CN111533923A - High-wear-resistance and high-cutting-resistance graphene-hard material base composite latex and application thereof - Google Patents

High-wear-resistance and high-cutting-resistance graphene-hard material base composite latex and application thereof Download PDF

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CN111533923A
CN111533923A CN202010256022.XA CN202010256022A CN111533923A CN 111533923 A CN111533923 A CN 111533923A CN 202010256022 A CN202010256022 A CN 202010256022A CN 111533923 A CN111533923 A CN 111533923A
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graphene
hard material
latex
resistance
composite
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CN111533923B (en
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沙嫣
沙晓林
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Nantong Qs Safety Protection Technology Co ltd
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Nantong Qs Safety Protection Technology Co ltd
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Abstract

The invention relates to high-wear-resistance and high-cutting-resistance graphene-hard material base composite latex and application thereof, wherein the composite latex comprises the following components in parts by weight: 1-9 parts of graphene modified composite hard material, 0.1-0.5 part of dispersant, 0.05-0.1 part of stabilizer, 0.2-1 part of accelerator and 80-90 parts of latex. The composite latex prepared by the invention can use common cotton yarn, chemical fiber or blended yarn and the like as a bottom lining, and the composite material of the textile fabric and the latex has high-grade wear resistance and cutting resistance through a dipping or coating process. The prepared gloves are tested by EN388 standard, the cutting resistance is up to 5 grade, the wear resistance is up to 4 grade, the tear resistance is up to 4 grade, and the puncture resistance is up to 4 grade.

Description

High-wear-resistance and high-cutting-resistance graphene-hard material base composite latex and application thereof
Technical Field
The invention relates to the technical field of security glove preparation, in particular to graphene-hard material base composite latex with high wear resistance and high cutting resistance and application thereof.
Background
At present, the method for improving the wear resistance and the cutting resistance of textiles is mainly to use high-strength fiber materials, such as aramid fibers, carbon fibers, high-modulus polyethylene, basalt fibers and the like to prepare glove blanks or other textile base fabrics, for example, patent CN106555244A discloses a cutting-resistant ultra-high molecular weight polyethylene fiber, including ultra-high molecular weight polyethylene fiber; hard fibers dispersed in the ultra high molecular weight polyethylene fibers; the mass ratio of the ultra-high molecular weight polyethylene fibers to the hard fibers is 100: (2-8). According to the preparation method, the tensile viscosity of the spinning solution in the preparation process is improved by controlling the content of the hard fibers, so that the mechanical property of the finished fiber is further improved, the obtained finished fiber has higher strength, the elongation at break is high, the number of broken ends is low, and the cutting resistance of the fiber reaches the European standard 5 (equivalent to American standard 3). As another example, patent CN106555245A discloses a cut-resistant ultra-high molecular weight polyethylene fiber, including ultra-high molecular weight polyethylene fiber; hard fibers and solvent oil dispersed in the ultra-high molecular weight polyethylene fibers; the mass ratio of the ultrahigh molecular weight polyethylene fibers to the hard fibers to the solvent oil is 100: (3-6): (0.3-2). According to the method, the hard fibers are better compatible with the ultra-high molecular weight polyethylene through the infiltration effect of the solvent oil on the hard fibers, and meanwhile, the addition of the solvent oil is beneficial to the uniform distribution of the hard fibers in the ultra-high molecular weight polyethylene, so that the finished fibers have higher elongation at break, and the cutting resistance of the finished fibers can reach the European standard 5 (equivalent to American standard 3).
However, the special functional fibers have the problems of high cost, relatively complex fiber processing technology and weaving technology, and hard hand feeling and poor comfort of finished gloves and other products prepared by the fibers.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the graphene-hard material base composite latex with high wear resistance and cutting resistance and the application thereof.
