CN113861564B - Laser-markable organic/inorganic polypropylene composite material and preparation method and application thereof - Google Patents
Laser-markable organic/inorganic polypropylene composite material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses an organic-inorganic polypropylene composite material capable of being marked by laser, a preparation method and application thereof, and belongs to the fields of high polymer polypropylene composite materials and laser marking. BNSs are prepared by adopting a solvent-assisted ultrasonic stripping method, then the BNSs are subjected to heat treatment in the air at 850 ℃ for 6 hours, and the BNSs are subjected to thermal oxidation to obtain BNSs-OH. BNSs-OH is added into polypropylene, and a melt blending method is adopted to prepare the polypropylene composite material. And selecting a proper formula through laser marking comparison and various test comparison to prepare the polypropylene marking material with excellent laser marking performance. The surface laser radiation treatment is carried out on the polypropylene composite material by utilizing the laser marking machine to generate black mark patterns, so that the cost is effectively reduced, and continuous, environment-friendly, efficient and large-scale marking of the polypropylene composite material is realized.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an organic/inorganic polypropylene composite material capable of being marked by laser, and a preparation method and application thereof.
Background
The polypropylene has high crystallinity, regular structure, excellent mechanical performance and heat resistance, and the product can be sterilized at 100 deg.c or higher and is not deformed at 150 deg.c. The polypropylene has good chemical stability, can be corroded by concentrated sulfuric acid and concentrated nitric acid, is relatively stable to other various chemical reagents, is suitable for manufacturing various chemical pipelines and accessories, and has good anti-corrosion effect. The polypropylene is excellent in high-frequency insulating property, and since it hardly absorbs water, the insulating property is not affected by humidity. It has a high dielectric constant and can be used to make electrically insulating articles that are heated as the temperature increases. It also has high breakdown voltage, is suitable for being used as electric fittings and the like, the voltage resistance and the arc resistance are good.
Polypropylene materials require marking of their surfaces to provide information on product date, expiration date, serial number, and corporate logo, for some specific applications. However, the laser marking effect is not ideal, and polypropylene itself does not absorb 1064nm wavelength, so that the polypropylene cannot be carbonized under the irradiation of a laser marking machine. Therefore, the method has important research significance for realizing convenient, quick and efficient marking and identification of the polypropylene material and the polypropylene product.
The laser marking technology is an emerging and rapidly developed laser technology, and selectively scans and irradiates the surface area of a material according to patterning or literal instructions given by a computer program, wherein the irradiated area on the surface of the material can absorb laser energy to be heated to generate thermo-chemical change, so that black marks are formed. The computer software is used to design various patterns and control pulse laser, so that various mark patterns such as characters, figures, symbols, bar codes, images and the like can be generated. The laser marking does not need ink, does not need a high-intensity energy drying process of the ink marking technology, does not need a solvent, and is more environment-friendly. The surface marking method is widely applied to surface marking of various materials such as plastic polymers, metals, ceramics and the like due to the characteristics of quick marking, excellent durability, high contrast and environmental friendliness. In practice, laser marking has been widely used in the fields of electronic components, insulation, plastics, packaging, and the like. By varying the operating parameters of the laser beam, such as scan speed, current, spot size, line width, etc., the laser marking effect on the material surface, including surface roughness, contrast and sharpness of the mark, and chromatic aberration, etc., can be modulated.
The laser sensitive additive is generally inorganic oxide particles sensitive to laser, such as mica, bismuth oxide, titanium dioxide and the like, and the inorganic oxide particles are dispersed in plastic resin, so that the laser sensitive additive can effectively absorb laser energy, photo-chemical change occurs to the laser sensitive additive, and meanwhile, the absorbed energy enables polymer molecular chains around the particles to be pyrolyzed and carbonized to form black marks, so that the effect of laser marking is achieved, and the laser marking mechanism is a traditional laser marking mechanism. The traditional laser additives are inorganic oxide additives, which have poor compatibility with the polymer matrix, and some inorganic oxide additives can change the color of the polymer matrix and even reduce the mechanical properties of the polymer itself. For example, bismuth oxide additives are toxic and, due to their nature, have non-uniform particle dispersion during melt blending.
