspect, the present invention provides a method for preparing the composite material described in the fourth aspect, and the method for preparing the composite material comprises the following steps:

[0103] Infiltrate the polyethylene fibers with the resin composition dispersion liquid described in the third aspect, dry and hot press and compound to obtain the composite material.

[0104] Compared with the prior art, the present invention has the following beneficial effects:

[0105] The composite material formed by the resin composition of the present invention has excellent bulletproof performance, and the V50 value of the composite material formed by the resin composition is above 526 m / s; in addition, the resin composition of the present invention has the processing characteristics of thermoplastic resin, and the composite sheet formed by hot pressing has excellent performance and good forming effect. Description of the Drawings

[0106] Figure 1 is the infrared test chart of the resin composition described in Example 1;

[0107] Figure 2 is the infrared test chart of the resin composition described in Example 3;

[0108] Figure 3 is the infrared test chart of the resin composition described in Example 4. Detailed Embodiments

[0109] For the convenience of understanding the present invention, the following examples are listed. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0110] Example 1

[0111] This example provides a resin composition, which is composed of a polymer shown in Formula I and an organic small molecule containing a phenolic hydroxyl group with a mass ratio of 1000:50.

[0112] Among them, in the polymer, M:N = 20:80, X = Y = 0; the organic small molecule containing a phenolic hydroxyl group is 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.

[0113] The resin composition is prepared by the following method, and the preparation method comprises the following steps:

[0114] Step 1: Add 80 mL of deionized water, 1.40 g of OP-10 emulsifier, 0.90 g of sodium dodecyl sulfate (SDS), and 0.30 g of NaHCO3 into a reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel. Under stirring conditions, heat up to 80 °C and stir to dissolve for 15 minutes. Then, dropwise add a mixed monomer of 2.58 g of methyl acrylate and 15.36 g of butyl acrylate and 0.13 g of potassium persulfate (KPS) initiator solution within 15 minutes, and continue to react at 80 °C for 45 minutes;

[0115] Step 2: Uniformly dropwise add the remaining mixed monomer of 6.02 g of methyl acrylate and 35.84 g of butyl acrylate and 0.31 g of potassium persulfate (KPS) initiator solution into the reactor within 3 hours, then heat up to 90 °C and stir to react for 1 hour. Stop the reaction, cool down to room temperature, adjust the pH value to 6 - 7 with ammonia water, and then pour out the emulsion and filter it to obtain the target polymer emulsion;

[0116] Step 3: Dissolve 0.30 g of 1,3,5 - trimethyl - 2,4,6 - tris(3,5 - di - tert - butyl - 4 - hydroxybenzyl)benzene in 2 mL of xylene, fully dissolve it, then add 0.10 g of OP - 10 emulsifier and fully dissolve it. Finally, add 13 mL of deionized water while stirring at high speed to obtain a uniformly dispersed emulsion.

[0117] Step 4: Slowly add the emulsion prepared in Step 3 into the emulsion prepared in Step 2 under high - speed stirring conditions to obtain the resin dispersion for use.

[0118] Characterization and analysis of the polymer emulsion: Take a small amount of the emulsion prepared in Step 2, pour it into 500 mL of ethanol for sedimentation, wash it with ethanol, dry it, and then perform infrared absorption spectroscopy test. The results are as Figure 1 follows. The ordinate in the figure is the transmittance, and the abscissa is the wavelength. 2922 cm -1 and 2850 cm -1 are the stretching vibration peaks of methylene, 1732 cm -1 is the stretching vibration of the C=O bond in acrylate, 1466 cm -1 is the in - plane bending vibration peak of methylene, 1377 cm -1 is the bending vibration peak of methyl, 1239 cm -1 and 1112 cm -1 are the stretching vibration peaks of C - O - C in the ester group, 948 cm -1 is the characteristic peak of butyl acrylate.

