WO2024103812A1 - Method and tool for evaluating and testing performance of inner layer adhesive for aluminum-plastic film - Google Patents

Method and tool for evaluating and testing performance of inner layer adhesive for aluminum-plastic film Download PDF

Info

Publication number
WO2024103812A1
WO2024103812A1 PCT/CN2023/107183 CN2023107183W WO2024103812A1 WO 2024103812 A1 WO2024103812 A1 WO 2024103812A1 CN 2023107183 W CN2023107183 W CN 2023107183W WO 2024103812 A1 WO2024103812 A1 WO 2024103812A1
Authority
WO
WIPO (PCT)
Prior art keywords
inner layer
aluminum
window
polyolefin
sample
Prior art date
Application number
PCT/CN2023/107183
Other languages
French (fr)
Chinese (zh)
Inventor
梁卓
刘德龙
黄晓华
Original Assignee
广东广麟材耀新能源材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东广麟材耀新能源材料有限公司 filed Critical 广东广麟材耀新能源材料有限公司
Publication of WO2024103812A1 publication Critical patent/WO2024103812A1/en

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
    • G01N2021/3572—Preparation of samples, e.g. salt matrices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of lithium battery soft packs, and in particular to an evaluation and testing method for the performance of an inner layer adhesive of an aluminum-plastic film and a tool thereof.
  • inner layer glues for aluminum-plastic films on the market.
  • the commonly used method on the market is mainly the direct method, that is, using glue to compare the peeling force generated by the glue on the standard sample, and verifying and evaluating it by directly producing aluminum-plastic films.
  • the advantage of the direct method for testing the inner layer glue of aluminum-plastic films is that it is intuitive and clear, and can directly feedback whether the inner layer glue is suitable for aluminum-plastic film manufacturing through peeling force, electrolyte resistance, heat sealing performance, etc.
  • the inner layer glue of aluminum-plastic film will be affected by parameters such as the proportion of curing agent used, curing conditions, and coating concentration, which will affect the specific performance of the inner layer glue.
  • parameters such as the proportion of curing agent used, curing conditions, and coating concentration, which will affect the specific performance of the inner layer glue.
  • the performance of the inner layer glue can only be analyzed under certain specific parameters.
  • using the direct method to test the inner layer glue of aluminum-plastic film requires the consumption of aluminum and other consumables, and the experimental cost is relatively high. The most important point is that the direct method is used to analyze the inner layer glue, and the analysis results are the difference in performance of the inner layer AB glue after proportioning. The main agent itself is not actually analyzed, and it is biased to directly equate the direct method test results to the performance of the inner layer glue body.
  • the inner layer of aluminum-plastic film its main component is acid-modified polyolefin material, the main component is polypropylene Olefin materials, but according to different usage conditions, there are different derivatives such as vinyl copolymerization and butene copolymerization.
  • the modified acid is generally maleic anhydride, occasionally acrylic acid, and other acids are almost not used. Therefore, if the acid group grafting rate of acid-modified polyolefin can be accurately determined, the active group ratio and polarity of the main agent of the inner layer glue can be effectively characterized, and then its performance potential level as an inner layer glue can be characterized.
  • the main method used in academia to characterize the acid-modified grafting rate is titration.
  • the advantage of this method is that for acid-modified products, it is quantitatively accurate and requires fewer instruments.
  • the inner layer glue of aluminum-plastic film due to the different polypropylene-based materials used in its main body, the titration method can only be used to test different batches of the same glue, and lacks the ability to compare different types of glue provided by different companies.
  • Another method, Fourier transform infrared spectroscopy is used for grafting rate analysis.
  • problems such as film thickness, test glue quantity, and uniformity control, it is usually only used in the direction of functional characterization, that is, qualitative rather than quantitative analysis.
  • the ATR method for this analysis due to weak reflection absorption, the working curve shifts greatly when the difference is small, and there will still be distortion problems.
  • the purpose of the present invention is to provide a testing method and tool for evaluating the performance of the inner layer glue of aluminum-plastic film, quantitatively analyze the grafting rate of the inner layer glue of aluminum-plastic film based on Fourier transform infrared spectroscopy, and evaluate the performance of the inner layer glue of aluminum-plastic film according to the grafting rate.
  • the present invention provides a method for evaluating the performance of the inner layer adhesive of an aluminum-plastic film, comprising the following steps:
  • Use a tool to combine one of the polyolefin window sheets with at least one of the modified acid window sheets, and perform Infrared analysis is performed to obtain the expected grafting rate by taking the percentage of the sum of the mass of the modified acid coated on all the modified acid windows after combination to the mass of the polyolefin coated on the polyolefin window, obtaining infrared spectra of standard samples under different expected grafting rates, and establishing an absorbance-grafting rate working curve according to the absorbance at a predetermined wavelength in the infrared spectrum;
  • the main agent of the inner layer adhesive of the aluminum-plastic film to be tested is placed in a predetermined amount of ethyl ester, and after the polymer in the inner layer adhesive of the aluminum-plastic film is fully precipitated, filtering, drying and extraction are performed in sequence to obtain the purified inner layer adhesive;
  • the purified inner layer rubber is prepared into a sample standard solution having the same concentration as the polyolefin standard solution, the sample standard solution is placed on a newly treated window, and after drying, Fourier infrared analysis is performed, the main polymer component of the sample to be tested and the absorbance at a predetermined wavelength are confirmed according to the infrared spectrum of the sample to be tested, and then the grafting rate of the sample to be tested is calculated according to the working curve;
