CN114645465B - Polyurea elastomer composite material and preparation method thereof - Google Patents

Polyurea elastomer composite material and preparation method thereof Download PDF

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Publication number
CN114645465B
CN114645465B CN202011495329.1A CN202011495329A CN114645465B CN 114645465 B CN114645465 B CN 114645465B CN 202011495329 A CN202011495329 A CN 202011495329A CN 114645465 B CN114645465 B CN 114645465B
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molecular weight
ultra
weight polyethylene
high molecular
polyurea
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CN114645465A (en
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刘若鹏
赵治亚
侯燕
张运湘
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Luoyang Institute of Cutting Edge Technology
Luoyang Cutting Edge Equipment Technology Ltd
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Luoyang Institute of Cutting Edge Technology
Luoyang Cutting Edge Equipment Technology Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/34—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxygen, ozone or ozonides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0038—Polyolefin fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • D06N3/009—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin by spraying components on the web
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups

Abstract

The invention relates to a preparation method of a polyurea elastomer composite material, which comprises the steps of carrying out ozone activation treatment on an ultra-high molecular weight polyethylene fiber base material; performing a surface treatment step on the ultra-high molecular weight polyethylene fiber substrate by using hydroxyl-terminated hyperbranched polyisocyanurate; and coating the polyurea coating on the surface to be treated of the ultra-high molecular weight polyethylene fiber substrate. The polyurea/ultra-high molecular weight polyethylene fiber composite material prepared by the invention can realize the effect of high strength and high modulus.

Description

Polyurea elastomer composite material and preparation method thereof
Technical Field
The invention relates to the field of resin reinforced materials, in particular to a polyurea elastomer composite material and a preparation method thereof.
Background
The fiber reinforced resin matrix composite material has light weight, simple preparation process and good damping and energy absorbing effects, and is widely researched and applied. However, the adhesive strength between the traditional resin and the fiber layers is not high, so that the strength of the traditional resin in the thickness direction is low, and the traditional resin is sensitive to impact, so that functional failure is very easy to generate after the traditional resin is impacted in the using process, and the safety of structural members is seriously threatened.
The polyurea is an elastomer material, has excellent damping and energy absorbing effects, high elastic modulus and high tensile strength, and is widely applied to the fields of bulletproof armor and the like. The high-strength fiber mainly comprises carbon fiber, glass fiber, aramid fiber and the like, the ultra-high molecular weight polyethylene fiber (UHMWPE) is another high-performance fiber appearing after the carbon fiber and the aramid fiber, is a fiber spun by polyethylene with the molecular weight of 100-500 ten thousand, has the advantages of high strength, high modulus, low fiber density, chemical corrosion resistance, high specific energy absorption, high electromagnetic wave transmittance, low friction coefficient and excellent impact resistance, and is an excellent choice for light bulletproof clothing, stab-resistant clothing and bulletproof helmets. However, ultra-high molecular weight polyethylene fibers are nonpolar materials, have low surface energy, and have low interlayer bonding strength with resins.
Therefore, the development of the preparation method of the polyurea elastomer composite material, which can effectively increase the polarity of the fiber surface and improve the binding force of the fiber and the resin, ensures that the prepared polyurea elastomer composite material has high strength and high impact resistance effect, has important significance.
Disclosure of Invention
Based on the above, the invention provides the polyurea elastomer composite material and the preparation method thereof, and the preparation method can effectively increase the polarity of the fiber surface, improve the binding force between the fiber and the resin, and the prepared polyurea elastomer composite material has the protective effect of high strength and high impact resistance.
A method for preparing a polyurea elastomer composite, comprising the steps of:
1) Carrying out ozone activation treatment on the ultra-high molecular weight polyethylene fiber substrate;
2) Surface treating the ultra-high molecular weight polyethylene fiber substrate with hydroxyl-terminated hyperbranched polyisocyanurate;
3) The polyurea coating is coated on the surface to be treated of the ultrahigh molecular weight polyethylene fiber substrate subjected to surface treatment.