[0119] Example 2

[0120] This embodiment provides a resin composition, which is composed of a polymer represented by Formula I and an organic small molecule containing a phenolic hydroxyl group in a mass ratio of 1000:50.

[0121] Among them, in the polymer, the ratio of N to X is 10.5:89.5, M = Y = 0; the organic small molecule containing a phenolic hydroxyl group is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0122] The resin composition is prepared by the following method, and the preparation method includes the following steps:

[0123] First step: Using the SK Chemical commercial 35B320 polymer as the raw material, take 24 g of 35B320 polymer, dissolve it in 12 mL of xylene solvent, and then add 2 g of OP-10 emulsifier, and heat to dissolve it completely.

[0124] Second step: Take 0.12 g of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and dissolve it in 2 mL of xylene,

[0125] stir and dissolve it completely, then add 0.5 g of OP-10 emulsifier, and stir and dissolve it completely.

[0126] Third step: Slowly add the solution prepared in the second step to the solution prepared in the first step under high-speed stirring, heat, and stir to mix and dissolve completely.

[0127] Fourth step: Dissolve 0.5 g of OP-10 emulsifier in 50 mL of water to prepare an aqueous solution of a certain concentration, heat, and then slowly add the aqueous solution to the solution in the third step while stirring at high speed. Through sufficient high-speed stirring, a resin dispersion for use can be obtained.

[0128] Example 3

[0129] This embodiment provides a resin composition, which is composed of a polymer represented by Formula I and an organic small molecule containing a phenolic hydroxyl group in a mass ratio of 1000:50.

[0130] M:N = 10:90 to 1:99, X = 0, (M+N):Y = 70:30 to 95:5; among them, in the polymer, M:N = 5:95, X = 0, (M+N):Y = 85:15; the organic small molecule containing a phenolic hydroxyl group is pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)benzoate.

[0131] The resin composition is prepared by the following method, and the preparation method includes the following steps:

[0132] The first step: Dissolve 2.07 g of sodium dodecyl sulfate (SDS) and 2.5 g of OP-10 in 180 mL of water, stir until fully dissolved, and then add 4.3 g of methyl acrylate monomer, 121.6 g of butyl acrylate monomer, and 12.0 g of isoprene monomer, and stir at high speed to obtain a pre-emulsion.

[0133] The second step: Dissolve 1.03 g of potassium persulfate (KPS) initiator and 0.5 g of OP-10 in 20 mL of water. Heat the pre-emulsion prepared in the first step to 50 °C, then slowly add the KPS initiator solution to the pre-emulsion at a constant speed, and then raise the temperature to 80 °C and stir and react for 4 hours.

[0134] The third step: Dissolve 0.69 g of pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) in 5 mL of xylene, stir until fully dissolved, then add 0.45 g of OP-10 emulsifier, stir until fully dissolved, and finally add 65 mL of deionized water while stirring at high speed to obtain a uniformly dispersed emulsion.

[0135] The fourth step: Slowly add the emulsion prepared in the third step to the emulsion prepared in the second step under the condition of high-speed stirring to obtain a resin dispersion for use.

[0136] Characterization and analysis of the polymer emulsion: Take a small amount of the emulsion prepared in the second step, pour it into 500 mL of ethanol for sedimentation, wash it with ethanol, and dry it, and then perform infrared absorption spectroscopy test. The results are as Figure 2 . In the figure, the ordinate is the transmittance, the abscissa is the wavelength, 2956 cm -1 is the stretching vibration peak of methyl, 2930 cm -1 and 2874 cm -1 are the stretching vibration peaks of methylene, 1727 cm -1 is the stretching vibration of the C=O bond in acrylate, 1664 cm -1 is the stretching vibration peak of the C=C bond formed after the reaction of isoprene, 1450 cm -1 is the in-plane bending vibration peak of methylene, 1385 cm -1 is the bending vibration peak of methyl, 1236 cm -1 and 1160 cm -1 are the stretching vibration peaks of C-O-C in the ester group, 940 cm -1 is the characteristic peak of butyl acrylate.