Disclosure of Invention
The invention provides an organic-inorganic polypropylene composite material and a preparation method thereof, which utilize good heat conduction performance and dielectric property of a functionalized boron nitride nano-sheet to be added into polypropylene to form a heat conduction path, and the functionalized boron nitride nano-sheet absorbs laser energy, performs photo-thermal conversion and transmits heat well in a polypropylene matrix. The polypropylene composite material with high strength, high hydrophobicity, high thermal conductivity and high dielectric property, which is obtained by the preparation method, can generate black marks with high contrast and definition on the surface through pulse laser irradiation, can realize rapid, efficient and nondestructive marking under the laser irradiation, and is suitable for application in the fields of commodity information marking, identification, surface modification and the like of the high-molecular polypropylene composite material.
The invention does not need to design a patterned die or substrate in advance, does not need to use special chemical reagents and etching technology, does not generate environmental pollution, introduces the functionalized boron nitride nanosheets into the existing common polypropylene material structure to prepare the organic-inorganic polypropylene composite material, and utilizes the emerging laser marking technology to rapidly and efficiently laser mark the polypropylene material so as to solve the problems existing in the existing polypropylene marking technology, thereby realizing simplified technology, controllable marking and identification.
The technical scheme of the invention is as follows:
the organic-inorganic polypropylene composite material capable of being marked by laser comprises the following components in parts by weight: 0.5-2 parts of functionalized boron nitride nano-sheet, 10 parts of compatilizer and 100 parts of polypropylene.
Wherein, the compatilizer is polypropylene grafted maleic anhydride (PP-g-MAH), and the grafting rate of the maleic anhydride is 1%.
The preparation method of the modified boron nitride nanosheets comprises the following steps: firstly, preparing boron nitride nano-sheets (BNSs) by adopting a solvent-assisted ultrasonic stripping method, specifically comprising the following steps: dispersing Boron Nitride (BN) particles in N, N-dimethylacetamide (DMAc), and performing ultrasonic stripping for 12 hours; the supernatant dispersion was then centrifuged at 3000r/min for 15min, filtered through a polytetrafluoroethylene membrane having a pore size of 0.1. Mu.m, and the product was subsequently dried at 100℃to give BNSs. And then carrying out heat treatment on BNSs for 6 hours at 850 ℃, carrying out thermal oxidation on the BNSs in high-temperature air, and grafting hydroxyl (-OH) on the surface of the BNSs to obtain the BNSs-OH.
The purity of the Boron Nitride (BN) is 98wt%, the grain size is 0.1-0.4 mu m, and the crystal form is hexagonal.
The invention also provides a preparation method of the laser-markable organic-inorganic polypropylene composite material, which comprises the following steps: the polypropylene, the compatilizer and the functionalized boron nitride nano-sheet are firstly melted and blended, and then pressed and formed by a plate vulcanizing machine to obtain the PP/BNSs-OH composite material.
The melt blending is carried out for 3 minutes by a torque rheometer at 190 ℃; the functionalized boron nitride nano-sheets are placed in a blast drying oven for drying at 70 ℃ for 30min before melt blending.
The organic-inorganic polypropylene composite material capable of being marked by laser can be used for marking the patterns such as characters, figures, images, symbols and the like such as production date, effective period, two-dimensional codes and the like on the surface by using a semiconductor laser marking machine, thereby realizing the application of identifying, marking and modifying polypropylene products.
The specific application method comprises the following steps: carrying out surface laser marking treatment on the organic/inorganic polypropylene composite material by using a semiconductor pulse laser (KDD-50, wavelength 1064 nm), wherein the maximum output power of a laser marking machine is 50W, and the pulse laser wavelength is as follows: and 1064nm, the surface of the polypropylene composite material presents black laser characters and pattern marks, and the depth can reach 200-400 mu m.
The principle of the invention is as follows:
(1) And (3) melting and blending the functionalized boron nitride nano-sheet with polypropylene after adding a compatilizer to obtain the organic-inorganic polypropylene composite material. BN is a heat-conducting nano sheet, has good heat-conducting property, and can form a heat-conducting passage by modifying and adding PP; BNSs-OH absorbs laser energy, converts light and heat, and transmits the matrix PP well, so that the good laser carbonization marking performance is achieved.