In some embodiments, the polyurea elastomer composite is prepared by a method wherein the ozone is activated by a flow rate of ozoneIs 50mL/min -1 ～200mL·min -1 。
In some of these embodiments, the process for preparing the polyurea elastomer composite, the synthesis of the hydroxyl-terminated hyperbranched polyisocyanurate comprises the steps of:
the AB is prepared from diisopropanolamine and methyl acrylate serving as raw materials through Michael addition reaction 2 The monomer or, take diethanolamine and methyl acrylate as raw materials, prepare AB through Michael addition reaction 2 A monomer;
by AB 2 The hydroxyl-terminated hyperbranched polyisocyanurate is prepared by transesterification reaction with the monomer and tris- (2-hydroxyethyl) isocyanurate as reaction substrates.
In some of these embodiments, the polyurea elastomer composite is prepared by a process wherein the mole ratio of diisopropanolamine to methyl acrylate is 1:2, the solvent used in the Michael addition reaction is methanol.
In some embodiments, the catalyst used in the transesterification reaction is p-toluenesulfonic acid and the solvent is N, N-dimethylformamide.
In some of these embodiments, the surface treatment is performed by immersing the ultra-high molecular weight polyethylene fiber substrate in a hydroxyl-terminated hyperbranched polyisocyanurate solution.
In some embodiments, the preparation method of the polyurea elastomer composite material comprises the steps that the hydroxyl-terminated hyperbranched polyisocyanurate solution is a mixed solution of the hydroxyl-terminated hyperbranched polyisocyanurate dissolved in N, N-dimethylformamide, the concentration is 0.5g/L-3g/L, and the soaking time is 0.5 h-6 h.
In some of these embodiments, the polyurea coating comprises a polyurea coating a and a polyurea coating B;
the polyurea coating A is isocyanate;
the polyurea coating B is a mixture containing polyaspartic acid ester, an antifoaming agent, an adhesion promoter, a leveling agent and a pigment-filler grouting agent.
In some embodiments, in the method for preparing the polyurea elastomer composite, the ultra-high molecular weight polyethylene fiber base material is ultra-high molecular weight polyethylene fiber cloth, and the polyurea coating is sprayed on two sides of the ultra-high molecular weight polyethylene fiber cloth.
In some embodiments, the polyurea elastomer composite is prepared by spraying a polyurea coating having a thickness of 1mm to 2mm on each side.
The invention also provides the polyurea elastomer composite material obtained by the preparation method of the polyurea elastomer composite material.
Compared with the prior art, the invention has the following beneficial effects:
the high-oxidation property of ozone is utilized to generate active groups on the surface of the ultra-high molecular weight polyethylene fiber by carrying out ozone treatment on the ultra-high molecular weight polyethylene fiber, so that the polarity of the fiber surface is increased. Further, through the treatment of the hydroxyl-terminated hyperbranched polyisocyanurate, the peroxy groups generated on the surface of the ultra-high molecular weight polyethylene fiber treated by ozone react with the hydroxyl-terminated hyperbranched polyisocyanurate, and when a polyurea elastomer (SPU) is sprayed on the surface of the ultra-high molecular weight polyethylene fiber woven cloth, a good synergistic effect can be achieved with the polyurea, the interfacial compatibility of the fiber and the resin is improved, the binding force of the fiber and the resin is further improved, and the resin and the fiber are prevented from being separated from each other to fail when the material is impacted, so that the high-strength and high-impact-resistance protection effect is achieved.
The polyurea/ultra-high molecular weight polyethylene fiber composite material prepared by the invention can realize the effect of high strength and high modulus.
Drawings
FIG. 1 is a schematic structural view of an example polyurea elastomer composite.
Detailed Description
The polyurea elastomer composite of the present invention and the method of making the same are described in further detail below in conjunction with the specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
An embodiment of the invention provides a preparation method of a polyurea elastomer composite material, which comprises the steps S10-S30.
Step S10: and (3) carrying out ozone activation treatment on the ultra-high molecular weight polyethylene fiber substrate.
Step S20: the surface treatment of ultra-high molecular weight polyethylene fiber substrates using hydroxyl-terminated hyperbranched polyisocyanurates.
Step S30: the polyurea coating is coated on the surface to be treated of the ultrahigh molecular weight polyethylene fiber substrate subjected to surface treatment.