[0137] Example 4

[0138] This embodiment provides a resin composition, which is composed of a polymer shown in Formula I and an organic small molecule containing a phenolic hydroxyl group in a mass ratio of 1000:50.

[0139] Among them, in the polymer, M:X = 8:92, N = 0, Y = 0; the organic small molecule containing a phenolic hydroxyl group is 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0140] The resin composition is prepared by the following method, and the preparation method includes the following steps:

[0141] First step: Dissolve 46 g of low-density polyethylene wax (Honeywell 1702) in 220 mL of xylene solvent, and heat to 90 °C and stir thoroughly for 30 minutes to dissolve.

[0142] Second step: Dissolve 4.0 g of acrylic acid and 0.37 g of benzoyl peroxide (BPO) in an appropriate amount of 30 mL of xylene, and stir at room temperature.

[0143] Third step: Keep the solution in the first step at 90 °C, slowly add the solution in the second step to the solution in the first step, and then stir and react fully for 4 hours.

[0144] Fourth step: Stop the reaction, cool down to room temperature, then pour the reaction solution into 2000 mL of ethanol for sedimentation and washing, and dry the solid for use.

[0145] Fifth step: Take 35 g of the polymer solid prepared in the fourth step, 3.0 g of emulsifier OP10, 0.2 g of emulsifier sodium dodecyl sulfate (SDS), 0.18 g of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, etc. and put them into 10 mL of xylene solvent, heat and dissolve, then add 61 mL of hot water, and stir at high speed to form an emulsion, and the resin dispersion for use can be obtained.

[0146] Characterization and analysis of the polymer emulsion: Take a small amount of the solid prepared in the fourth step and dry it, and then perform infrared absorption spectroscopy test. The results are as Figure 3 . In the figure, the ordinate is the transmittance, and the abscissa is the wavelength 3370 cm -1 is the hydroxyl absorption peak in acrylic acid, 2917 cm -1 and 2850 cm -1 are the stretching vibration peaks of methylene, 1702 cm -1 is the C=O stretching vibration peak in acrylic acid, 1465 cm -1 is the in-plane bending vibration peak of methylene, 1126 cm -1It is the C-O stretching vibration in acrylic acid.

[0147] Example 5

[0148] This example provides a resin composition, which is composed of a polymer shown in Formula I and an organic small molecule containing phenolic hydroxyl groups with a mass ratio of 1000:50.

[0149] M:N = 10:90 to 1:99, X = 0, (M + N):Y = 70:30 to 95:5; wherein, in the polymer, M:N = 5:95, X = 0, (M + N):Y = 85:15; the organic small molecule containing phenolic hydroxyl groups is pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate).

[0150] The resin composition is prepared by the following method, and the preparation method includes the following steps:

[0151] First step: Dissolve 2.07 g of sodium dodecyl sulfate (SDS) and 3.0 g of OP-10 in 250 mL of water, stir until fully dissolved, and then add 4.3 g of methyl acrylate monomer, 121.6 g of butyl acrylate monomer, and 12.0 g of isoprene monomer, and stir at high speed to obtain a pre-emulsion.

[0152] Second step: Dissolve 1.03 g of potassium persulfate (KPS) initiator and 0.45 g of OP-10 in 20 mL of water. Heat the pre-emulsion prepared in the first step to 50 °C, then slowly add the KPS initiator solution to the pre-emulsion at a constant speed, and then raise the temperature to 80 °C and stir and react for 4 hours.

[0153] Third step: Pour the emulsion prepared in the second step into 2000 mL of ethanol for sedimentation, wash the sedimented solid with ethanol, and dry it to obtain a polymer sample.

[0154] Fourth step: Take 58 g of the polymer sample prepared in the third step, 0.29 g of pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), and 0.58 g of OP-10 and dissolve and disperse them in 60 mL of xylene under high-speed stirring and heating, and then a resin dispersion for use can be obtained.