(2) The BNSs grafted with hydroxyl (-OH) through high-temperature thermal oxidation has good compatibility with a compatilizer (PP-g-MAH), so that the agglomeration phenomenon of boron nitride in the composite material is reduced, the dispersibility of the boron nitride in polypropylene is improved, the compatibility and the binding force of BN nano-sheets and the polypropylene are improved, and the mechanical strength of the composite material is improved.
(3) And adding a compatilizer into the functionalized boron nitride nano-sheet, and then carrying out melt blending with polypropylene to obtain the organic-inorganic polypropylene composite material. The polypropylene surface is subjected to laser marking under the effect of controllable pulse laser irradiation of the laser marking machine, the laser marked patterns can be designed through software communicated with the laser marking machine in a computer, the patterns comprise characters, symbols, figures, images and the like, the selection is various, the size is adjustable, and the laser working parameters can also be adjusted. The modified boron nitride nano-sheet embedded in the polypropylene material absorbs laser energy entering the surface of the polypropylene, and generates thermo-chemical change to generate black marks. In this process, the black laser mark may have a depth of 200-400 μm. By controlling the content of the modified boron nitride nano-sheet and the laser power, black mark characters and patterns with different contrast and definition can be generated on the surface of the organic-inorganic polypropylene material without affecting the structure of the high-density polypropylene.
Compared with other traditional polypropylene marking methods, the method has the following advantages:
1. the polypropylene composite material provided by the invention contains a compatilizer (PP-g-MAH) and a laser-sensitive functionalized boron nitride nano-sheet, and the prepared organic-inorganic polypropylene composite material can be subjected to laser marking, and has good mechanical properties, stable chemical properties and the like due to the reinforcing effect of the inorganic material.
2. The preparation method adopted by the invention comprises the steps of dispersing BN particles in N, N-dimethylacetamide (DMAc), and carrying out ultrasonic stripping for 12 hours; centrifuging at 3000r/min for 15min, filtering the upper dispersion with polytetrafluoroethylene membrane with pore diameter of 0.1 μm, drying at 100deg.C to obtain BNSs, heat treating BNSs at 850 deg.C for 6 hr, and thermally oxidizing BNSs at high temperature to obtain hydroxyl functional to obtain BNSs-OH. And (3) melting and blending BNSs-OH and PP to obtain the polypropylene composite material embedded with the laser sensitive particles, thereby forming the organic-inorganic polypropylene composite material.
3. The marking method adopted by the invention does not need to produce and manufacture a patterned die and a silicon wafer substrate in advance and does not need chemical etching, thereby effectively reducing cost, reducing consumption of chemical reagents and reducing environmental pollution. The new developed laser marking machine is utilized for marking, and the industrialized, continuous and high-efficiency large-scale marking of the polypropylene material can be realized. By changing the content of the functionalized boron nitride nano-sheet and the laser power in the marking process, characters and patterns with different contrast and definition can be obtained on the surface of polypropylene, and the marking method has more advantages than the marking obtained by the traditional cutting and etching technology.
Drawings
FIG. 1 shows the marking effect of pure PP and functionalized boron nitride composite polypropylene materials with different contents.
FIG. 2 shows a color difference analysis chart of pure PP and functionalized boron nitride composite polypropylene materials with different contents after marking.
FIG. 3 shows a scanning electron microscope after marking with different content of functionalized boron nitride composite polypropylene materials.
FIG. 4 is a graph showing the comparison of the label of pure PP, PP/BN, BNSs-OH/PP-g-MAH/PP.
FIG. 5 is a graph of water contact angle at the marking position, wherein a, b, c, d, e are pure PP, BNSs-OH/PP-g-MAH/PP (0.5/10/100), BNSs-OH/PP-g-MAH/PP (1/10/100), BNSs-OH/PP-g-MAH/PP (1.5/10/100), BNSs-OH/PP-g-MAH/PP (2/10/100), respectively.
Detailed Description
The invention is further described in detail below in connection with the examples:
example 1:
(1) The raw materials are respectively weighed: BN, PP-g-MAH, PP;
(2) The preparation method of the functionalized boron nitride nanosheets comprises the following steps: 10g BN particles are dispersed in 100mL of N, N-dimethylacetamide (DMAc) and ultrasonically peeled for 12h; centrifuging at 3000r/min for 15min, filtering the upper dispersion with polytetrafluoroethylene membrane with pore diameter of 0.1 μm, drying the BNSs precipitate at 100deg.C to obtain BNSs, heat treating 10g BNSs in 850 deg.C air for 6 hr, and thermally oxidizing BNSs at high temperature to obtain hydroxyl functional group 11.8g BNSs-OH.