It is understood that ultra-high molecular weight polyethylene fibers are fibers spun from polyethylene having a molecular weight of 100 to 500 tens of thousands.
In some of these embodiments, in step S10, the ultra-high molecular weight polyethylene fiber substrate is an ultra-high molecular weight polyethylene fiber cloth.
In some embodiments, in step S10, the method further comprises a step of drying the ultra-high molecular weight polyethylene fiber substrate before the ozone activation treatment.
In some embodiments, in step S10, the flow rate of ozone at the time of the ozone activation treatment is 50mL/min -1 ～200mL·min -1 。
Preferably, the flow rate of ozone is 100 mL-min -1 。
In some of these embodiments, in step S20, the surface treatment is performed by immersing the ultra-high molecular weight polyethylene fiber substrate in a hydroxyl-terminated hyperbranched polyisocyanurate solution.
In some of these embodiments, in step S20, the hydroxyl-terminated hyperbranched polyisocyanurate solution is a mixed solution of hydroxyl-terminated hyperbranched polyisocyanurate dissolved in N, N-dimethylformamide.
In some of these embodiments, in step S20, the hydroxyl-terminated hyperbranched polyisocyanurate solution concentration is from 0.5g/L to 3g/L.
Preferably, the concentration of the hydroxyl-terminated hyperbranched polyisocyanurate solution is 2g/L.
In some embodiments, the time for soaking the ultra-high molecular weight polyethylene fiber substrate in step S20 is 0.5 to 6 hours.
Optionally, the ultra-high molecular weight polyethylene fiber substrate is soaked for 1-4 hours.
Preferably, the ultra-high molecular weight polyethylene fiber substrate is soaked for 3 hours.
In some of these embodiments, in step S20, the baking step is involved after the soaking of the ultra-high molecular weight polyethylene fiber substrate is completed.
In some of these embodiments, step S20 includes steps S210-S220 of synthesizing hydroxyl-terminated hyperbranched polyisocyanurate.
Step S210: AB is prepared from diisopropanolamine and methyl acrylate by Michael addition reaction 2 And (3) a monomer.
Step S220: by AB 2 The hydroxyl-terminated hyperbranched polyisocyanurate is prepared by transesterification reaction with the monomer and tris- (2-hydroxyethyl) isocyanurate as reaction substrates.
In some of these embodiments, in step S210, the molar ratio of diisopropanolamine to methyl acrylate is 1:2.
in some of these embodiments, in step S210, the molar ratio of diethanolamine to methyl acrylate is 1:2.
in some of these embodiments, in step S210, the solvent used in the Michael addition reaction is methanol.
In some of these embodiments, in step S210, the reaction concentration of diisopropanolamine is 10mmol/mL.
In some of these embodiments, in step S210, diisopropanolamine is mixed with methanol and then methyl acrylate is added dropwise at room temperature.
In some of these embodiments, in step S210, the Michael addition reaction temperature is 35 ℃.
In some embodiments, in step S210, the Michael addition reaction is completed with a post-treatment step S211.
Step S211: the reaction solution was filtered under vacuum, and the methanol was removed by extraction with diethyl ether to give a colorless transparent oily product.
In some of these embodiments, in step S220, the catalyst used in the transesterification reaction is p-toluene sulfonic acid.
In some embodiments, in step S220, the solvent used in the transesterification reaction is N, N-dimethylformamide.
In some of these embodiments, in step S220, tris- (2-hydroxyethyl) isocyanurate and N, N-dimethylformamide are mixed, a catalyst is added, and AB is added dropwise 2 And (3) a monomer.
In some of these embodiments, the temperature of the transesterification reaction in step S220 is 115 ℃.
In some embodiments, in step S220, the post-treatment step S221 is further included after the transesterification reaction is completed.
Step S221: vacuum filtering, dissolving with acetone, reprecipitating with dichloromethane, extracting with diethyl ether, washing, repeating the operation for 3 times, and concentrating the upper liquid.
In some of these embodiments, step S30 also involves fixing the surface treated ultra high molecular weight polyethylene fiber substrate to a composite or glass sheet prior to spraying.
In some of these embodiments, in step S30, the polyurea coating comprises a mixture of polyurea coating a, which is an isocyanate, and polyurea coating B, which is a mixture comprising a polyaspartic acid ester, an antifoaming agent, an adhesion promoter, a leveling agent, and a pigment-filler slip agent.