[0155] Comparative Example 1

[0156] The difference between this comparative example and Example 1 is that it does not include the organic small molecule containing phenolic hydroxyl groups, and the rest are the same as those in Example 1.

[0157] Comparative Example 2

[0158] The difference between this comparative example and Example 2 is that it does not include the organic small molecule containing phenolic hydroxyl groups, and the rest are the same as those in Example 2.

[0159] Comparative Example 3

[0160] The difference between this comparative example and Example 3 is that it does not include the organic small molecule containing a phenolic hydroxyl group, and the rest are the same as those in Example 3.

[0161] Comparative Example 4

[0162] The difference between this comparative example and Example 4 is that it does not include the organic small molecule containing a phenolic hydroxyl group, and the rest are the same as those in Example 4.

[0163] Comparative Example 5

[0164] The difference between this comparative example and Example 5 is that it does not include the organic small molecule containing a phenolic hydroxyl group, and the rest are the same as those in Example 5.

[0165] Application Example 1

[0166] This application example provides a composite material, which includes UHMWPE fibers selected from Hyosung, with a strength > 30 cN / dtex, an elongation at break < 5%, a modulus > 1100 cN / dtex, and the resin composition described in Example 1.

[0167] The composite material is prepared by the following method, and the preparation method includes the following steps:

[0168] (1) Form a water emulsion (solid content 40%) of the resin composition described in Example 1, dilute it with deionized water to a dilute emulsion with a mass concentration of 10%, place the dilute emulsion in an impregnation tank, and then pass the flattened UHMWPE fibers through the glue tank for impregnation, so that the resin dispersion is evenly dispersed on the fiber surface;

[0169] (2) Composite the fibers impregnated with the resin dispersion with a PE film, and then dry it to obtain a composite sheet of resin and fibers; here, the PE film is a common commercially available LDPE film with a melting point below 125°C.

[0170] (3) Stack the composite sheets alternately at 0° / 90°, and then thermally composite them under certain temperature and pressure to obtain a composite target sheet of UHMWPE fibers and matrix resin, which is the composite material, with a areal density of 5.4 m 2 / kg.

[0171] Application Example 2

[0172] This application example provides a composite material, which includes UHMWPE fibers selected from Hyosung, with a strength > 30 cN / dtex, an elongation at break < 5%, a modulus > 1100 cN / dtex, and the resin composition described in Example 2.

[0173] The composite material is prepared by the following method, and the preparation method includes the following steps:

[0174] (1) Dilute the resin composition described in Example 2 to form an aqueous emulsion (solid content 30%) with deionized water to a dilute emulsion with a mass concentration of 10%. Place the dilute emulsion in an impregnation tank, then pass the flattened UHMWPE fibers through the tank for impregnation, so that the resin dispersion is evenly dispersed on the fiber surface;

[0175] (2) Compound the fibers impregnated with the resin dispersion with a PE film, and then dry it to obtain a composite sheet of resin and fibers; here, the PE film is a common commercially available LDPE film with a melting point below 125 °C.

[0176] (3) Stack the composite sheets alternately at 0° / 90°, and then thermally compound them under certain temperature and pressure to obtain a composite target sheet of UHMWPE fibers and matrix resin, which is the said composite material, with a areal density of 5.4 m 2 / kg.

[0177] Application Example 3

[0178] This application example provides a composite material, which includes UHMWPE fibers selected from Hyosung, with a strength > 30 cN / dtex, an elongation at break < 5%, a modulus > 1100 cN / dtex and the resin composition described in Example 3.

[0179] The said composite material is prepared by the following method, and the preparation method includes the following steps:

[0180] (1) Dilute the resin composition described in Example 3 to form an aqueous emulsion (solid content 35%) with deionized water to a dilute emulsion with a mass concentration of 10%;

[0181] (2) Place the dilute emulsion in an impregnation tank, then pass the flattened UHMWPE fibers through the tank for impregnation, so that the resin dispersion is evenly dispersed on the fiber surface;

[0182] (3) Compound the fibers impregnated with the resin dispersion with a PE film, and then dry it to obtain a composite sheet of resin and fibers; here, the PE film is a common commercially available LDPE film with a melting point below 125 °C.