The purpose of the invention is realized by the following technical scheme:
the invention provides high-wear-resistance and cutting-resistance graphene-hard material base composite latex which comprises the following components in percentage by mass:
Figure BDA0002437353610000021
preferably, the hard material comprises one or more of silicon nitride, silicon carbide, glass powder, glass fiber powder, carbon fiber powder, basalt fiber powder and ceramic powder, and the particle size of the hard material is 1-20 μm.
Preferably, the hard material is a combination of silicon nitride, zirconia, carbon fiber powder.
More preferably, the mass ratio of the silicon nitride to the zirconium oxide to the carbon fiber powder is 0.1-5: 0.2-1: 1.
Preferably, in the graphene modified composite hard material, the adopted graphene is modified graphene; the modifying agent adopted by the modified graphene comprises one or more of a coupling agent, a surfactant and alkyl halide.
Preferably, the preparation method of the graphene modified composite hard material comprises the following steps:
s1, mixing graphene with a modifier, and preparing modified graphene through an ion reaction;
s2, reacting the hard material with the modified graphene for 0.5-2.5 hours under stirring or ultrasonic treatment to obtain a graphene modified composite hard material;
in the step S1, the addition amount of the modifier is 12-38% of the mass of the graphene;
in step S2, the mass ratio of the hard material to the modified graphene is 1-7: 0.1-2.
According to the invention, the graphene modified composite hard material can improve the performance of the hard material, the modified hard material is added into the latex, the latex has more excellent cutting resistance, wear resistance and strength, and the modified hard material can be more uniformly dispersed in the latex.
Preferably, the dispersant is selected from one or more of sodium methylene dinaphthalene sulfonate, polyacrylamide and sodium dibutyl naphthalenesulfonate;
the stabilizer is selected from one or more of zinc-calcium stabilizer, mannitol and sodium dodecyl sulfate;
the accelerant is one or more selected from ethylene thiourea, zinc dibutyl dithiocarbamate and dibenzothiazyl disulfide.
Preferably, the latex is selected from one or more of butyronitrile, PE, PU, PVC, natural latex, styrene-butadiene latex and chloroprene latex.
The invention also provides a preparation method of the high-wear-resistance and cutting-resistance hard material-based composite latex, which comprises the following steps:
A. adding dispersant, stabilizer and accelerator into partial latex (natural latex needs to be heated to 45-65 deg.C, and other latexes are at normal temperature), and stirring for 1-5 hr;
B. adding the graphene modified composite hard material into the rest latex, and mechanically stirring for 1-5h to graft the graphene modified composite hard material onto latex particles;
C. and C, mixing the latexes treated in the step A and the step B, and stirring for 3-8 hours at the temperature of 10-60 ℃ to obtain the composite latex.
The invention also provides a high-strength, cutting-resistant and wear-resistant fabric product or yarn prepared from the graphene-hard material-based composite latex with high wear resistance and cutting resistance, wherein the fabric product comprises cloth, gloves and the like made of cotton yarn, nylon, terylene, polypropylene or blended yarn; the yarn is selected from cotton yarn, nylon, terylene, polypropylene or blended yarn.
The invention also provides a preparation method of the high-strength, cutting-resistant and wear-resistant fabric product or yarn, which comprises the following steps: and (3) dipping the fabric product or the yarn in the composite latex or coating the composite latex, and drying to obtain the fabric product or the yarn with high strength, cutting resistance and wear resistance.
The invention also provides a preparation method of the high-strength, cutting-resistant and wear-resistant gloves, which comprises the following steps:
A. soaking the prepared glove blank with a coagulant, and drying at 30-50 deg.C for 2-5 min;
B. dipping the glove blank treated by the A into the composite latex, and then drying for 15-30min at the temperature of 50-80 ℃;
C. cleaning the glove blank treated in the step B with redundant composite rubber materials, vulcanizing,
D. and D, repeating the processes of the step B and the step C, and then demoulding to obtain the gloves with the functions of high strength, cutting resistance and wear resistance.
Preferably, the glove blank is made of cotton yarn, nylon, terylene, polypropylene or blended yarn.