In one specific example, polyurea coating B is a mixture comprising polyaspartic acid ester, defoamer, adhesion promoter, leveling agent, and pigment and filler grouting agent.
In some of these embodiments, in step S30, the mixing volume ratio of polyurea coating A to polyurea coating B is 1 (1-1.5).
It will be appreciated that too large a ratio results in curing too fast to react.
Preferably, the mixing volume ratio of polyurea coating A to polyurea coating B is 1:1.
In some of these embodiments, in step S30, the polyurea coating is sprayed onto the surface to be treated of the ultra-high molecular weight polyethylene fiber substrate.
In some of these embodiments, in step S30, the polyurea coating is sprayed on both sides of the ultra-high molecular weight polyethylene fiber cloth.
In some of these embodiments, in step S30, the polyurea coating is sprayed at a thickness of 1mm to 2mm on each side.
The invention also provides the polyurea elastomer composite material obtained by the preparation method.
Referring to fig. 1, in the specific example shown in fig. 1, the polyurea elastomer composite 10 includes a substrate 11 and polyureas 12 disposed on both side surfaces of the substrate 11.
It will be appreciated that in other specific examples, polyurea 12 may be provided on only one side surface of substrate 11.
The high-oxidation property of ozone is utilized to generate active groups on the surface of the ultra-high molecular weight polyethylene fiber by carrying out ozone treatment on the ultra-high molecular weight polyethylene fiber, so that the polarity of the fiber surface is increased. Further, through the treatment of the hydroxyl-terminated hyperbranched polyisocyanurate, the peroxy groups generated on the surface of the ultra-high molecular weight polyethylene fiber treated by ozone react with the hydroxyl-terminated hyperbranched polyisocyanurate, and when a polyurea elastomer (SPU) is sprayed on the surface of the ultra-high molecular weight polyethylene fiber woven cloth, a good synergistic effect can be achieved with the polyurea, the interfacial compatibility of the fiber and the resin is improved, the binding force of the fiber and the resin is further improved, and the resin and the fiber are prevented from being separated from each other to fail when the material is impacted, so that the high-strength and high-impact-resistance protection effect is achieved.
The polyurea/ultra-high molecular weight polyethylene fiber composite material prepared by the invention can realize the effect of high strength and high modulus.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following examples of the polyurea elastomer composite according to the present invention and the method for preparing the same are given below, and it is understood that the polyurea elastomer composite according to the present invention and the method for preparing the same are not limited to the following examples.
The hydroxyl-terminated hyperbranched polyisocyanurates used in the examples below were synthesized according to the following procedure:
0.1mol of diisopropanolamine was weighed and dissolved in 10mL of CH at room temperature 3 In the OH solution, the mol ratio of diisopropanolamine to methyl acrylate is 1:2, dropwise adding methyl acrylate, heating to 35 ℃, stirring, and reacting for 3.5h to obtain AB 2 And (3) extracting and washing the monomer with diethyl ether to remove methanol after vacuum filtration to obtain a colorless transparent oily product for later use.
13.1g of tris- (2-hydroxyethyl) isocyanurate are dissolved in 50mL of DMF and the catalyst p-toluenesulfonic acid 0.675g is added and AB is added dropwise 2 The reaction was carried out at 115℃for 4h. And carrying out vacuum filtration, acetone dissolution, methylene dichloride reprecipitation and diethyl ether extraction washing on the obtained crude product. Repeating the above operation for 3 times, mixing the obtained upper layer liquid, and distilling off the solvent under reduced pressure on a rotary evaporator to obtain the hydroxyl-terminated hyperbranched polyisocyanurate.
Example 1
Preparation of polyurea elastomer/ultra-high molecular weight polyethylene fiber composite material
1) Surface ozone treatment for ultra-high molecular weight polyethylene fiber cloth
And (3) putting the cut ultra-high molecular weight polyethylene fiber cloth with the size of 300mm multiplied by 300mm into an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 1h, removing water and taking out.
Placing the dried ultra-high molecular weight polyethylene fiber cloth into ozone activation equipment, controlling the flow rate of ozone at 100mL/min, and treating for 1h.