(3) And (3) melting and blending polypropylene, a compatilizer and the functionalized boron nitride nano-sheet, and performing compression molding to obtain the PP/BNSs-OH composite material capable of being marked by laser.
The PP/BNSs-OH composite material prepared by the method can be used for representing the morphology, the structure and the performance change before and after laser marking, the laser marking mechanism, the structure and the performance change and the laser marking mechanism of the organic/inorganic polypropylene composite material by means of laser marking performance test, scanning electron microscope, thermogravimetric analysis, XRD (X-ray diffraction) contrast analysis, contact angle contrast analysis, mechanical property test and the like, and the specific test is as follows.
Laser marking of pure PP and composite polypropylene materials with different content of functionalized boron nitride in the figure 1, wherein a, b, c and d and e are respectively pure PP, BNSs-OH/PP-g-MAH/PP
(0.5/10/100), BNSs-OH/PP-g-MAH/PP (1/10/100), BNSs-OH/PP-g-MAH/PP (1.5/10/100), BNSs-OH/PP-g-MAH/PP (2/10/100) with a linear velocity of 200mm/s, laser marking graph at 60% output power. After the laser marking is seen from the graph a, only a few sporadic black spots are arranged on the PP plate, which indicates that the pure PP has no obvious laser marking effect, shallow marking, unclear square blocks and less photo-thermal decomposition and carbonization. When BNSs-OH/PP-g-MAH/PP ratio is 0.5/10/100, the composite mark is still shallow, the marked square is complete, but the contrast is improved. When the BNSs-OH/PP-g-MAH/PP ratio is 1/10/100, the composite mark is still lighter, but the contrast is already high. When BNSs-OH/PP-g-MAH/PP ratio is 1.5/10/100, the color of the laser mark becomes dark and can be clearly seen by naked eyes. When the ratio of BNSs-OH/PP-g-MAH/PP is 2/10/100, the color of the laser mark of the composite material becomes light, and the surface of the material is rougher, because the BNSs-OH content is too high to absorb energy, larger discontinuous cavities are formed on the surface of the material. Therefore, the composite labeling effect is best when BNSs-OH/PP-g-MAH/PP ratio is 1.5/10/100.
Color difference analysis of marked pure PP and functionalized boron nitride composite polypropylene materials with different contents
The error is larger from naked eyes, so that the color difference analysis is carried out on the composite material by a light-splitting color difference meter. FIG. 2 shows the color differences of pure PP, BNSs-OH/PP-g-MAH/PP (0.5/10/100), BNSs-OH/PP-g-MAH/PP (1/10/100), BNSs-OH/PP-g-MAH/PP (1.5/10/100), BNSs-OH/PP-g-MAH/PP (2/10/100), respectively. From the curves in the figure, it can be derived: along with the increase of laser power, the color difference values of the pure PP and the PP composite material are improved. The higher the laser power, the better the laser marking effect. Compared with pure PP, the color difference value of the composite material is obviously improved after BNSs-OH is added into the PP, which proves that the BNSs-OH has better laser absorption performance. When the laser power is 30%, the maximum color difference value of BNSs-OH/PP-g-MAH/PP (1.5/10/100) is seen after comparing the five curves, which shows that the laser marking effect of BNSs-OH/PP-g-MAH/PP (1.5/10/100) is the best.
Scanning electron microscope analysis of the marked functionalized boron nitride composite polypropylene materials with different contents in the figure 3 shows that a, b, c and d are respectively BNSs-OH/PP-g-MAH/PP (0.5/10/100), BNSs-OH/PP-g-MAH/PP (1/10/100), BNSs-OH/PP-g-MAH/PP (1.5/10/100) and BNSs-OH/PP-g-MAH/PP (2/10/100). The graph a and the graph b show that the marked surface of the graph a and the graph b has quite uniform color, smooth surface, no obvious bubbles and holes on the surface, quite uniform and regular distribution of carbonization points, good laser marking effect, good dispersion of BNSs-OH in PP and unobvious agglomeration, and the dispersibility of the formula in the design is better. The surface of the graph c is provided with uniform and dense holes, the carbonization effect is good, the holes of the graph d are unevenly distributed, the aperture is larger, the surface is rougher, and the laser marking effect is not ideal.