Compared with the prior art, the invention has the following beneficial effects:
the composite latex prepared by the invention can use common cotton yarn, nylon, terylene, polypropylene fiber or blended yarn and the like as a bottom lining, and the composite material of the textile and the latex has high-grade wear resistance and cutting resistance through a dipping or coating process. Compared with gloves prepared from special functional fibers, the gloves have the advantages of softer hand feeling, better comfort, better cutting resistance, better wear resistance and better tear resistance. Can be widely applied to the special fields of individual safety protection, sports protection, engineering safety, field survival and the like with higher wear resistance and cutting resistance requirements.
The gloves prepared by dipping the composite latex are tested by EN388 standard, the cutting resistance of the gloves is up to 5 grade, the wear resistance of the gloves is up to 4 grade, the tearing resistance of the gloves is up to 4 grade, and the puncture resistance of the gloves is up to 4 grade.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Examples 1 to 10
The embodiment 1 to 10 provides a preparation method of graphene-hard material-based composite latex with high wear resistance and high cutting resistance, which comprises the following steps:
1. mixing graphene with a silane coupling agent (the addition amount is 28% of the mass of the graphene) to prepare modified graphene;
2. reacting a hard material (the hard material adopted in each example is shown in table 1, the particle size of each hard material is 10-20 μm) with the modified graphene for 2 hours under stirring or ultrasonic waves to obtain a graphene modified composite hard material;
3. adding a dispersant of sodium methylene dinaphthalene sulfonate, a stabilizer of mannitol and an accelerator of ethylene thiourea into part of nitrile latex (at normal temperature) in turn according to a certain proportion, and fully stirring for 1-5 h;
4. adding the graphene modified composite hard material into the rest latex, and mechanically stirring for 1-5h to graft the graphene modified composite hard material onto latex particles;
it should be noted that, in the step 3 and the step 4, the latex is distributed only by being capable of being fully and uniformly stirred with other components;
5. and (4) mixing the latexes treated in the steps (3) and (4), and stirring for 5 hours at the temperature of 40 ℃ to obtain the composite latex.
In the preparation method, the weight parts of the components are shown in table 1.
TABLE 1
Figure BDA0002437353610000041
Figure BDA0002437353610000051
Example 11
The embodiment provides a preparation method of graphene-hard material-based composite latex with high wear resistance and high cutting resistance, which comprises the following steps:
1. mixing graphene with a surfactant (specifically, quaternary ammonium salt, the addition amount is 32% of that of the graphene) to prepare modified graphene;
2. reacting a hard material (the hard material adopted in each example is shown in table 2, the particle size of each hard material is 10-20 μm) with the modified graphene for 0.5 hour under stirring or ultrasound to obtain a graphene modified composite hard material;
3. adding a dispersant polyacrylamide, a sodium dodecyl sulfate as a fixing agent and an accelerator dibenzothiazyl disulfide into part of PE (normal temperature) in sequence according to a proportion, and fully stirring for 1-5 h;
4. adding the graphene modified composite hard material into the rest PE, and mechanically stirring for 1-5h to graft the graphene modified composite hard material onto the PE particles;
5. and (4) mixing the latexes treated in the steps (3) and (4), and stirring for 8 hours at the temperature of 10 ℃ to obtain the composite latex.
In the preparation method, the weight parts of the components are shown in table 2.
Example 12
The embodiment provides a preparation method of graphene-hard material-based composite latex with high wear resistance and high cutting resistance, which comprises the following steps:
1. mixing graphene with a silane coupling agent (the addition amount is 31% of the mass of the graphene) to prepare modified graphene;
2. reacting a hard material (the hard material adopted in each example is shown in table 2, the particle size of each hard material is 10-20 μm) with the modified graphene for 2.5 hours under stirring or ultrasound to obtain a graphene modified composite hard material;
3. adding a dispersant polyacrylamide, a stabilizer sodium dodecyl sulfate and an accelerator dibenzothiazyl disulfide into partial natural latex (the temperature of the natural latex needs to be raised to 45-65 ℃) in sequence according to a proportion, and fully stirring for 1-5 hours;
4. adding the graphene modified composite hard material into the rest PE, and mechanically stirring for 1-5h to graft the graphene modified composite hard material onto natural latex particles;
5. and (4) mixing the latexes treated in the steps (3) and (4), and stirring for 3 hours at the temperature of 60 ℃ to obtain the composite latex.