2) 0.05g of hydroxyl-terminated hyperbranched polyisocyanurate is taken and dissolved in 100mL of N, N-dimethylformamide solution, and the ultra-high molecular weight polyethylene fiber cloth treated by ozone is soaked for 1h, taken out and dried.
3) The ultra-high molecular weight polyethylene fiber cloth soaked in the hydroxyl-terminated hyperbranched polyisocyanurate solution is fixed on a 500mm multiplied by 500mm composite board.
4) Preparing an isocyanate-HDI trimer of the polyurea coating A, which is purchased from Wanhua company of a tobacco stand;
polyurea coating B, purchased from Zhuhai flying chemical company, model F520.
The H-XP3 spraying machine of the solid Rake company in the United states is adopted, and the main technological parameters are as follows: the hydraulic pressure is 50kg/cm 2 ～60kg/cm 2 The temperature of the materials is 60-77 ℃, the mixing volume ratio is 1:1, the front and the back are sprayed, and the thickness of the coating is controlled to be 1mm.
Example 2
Preparation of polyurea elastomer/ultra-high molecular weight polyethylene fiber composite material
1) Surface ozone treatment for ultra-high molecular weight polyethylene fiber cloth
And (3) putting the cut ultra-high molecular weight polyethylene fiber cloth with the size of 300mm multiplied by 300mm into an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 1h, removing water and taking out.
Placing the dried ultra-high molecular weight polyethylene fiber cloth into ozone activation equipment, controlling the flow rate of ozone at 50mL/min, and treating for 1h.
2) 0.1g of hydroxyl-terminated hyperbranched polyisocyanurate is taken and dissolved in 100mL of N, N-dimethylformamide solution, and the ultra-high molecular weight polyethylene fiber cloth treated by ozone is soaked for 2 hours, taken out and dried.
3) The ultra-high molecular weight polyethylene fiber cloth soaked in the hydroxyl-terminated hyperbranched polyisocyanurate solution is fixed on a 500mm multiplied by 500mm composite board.
4) Preparing an isocyanate-HDI trimer of the polyurea coating A, which is purchased from Wanhua company of a tobacco stand;
polyurea coating B, purchased from Zhuhai flying chemical company, model F520.
The H-XP3 spraying machine of the solid Rake company in the United states is adopted, and the main technological parameters are as follows:the hydraulic pressure is 50kg/cm 2 ～60kg/cm 2 The temperature of the materials is 60-77 ℃, the mixing volume ratio is 1:1, the front and the back are sprayed, and the thickness of the coating is controlled to be 1.5mm.
Example 3
Preparation of polyurea elastomer/ultra-high molecular weight polyethylene fiber composite material
1) Surface ozone treatment for ultra-high molecular weight polyethylene fiber cloth
And (3) putting the cut ultra-high molecular weight polyethylene fiber cloth with the size of 300mm multiplied by 300mm into an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 1h, removing water and taking out.
Placing the dried ultra-high molecular weight polyethylene fiber cloth into ozone activation equipment, controlling the flow rate of ozone at 100mL/min, and treating for 1h.
2) 0.2g of hydroxyl-terminated hyperbranched polyisocyanurate is taken and dissolved in 100mL of N, N-dimethylformamide solution, and the ultra-high molecular weight polyethylene fiber cloth treated by ozone is soaked for 3 hours, taken out and dried.
3) The ultra-high molecular weight polyethylene fiber cloth soaked in the hydroxyl-terminated hyperbranched polyisocyanurate solution is fixed on a 500mm multiplied by 500mm composite board.
4) Preparing an isocyanate-HDI trimer of the polyurea coating A, which is purchased from Wanhua company of a tobacco stand;
polyurea coating B, purchased from Zhuhai flying chemical company, model F520.
The H-XP3 spraying machine of the solid Rake company in the United states is adopted, and the main technological parameters are as follows: the hydraulic pressure is 50kg/cm 2 ～60kg/cm 2 The temperature of the materials is 60-77 ℃, the mixing volume ratio is 1:1, the front and the back are sprayed, and the thickness of the coating is controlled to be 2mm.