[0183] (4) Stack the composite sheets alternately at 0° / 90°, and then thermally compound them under certain temperature and pressure to obtain a composite target sheet of UHMWPE fibers and matrix resin, which is the said composite material, with a areal density of 5.4 m 2 / kg.

[0184] Application Example 4

[0185] This application example provides a composite material, which includes UHMWPE fibers selected from Weia, with a strength > 30 cN / dtex, an elongation at break < 5%, a modulus > 1100 cN / dtex, and the resin composition described in Example 4.

[0186] The composite material is prepared by the following method, and the preparation method includes the following steps:

[0187] (1) Dilute the water emulsion (solid content 35%) formed from the resin composition described in Example 4 with deionized water to a dilute emulsion with a mass concentration of 10%.

[0188] (2) Place the dilute emulsion in an impregnation tank, and then pass the flattened UHMWPE fibers through the glue tank for impregnation, so that the resin dispersion is evenly dispersed on the fiber surface.

[0189] (3) Composite the fibers impregnated with the resin dispersion with a PE film, and then dry it to obtain a composite sheet of resin and fibers; here, the PE film is a common commercially available LDPE film with a melting point below 125 °C.

[0190] (4) Stack the composite sheets alternately at 0° / 90°, and then thermally composite them under certain temperature and pressure to obtain a composite target sheet of UHMWPE fibers and matrix resin, which is the composite material, with a areal density of 5.4 m 2 / kg.

[0191] Application Example 5

[0192] This application example provides a composite material, which includes UHMWPE fibers with a strength > 30 cN / dtex, an elongation at break < 5%, a modulus > 1100 cN / dtex, and the resin composition described in Example 5.

[0193] The composite material is prepared by the following method, and the preparation method includes the following steps:

[0194] (1) Dilute the dispersion (solid content 50%) formed from the resin composition described in Example 5 with xylene to a dispersion with a mass concentration of 10%.

[0195] (2) Place the dispersion in an impregnation tank, and then pass the flattened UHMWPE fibers through the glue tank for impregnation, so that the resin dispersion is evenly dispersed on the fiber surface.

[0196] (3) Composite the fibers impregnated with the resin dispersion with a PE film, and then dry it to obtain a composite sheet of resin and fibers; here, the PE film is a common commercially available LDPE film with a melting point below 125 °C.

[0197] (4) The composite sheets are stacked alternately at 0° / 90°, and then thermally compounded under certain temperature and pressure to obtain a composite target sheet of UHMWPE fibers and matrix resin, which is the said composite material, with a areal density of 5.4 m 2 / kg.

[0198] Application Comparative Example 1

[0199] The difference between this application comparative example and Application Example 1 is that the resin composition is replaced with the resin composition described in Comparative Example 1, and the rest are the same as those in Application Example 1.

[0200] Application Comparative Example 2

[0201] The difference between this application comparative example and Application Example 2 is that the resin composition is replaced with the resin composition described in Comparative Example 2, and the rest are the same as those in Application Example 2.

[0202] Application Comparative Example 3

[0203] The difference between this application comparative example and Application Example 3 is that the resin composition is replaced with the resin composition described in Comparative Example 3, and the rest are the same as those in Application Example 3.

[0204] Application Comparative Example 4

[0205] The difference between this application comparative example and Application Example 4 is that the resin composition is replaced with the resin composition described in Comparative Example 4, and the rest are the same as those in Application Example 4.

[0206] Application Comparative Example 5

[0207] The difference between this application comparative example and Application Example 5 is that the resin composition is replaced with the resin composition described in Comparative Example 4, and the rest are the same as those in Application Example 5.