In the preparation method, the weight parts of the components are shown in table 2.
Example 13
The embodiment provides a preparation method of graphene-hard material-based composite latex with high wear resistance and high cutting resistance, which comprises the following steps:
1. mixing graphene with alkyl halide (specifically bromododecane, the addition amount is 23% of the mass of the graphene) to prepare modified graphene;
2. reacting a hard material (the hard material adopted in each example is shown in table 2, the particle size of each hard material is 10-20 μm) with the modified graphene for 2 hours under stirring or ultrasonic waves to obtain a graphene modified composite hard material;
3. adding a dispersant polyacrylamide, a stabilizer sodium dodecyl sulfate and an accelerator dibenzothiazyl disulfide into part of nitrile latex (at normal temperature) in turn according to a proportion, and fully stirring for 1-5 h;
4. adding the graphene modified composite hard material into the rest latex, and mechanically stirring for 1-5h to graft the graphene modified composite hard material onto latex particles;
5. and (4) mixing the latexes treated in the steps (3) and (4), and stirring for 4 hours at the temperature of 40 ℃ to obtain the composite latex.
In the preparation method, the weight parts of the components are shown in table 2.
TABLE 2
Figure BDA0002437353610000061
Figure BDA0002437353610000071
Comparative example 1
This comparative example differs from example 8 only in that: in the comparative example, the basalt fiber powder is replaced by the montmorillonite.
Comparative example 2
This comparative example differs from example 8 only in that: in the comparative example, the basalt fiber powder and the silicon oxide are replaced by the montmorillonite.
Comparative example 3
This comparative example differs from example 5 only in that: in this comparative example, the modification treatment of step 1 was not performed, and the unmodified graphene was directly subjected to the treatment of step 2.
Comparative example 4
This comparative example differs from example 5 only in that: in this comparative example, the hard material was directly subjected to the treatment of step 3 without adding modified graphene.
Comparative example 5
This comparative example differs from example 9 only in that: in this comparative example, the carbon fiber powder was 4 parts by weight.
Comparative example 6
This comparative example differs from example 10 only in that: in this comparative example, the modified graphene prepared in step 1 was added to step 4 for processing without adding a hard material.
And (3) performance testing:
a method of making a glove, comprising the steps of:
A. firstly, soaking a prepared glove blank (prepared from cotton yarn) in a coagulant (the coagulant is a mixture of calcium nitrate and ethanol in a weight ratio of 1: 100), and then drying for 1-3h at normal temperature;
B. respectively dipping the glove blanks treated in the step A into the composite latex prepared in each embodiment and comparative example, and then drying for 1-4h at the temperature of 60-120 ℃;
C. and (5) demolding to obtain the glove.
The gloves prepared by dipping the composite latexes prepared in the examples and comparative examples were subjected to a performance test using the method in the EN388 standard (the specific measurement method used in the examples and comparative examples is exactly the same), and the test results are shown in Table 2.
TABLE 3
Figure BDA0002437353610000081
The same procedure was used for nylon glove blanks prepared using the glove preparation method described above, wherein the compounded latex used was prepared as in example 2, and the resulting gloves were tested using the method in the EN388 standard, and the results were: the cutting resistance is up to 4 grade, the wear resistance is up to 4 grade, the tear resistance is up to 4 grade, and the puncture resistance is up to 4 grade.
The glove blanks made of polyester were subjected to the same treatment using the glove preparation method described above, wherein the composite latex used was prepared as in example 2, and the gloves obtained were tested using the method in the EN388 standard, with the following results: the cutting resistance is up to 4 grade, the wear resistance is up to 4 grade, the tear resistance is up to 4 grade, and the puncture resistance is up to 4 grade.