Example 4
Preparation of polyurea elastomer/ultra-high molecular weight polyethylene fiber composite material
1) Surface ozone treatment for ultra-high molecular weight polyethylene fiber cloth
And (3) putting the cut ultra-high molecular weight polyethylene fiber cloth with the size of 300mm multiplied by 300mm into an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 1h, removing water and taking out.
Placing the dried ultra-high molecular weight polyethylene fiber cloth into ozone activation equipment, controlling the flow rate of ozone at 150mL/min, and treating for 1h.
2) 0.3g of hydroxyl-terminated hyperbranched polyisocyanurate is taken and dissolved in 100mL of N, N-dimethylformamide solution, and the ultra-high molecular weight polyethylene fiber cloth treated by ozone is soaked for 4 hours, taken out and dried.
3) The ultra-high molecular weight polyethylene fiber cloth soaked in the hydroxyl-terminated hyperbranched polyisocyanurate solution is fixed on a 500mm multiplied by 500mm composite board.
4) Preparing an isocyanate-HDI trimer of the polyurea coating A, which is purchased from Wanhua company of a tobacco stand;
polyurea coating B, purchased from Zhuhai flying chemical company, model F520.
The H-XP3 spraying machine of the solid Rake company in the United states is adopted, and the main technological parameters are as follows: the hydraulic pressure is 50kg/cm 2 ～60kg/cm 2 The temperature of the materials is 60-77 ℃, the mixing volume ratio is 1:1, the front and the back are sprayed, and the thickness of the coating is controlled to be 1.5mm.
Comparative example 1
Preparation of polyurea elastomer/ultra-high molecular weight polyethylene fiber composite material
1) Surface ozone treatment for ultra-high molecular weight polyethylene fiber cloth
And (3) putting the cut ultra-high molecular weight polyethylene fiber cloth with the size of 300mm multiplied by 300mm into an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 1h, removing water and taking out.
Placing the dried ultra-high molecular weight polyethylene fiber cloth into ozone activation equipment, controlling the flow rate of ozone at 100mL/min, and treating for 1h.
2) 0.2g of silane coupling agent KH550 is dissolved in 100mL of N, N-dimethylacetamide solution, and the ultra-high molecular weight polyethylene fiber cloth treated by ozone is soaked for 3 hours, taken out and dried.
3) The ultra-high molecular weight polyethylene fiber cloth soaked by the solution of the silane coupling agent KH550 is fixed on a 500mm multiplied by 500mm composite board.
4) Preparing an isocyanate-HDI trimer of the polyurea coating A, which is purchased from Wanhua company of a tobacco stand;
polyurea coating B, purchased from Zhuhai flying chemical company, model F520.
The H-XP3 spraying machine of the solid Rake company in the United states is adopted, and the main technological parameters are as follows: the hydraulic pressure is 50kg/cm 2 ～60kg/cm 2 The temperature of the materials is 60-77 ℃, the mixing volume ratio is 1:1, the front and the back are sprayed, and the thickness of the coating is controlled to be 2mm.
Comparative example 2
Preparation of polyurea elastomer/ultra-high molecular weight polyethylene fiber composite material
1) Surface ozone treatment for ultra-high molecular weight polyethylene fiber cloth
And (3) putting the cut ultra-high molecular weight polyethylene fiber cloth with the size of 300mm multiplied by 300mm into an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 1h, removing water and taking out.
Placing the dried ultra-high molecular weight polyethylene fiber cloth into ozone activation equipment, controlling the flow rate of ozone at 100mL/min, and treating for 1h.
2) 0.2g of 3-ureidopropyltriethoxysilane is dissolved in 100mL of N, N-dimethylformamide solution, and the ultra-high molecular weight polyethylene fiber cloth is soaked for 3h, taken out and dried.
3) The ultra-high molecular weight polyethylene fiber cloth soaked in the 3-ureidopropyltriethoxysilane solution is fixed on a 500mm multiplied by 500mm composite board.
4) Preparing an isocyanate-HDI trimer of the polyurea coating A, which is purchased from Wanhua company of a tobacco stand;
polyurea coating B, purchased from Zhuhai flying chemical company, model F520.