In FIG. 5, a, b, c, d, e are the water contact angle diagrams of the marking positions of pure PP, BNSs-OH/PP-g-MAH/PP (0.5/10/100), BNSs-OH/PP-g-MAH/PP (1/10/100), BNSs-OH/PP-g-MAH/PP (1.5/10/100), BNSs-OH/PP-g-MAH/PP (2/10/100), the angles in the diagrams are 70 degrees, 72 degrees, 78 degrees, 89 degrees and 93 degrees respectively, and the contact angle increases with the increase of the functionalized boron nitride content. As the carbonization structure is formed on the surface of the PP by laser marking, the roughness of the surface of the composite material is increased, and the hydrophobicity of the surface of the material is increased. Therefore, the marking performance of the composite material is improved along with the increase of the adding amount of the functionalized boron nitride.
Comparative example 1
And (3) melting and blending polypropylene, a compatilizer and a boron nitride nano sheet, and performing compression molding to obtain the PP/BNSs-OH composite material capable of being marked by laser.
In fig. 4, a, b and c are graphs of laser marking effect of pure PP, BN/PP (1.5/100), BNNSs-OH/PP-g-MAH/PP (1.5/10/100) at the same laser power, respectively, it is not difficult to see that pure PP does not respond to laser by comparing the effects of the three images, unmodified BN is added into PP to form black marks by laser marking, but the contrast of the pattern and uniformity of the pattern are not good as those of BNNSs-OH/PP-g-MAH/PP composites, so the addition of modified boron nitride makes PP polymers have excellent marking effect.
While the invention has been described with respect to several embodiments thereof, it should be understood by those skilled in the art that many variations and modifications may be made without departing from the scope of the invention as defined in the appended claims.
Claims (6)
1. A laser markable organic-inorganic polypropylene composite for identification, marking and modification of polypropylene, characterized by: the polypropylene composite material comprises the following components in parts by mass: 0.5-2 parts of functionalized boron nitride nano-sheet, 10 parts of compatilizer and 100 parts of polypropylene;
the functionalized boron nitride nano-sheet is obtained by performing heat treatment on boron nitride nano-sheet (BNSs) obtained by ultrasonic stripping for 6 hours in an environment of 850 ℃ to perform functionalization, so as to obtain BNSs-OH;
the compatilizer is polypropylene grafted maleic anhydride, and the grafting rate of the maleic anhydride is 1%.
2. The laser markable organic-inorganic polypropylene composite material according to claim 1, wherein: the boron nitride nano-sheet is prepared by adopting a solvent-assisted ultrasonic stripping method, and specifically comprises the following steps: dispersing Boron Nitride (BN) particles in N, N-dimethylacetamide (DMAc), and performing ultrasonic stripping for 12 hours; then, the supernatant was centrifuged at 3000/r/min for 15min, and the dispersion was filtered through a polytetrafluoroethylene membrane having a pore size of 0.1. Mu.m, and then the product was dried at 100℃to obtain BNSs.
3. The laser markable organic-inorganic polypropylene composite material according to claim 2, wherein: the purity of the Boron Nitride (BN) is 98wt%, the grain size is 0.1-0.4 mu m, and the crystal form is hexagonal.
4. A method of preparing a laser markable organic-inorganic polypropylene composite material according to claim 1 wherein: the preparation method comprises the following steps: the polypropylene, the compatilizer and the functionalized boron nitride nano-sheet are firstly melted and blended, and then pressed and formed by a plate vulcanizing machine to obtain the PP/BNSs-OH composite material.
5. The method for preparing the laser-markable organic-inorganic polypropylene composite material according to claim 4, wherein: the melt blending is carried out by a torque rheometer at 190 ℃ for 3 minutes; and the functionalized boron nitride nano-sheets are placed in a blast drying oven for drying at 70 ℃ for 30min before being melted and blended.
6. The laser markable organic-inorganic polypropylene composite material according to claim 1, wherein the specific application method is: the surface laser marking treatment is directly carried out on the organic-inorganic polypropylene composite material by using a laser marking machine, the maximum output power of the laser marking machine is 50W, and the pulse laser wavelength is as follows: 1064 nm.
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