The invention can also use the composite latex prepared in the embodiment to prepare other high-strength, cutting-resistant and wear-resistant fabric products or yarns (such as fabric products or yarns, the fabric products include cloth made of cotton yarn, nylon, terylene, polypropylene or blended yarn, and also such as cotton yarn, nylon, terylene, polypropylene or blended yarn), and the specific method is as follows: the fabric product or the yarn is dipped in the composite latex prepared in the embodiment or coated with the composite latex prepared in the embodiment, and then dried at the temperature of 50-120 ℃. The obtained fabric product or yarn can also realize the effect of obviously improving the cutting resistance, the wear resistance, the tear resistance and the puncture resistance compared with the fabric product or yarn before dipping.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. The high-wear-resistance and high-cutting-resistance graphene-hard material base composite latex is characterized by comprising the following components in parts by weight:
Figure FDA0002437353600000011
2. the graphene-hard material based composite latex with high wear resistance and high cutting resistance according to claim 1, wherein the hard material comprises one or more of silicon nitride, aluminum oxide, zirconium oxide, carbon fiber powder, boron nitride, titanium diboride and ceramic powder.
3. The high wear resistant, high cut resistant graphene-hard material based composite latex according to claim 2, wherein the hard material is a combination of silicon nitride, zirconium oxide, carbon fiber powder.
4. The high-wear-resistance and high-cutting-resistance graphene-hard material-based composite latex according to claim 1 or 2, wherein in the graphene-modified composite hard material, the adopted graphene is modified graphene; the modifying agent adopted by the modified graphene comprises one or more of a coupling agent, a surfactant and alkyl halide.
5. The high wear-resistant high cutting-resistant graphene-hard material-based composite latex according to claim 1, wherein the preparation method of the graphene-modified composite hard material comprises the following steps:
s1, mixing graphene with a modifier, and preparing modified graphene through an ion reaction;
s2, reacting the hard material with the modified graphene for 0.5-2.5 hours under stirring or ultrasonic treatment to obtain a graphene modified composite hard material;
in the step S1, the addition amount of the modifier is 12-38% of the mass of the graphene;
in step S2, the mass ratio of the hard material to the modified graphene is 1-7: 0.1-2.
6. The graphene-hard material based composite latex with high wear resistance and high cutting resistance according to claim 1, wherein the dispersant is one or more selected from sodium methylene dinaphthalenesulfonate, polyacrylamide and sodium dibutylnaphthalenesulfonate;
the stabilizer is selected from one or more of zinc-calcium stabilizer, mannitol and sodium dodecyl sulfate;
the accelerant is one or more selected from ethylene thiourea, zinc dibutyl dithiocarbamate and dibenzothiazyl disulfide.
7. The graphene-hard material based composite latex with high wear resistance and high cutting resistance according to claim 1, wherein the latex is selected from one or more of butyronitrile, PE, PU, PVC, natural latex, styrene-butadiene latex and chloroprene latex.
8. The preparation method of the high wear-resistant and cut-resistant graphene-hard material-based composite latex according to claim 1, comprising the following steps:
A. adding the dispersant, the stabilizer and the accelerator into partial latex in proportion, and fully stirring for 1-5 h;
B. adding the graphene modified composite hard material into the rest latex, and mechanically stirring for 1-5h to graft the graphene modified composite hard material onto latex particles;
C. and C, mixing the latexes treated in the step A and the step B, and stirring for 3-8 hours at the temperature of 10-60 ℃ to obtain the composite latex.
9. A high strength, cut resistant, abrasion resistant fabric product or yarn made from the high abrasion resistant, cut resistant graphene-hard material based composite latex of claim 1.
10. A method of making a high strength, cut and abrasion resistant functional fabric product or yarn according to claim 9, comprising the steps of:
dipping the fabric product or yarn in the composite latex of claim 1 or coating the composite latex of claim 1, and drying to obtain the fabric product or yarn with high strength, cutting resistance and wear resistance.
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