The H-XP3 spraying machine of the solid Rake company in the United states is adopted, and the main technological parameters are as follows: the hydraulic pressure is 50kg/cm 2 ～60kg/cm 2 The temperature of the materials is 60-77 ℃, the mixing volume ratio is 1:1, the front and the back are sprayed, and the thickness of the coating is controlled to be 2mm.
Comparative example 3
Preparation of polyurea elastomer/ultra-high molecular weight polyethylene fiber composite material
1) Surface ozone treatment for ultra-high molecular weight polyethylene fiber cloth
And (3) putting the cut ultra-high molecular weight polyethylene fiber cloth with the size of 300mm multiplied by 300mm into an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 1h, removing water and taking out.
Placing the dried ultra-high molecular weight polyethylene fiber cloth into ozone activation equipment, controlling the flow rate of ozone at 100mL/min, and treating for 1h.
2) An ultra-high molecular weight polyethylene fiber cloth was fixed on a 500mm x 500mm composite plate.
4) Preparing an isocyanate-HDI trimer of the polyurea coating A, which is purchased from Wanhua company of a tobacco stand;
polyurea coating B, purchased from Zhuhai flying chemical company, model F520.
The H-XP3 spraying machine of the solid Rake company in the United states is adopted, and the main technological parameters are as follows: the hydraulic pressure is 50kg/cm 2 ～60kg/cm 2 The temperature of the materials is 60-77 ℃, the mixing volume ratio is 1:1, the front and the back are sprayed, and the thickness of the coating is controlled to be 2mm.
Comparative example 4
Preparation of polyurea elastomer/ultra-high molecular weight polyethylene fiber composite material
1) Surface ozone treatment for ultra-high molecular weight polyethylene fiber cloth
And (3) putting the cut ultra-high molecular weight polyethylene fiber cloth with the size of 300mm multiplied by 300mm into an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 1h, removing water and taking out.
2) 0.2g of hydroxyl-terminated hyperbranched polyisocyanurate is taken and dissolved in 100mL of N, N-dimethylformamide solution, and the ultra-high molecular weight polyethylene fiber cloth is soaked for 3 hours, taken out and dried.
3) The ultra-high molecular weight polyethylene fiber cloth soaked in the hydroxyl-terminated hyperbranched polyisocyanurate solution is fixed on a 500mm multiplied by 500mm composite board.
4) Preparing an isocyanate-HDI trimer of the polyurea coating A, which is purchased from Wanhua company of a tobacco stand;
polyurea coating B, purchased from Zhuhai flying chemical company, model F520.
The H-XP3 spraying machine of the solid Rake company in the United states is adopted, and the main technological parameters are as follows: the hydraulic pressure is 50kg/cm 2 ～60kg/cm 2 The temperature of the materials is 60-77 ℃, the mixing volume ratio is 1:1, the front and the back are sprayed, and the thickness of the coating is controlled to be 2mm.
Comparative example 5
Preparation of polyurea elastomer/ultra-high molecular weight polyethylene fiber composite material
1) Surface ozone treatment for ultra-high molecular weight polyethylene fiber cloth
And (3) putting the cut ultra-high molecular weight polyethylene fiber cloth with the size of 300mm multiplied by 300mm into an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 1h, removing water and taking out.
Placing the dried ultra-high molecular weight polyethylene fiber cloth into ozone activation equipment, controlling the flow rate of ozone at 100mL/min, and treating for 1h.
2) 1g of hydroxyl-terminated hyperbranched polyisocyanurate is taken to be dissolved in 100mL of N, N-dimethylformamide solution, and the ultra-high molecular weight polyethylene fiber cloth treated by ozone is soaked for 8 hours, taken out and dried.
3) The ultra-high molecular weight polyethylene fiber cloth soaked in the hydroxyl-terminated hyperbranched polyisocyanurate solution is fixed on a 500mm multiplied by 500mm composite board.
4) Preparing an isocyanate-HDI trimer of the polyurea coating A, which is purchased from Wanhua company of a tobacco stand;
polyurea coating B, purchased from Zhuhai flying chemical company, model F520.
The H-XP3 spraying machine of the solid Rake company in the United states is adopted, and the main technological parameters are as follows: the hydraulic pressure is 50kg/cm 2 ～60kg/cm 2 The temperature of the materials is 60-77 ℃, the mixing volume ratio is 1:1, the front and the back are sprayed, and the thickness of the coating is controlled to be 3mm.