[0208] Performance Test

[0209] The composite materials described in Application Examples 1-5 and Application Comparative Examples 1-5 were subjected to a ballistic test for the V50 value of 1.1 g fragments, and the test method was carried out in accordance with the GA / T 950-2019 standard.

[0210] The test results are summarized in Table 1.

[0211] Table 1

[0212]

[0213]

[0214] Analysis of the data in Table 1 shows that the V50 value of the composite material formed by the resin composition of the present invention is above 526 m / s, and the composite material formed by the resin composition has excellent bulletproof performance; in addition, the resin composition of the present invention has the processing characteristics of thermoplastic resins, and the composite sheet formed by hot pressing has excellent performance and good forming effect.

[0215] Analysis of Application Example 1 and Application Comparative Example 1 shows that the performance of Application Comparative Example 1 is inferior to that of Application Example 1, proving that the composite material formed by the resin composition of the present invention has better performance. The same applies to Application Example 2 and Application Comparative Example 2, Application Example 3 and Application Comparative Example 3, Application Example 4 and Application Comparative Example 4, and Application Example 5 and Application Comparative Example 5.

[0216] The applicant declares that the present invention uses the above embodiments to illustrate the detailed method of the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A bulletproof material, characterized in that, The bulletproof material comprises polyethylene fibers and a resin composition, and the resin composition is composed of a polymer and an organic small molecule; The structure of the polymer is shown in Formula I: ； Formula I Wherein, R1 is selected from C1-C2 alkyl; R2 is selected from C3-C8 alkyl; R3 and R4 are each independently selected from hydrogen or methyl; M + N ≥ 30, X + Y ≥ 0; The ratio of M to N is 10:90 - 1:99, X = 0, (M + N):Y = 70:30 - 95:5; The organic small molecule contains a phenolic hydroxyl group; A hydrogen bond is formed between the phenolic hydroxyl group in the organic small molecule and the carbonyl group in the polymer; The organic small molecule includes any one or at least two combinations of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)benzoate or 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; In the resin composition, the mass ratio of the polymer to the organic small molecule is 1000:(50 - 100).

2. The bulletproof material according to claim 1, wherein, M:N is 10:90 - 5:95, X = 0, (M + N):Y = 70:30 - 90:

10.

3. The bulletproof material according to claim 1, wherein The functionality of the organic small molecule is 3 or 4.

4. The bulletproof material according to claim 1, characterized in that, In the resin composition, the polymer includes any one or at least two combinations.

5. The bulletproof material according to claim 1, characterized in that, The preparation method of the resin composition comprises the following steps: Mix the polymer and the organic small molecule to obtain the resin composition.

6. The bulletproof material according to claim 5, characterized in that The preparation method of the polymer comprises the following steps: Mix the polymerization monomers and an initiator, and polymerize to form the polymer.

7. The bulletproof material according to claim 6, wherein The polymerization monomers include at least two combinations of methyl acrylate, butyl acrylate or isoprene.

8. The bulletproof material according to claim 6, characterized in that, The initiator includes potassium persulfate and / or benzoyl peroxide.

9. The bulletproof material according to claim 6, characterized in that, The mixed raw materials further include an emulsifier.

10. The bulletproof material according to claim 9, characterized in that, The emulsifier includes sodium dodecyl sulfate and / or OP-10 emulsifier.

11. The bulletproof material according to claim 1, characterized in that, The bulletproof material includes a resin composition dispersion liquid composed of the resin composition and a solvent.

12. The bulletproof material according to claim 11, characterized in that, The solvent includes any one or at least two combinations of water, n-hexane, petroleum ether, tetrahydrofuran, acetone, N,N-dimethylformamide, 1,4-dioxane, dichloromethane, chloroform, toluene or xylene.

13. The bulletproof material according to claim 11, characterized in that, The preparation method of the bulletproof material comprises the following steps: Soak the polyethylene fibers with the resin composition dispersion liquid, dry and hot press and laminate to obtain the bulletproof material.

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