Comparative example 6
Substantially the same as in example 3, except that the ultra high molecular weight polyethylene fiber cloth in example 3 was changed to a general polyethylene fiber cloth.
Tensile strength and impact resistance were measured for examples 1 to 4 and comparative examples 1 to 6, respectively.
Tensile Strength reference GB/T528-2009 "determination of tensile stress Strain Properties of vulcanized rubber or thermoplastic rubber"; impact resistance test reference GB/T1043.1-2008 "determination of impact resistance of Plastic simply supported beams".
The test results are shown in Table 1.
TABLE 1
The polyurea/hydroxyl-terminated hyperbranched polyisocyanurate achieves the effects of high strength and high modulus, the polarity of the fiber surface is increased by carrying out ozone treatment on the hydroxyl-terminated hyperbranched polyisocyanurate, and the binding force between the fiber and the resin is improved by the hyperbranched polyisocyanurate, so that the resin and the fiber are prevented from being separated to fail when the material is impacted.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. A method for preparing a polyurea elastomer composite, comprising the steps of:
1) Carrying out ozone activation treatment on the ultra-high molecular weight polyethylene fiber substrate;
2) Surface-treating the ultra-high molecular weight polyethylene fiber substrate subjected to the ozone activation treatment by using hydroxyl-terminated hyperbranched polyisocyanurate;
3) Coating polyurea coating on the surface of the ultrahigh molecular weight polyethylene fiber substrate subjected to surface treatment;
the synthesis steps of the hydroxyl-terminated hyperbranched polyisocyanurate comprise:
the AB is prepared from diisopropanolamine and methyl acrylate serving as raw materials through Michael addition reaction 2 The monomer or, take diethanolamine and methyl acrylate as raw materials, prepare AB through Michael addition reaction 2 A monomer;
by AB 2 The hydroxyl-terminated hyperbranched polyisocyanurate is prepared by transesterification reaction with the monomer and tris- (2-hydroxyethyl) isocyanurate as reaction substrates.
2. The method for producing a polyurea elastomer composite according to claim 1, wherein the flow rate of ozone is 50mL/min when the ozone activation treatment is performed -1 ～200mL·min -1 。
3. The method of preparing a polyurea elastomer composite according to claim 1, wherein the molar ratio of diisopropanolamine to methyl acrylate is 1:2, the solvent used in the Michael addition reaction is methanol.
4. The method for preparing a polyurea elastomer composite according to claim 1, wherein the catalyst used in the transesterification reaction is p-toluenesulfonic acid and the solvent is N, N-dimethylformamide.
5. The process for preparing a polyurea elastomer composite according to claim 1, wherein in step 2) the surface treatment is immersing the ultra-high molecular weight polyethylene fiber substrate in a solution of hydroxyl-terminated hyperbranched polyisocyanurate.
6. The process for producing a polyurea elastomer composite according to claim 5, wherein the solution of the hydroxyl-terminated hyperbranched polyisocyanurate is a mixed solution of the hydroxyl-terminated hyperbranched polyisocyanurate dissolved in N, N-dimethylformamide, the concentration is 0.5g/L to 3g/L, and the soaking time is 0.5h to 6h.
7. The method of producing a polyurea elastomer composite according to any one of claims 1 to 6, wherein the polyurea coating comprises a polyurea coating a and a polyurea coating B;
the polyurea coating A is isocyanate;
the polyurea coating B is a mixture containing polyaspartic acid ester, an antifoaming agent, an adhesion promoter, a leveling agent and a pigment-filler grouting agent.
8. The method for producing a polyurea elastomer composite according to any one of claims 1 to 6, wherein the ultra-high molecular weight polyethylene fiber base material is an ultra-high molecular weight polyethylene fiber cloth, and the polyurea coating is sprayed on both sides of the ultra-high molecular weight polyethylene fiber cloth.
9. The method of preparing a polyurea elastomer composite according to claim 8, wherein the thickness of each side of the polyurea coating is 1mm to 2mm.
10. Polyurea elastomer composite obtainable by the process according to any one of claims 1 to 9.
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