  • the polyolefin window and the modified acid window are combined according to the grafting rate of the sample to be tested, and then Fourier infrared analysis is performed to obtain a verification infrared spectrum; the verification infrared spectrum is compared with the infrared spectrum of the sample to be tested for consistency. If the consistency meets the requirements, the performance of the inner layer glue of the aluminum-plastic film is evaluated according to the grafting rate of the sample to be tested; if the consistency does not meet the requirements, it indicates that the working curve is invalid or the raw material is incorrectly selected, and the raw material needs to be reselected to draw the working curve.
  • the polyolefin in step (1) includes one or more of polypropylene, polyethylene, and polyolefin elastomer; the concentration of the predetermined concentration of the polyolefin standard solution is 10g/L; the predetermined concentration of the polyolefin standard solution is 1-10g/L; the predetermined volume is 10-100 ⁇ L.
  • the modified acid in step (1) includes maleic anhydride and acrylic acid; and the predetermined concentration of the modified acid standard solution is 0.1-1 g/L.
  • the window coated with the polyolefin standard solution is placed in an oven at 60-90° C. and baked for 30-90 min until the solvent is completely volatilized.
  • the window in step (1) is a potassium bromide window; the window is round or square, the diameter of the round window is 10-18 mm, and the side length of the square window is 10-18 mm; the treatment process of the treated window is: placing the white and foggy window on a 1200-2000 mesh metallographic sandpaper with an isopropyl alcohol mixture Rub until the surface is even. If the window is not foggy, skip this step. Then wipe the treated window dry, add isopropyl alcohol mixture to the window surface again, and polish with velvet metallographic polishing cloth.
  • the isopropanol mixed solution is prepared by mixing isopropanol and distilled water in a predetermined volume ratio, and the volume proportion of isopropanol in the isopropanol mixed solution is 85-95%.
  • the absorbance at the predetermined wavelength in step (2) is the absorbance at 1780 cm -1 .
  • the mass of the predetermined amount of ethyl ester in step (3) is 2-5 times that of the main agent of the inner layer adhesive of the aluminum-plastic film to be tested.
  • step (3) when the consistency comparison is performed in step (3), if the peak intensities of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 2960 cm -1 and 1780 cm -1 are consistent, or the peak intensity deviation of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 1780 cm -1 does not exceed 10% and the ratio of the peak intensities of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 2960 cm - 1 and 1780 cm -1 is consistent, then the consistency meets the requirements; if the ratio of the peak intensities of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 2960 cm -1 and 1780 cm -1 is inconsistent, or the ratio of the peak intensities at 2960 cm -1 and 1780 cm -1 is consistent but the peak intensity deviation at 1780 cm -1 exceeds 10%, then the consistency does not meet the requirements.
  • the present invention also provides an evaluation and testing tool for the performance of the inner layer adhesive of aluminum-plastic film, which has a plurality of slots arranged in parallel along a direction perpendicular to the infrared light irradiation for placing polyolefin windows and modified acid windows in different combinations.
  • the present invention provides a method for evaluating the performance of the inner layer adhesive of the aluminum-plastic film based on Fourier infrared
  • the principle of spectral method quantitatively analyzes the grafting rate of the inner layer glue of the aluminum-plastic film, and evaluates the performance of the inner layer glue of the aluminum-plastic film according to the grafting rate. In this way, the performance of the inner layer glue of different aluminum-plastic films can be conveniently and quickly evaluated.
  • the present invention not only reduces the required experimental consumables, but also removes the previous limitation of only being able to analyze the performance of the inner layer glue under specific parameters, and improves the accuracy of mixed glue analysis.
  • the present invention provides an evaluation test method for the performance of the inner layer adhesive of aluminum-plastic film.
  • Fourier infrared analysis on polyolefin windows and modified acid windows in different combinations, infrared spectra under different grafting rates can be obtained, and an absorbance-grafting rate working curve can be established.
  • the main polymer components and the absorbance at a predetermined wavelength are confirmed after separation and purification of the inner layer adhesive of the aluminum-plastic film to be tested, and the grafting rate can be obtained by substituting into the working curve, thus realizing the quantitative analysis of the grafting rate based on Fourier infrared spectroscopy.
  • test method provided by the present invention removes the previous limitation that only different batches of the same adhesive can be tested, broadens the scope of application, and can make a horizontal comparison of different types of inner layer adhesives of aluminum-plastic film.
  • the evaluation and testing tool for the performance of the inner layer adhesive of the aluminum-plastic film provided by the present invention can perform Fourier transform infrared analysis on the polyolefin window and the modified acid window in a variety of different combinations by opening a plurality of slots, so as to facilitate the establishment of an absorbance-grafting rate working curve and to obtain the grafting rate of the inner layer adhesive of the aluminum-plastic film simply and quickly.
  • FIG. 1 is a schematic diagram of the structure of a test tool for evaluating the performance of the inner adhesive layer of an aluminum-plastic film provided by the present invention.
  • FIG. 2 is an infrared spectrum diagram of Example 1 at a grafting rate of 0%.
  • FIG. 3 is an infrared spectrum diagram of Example 1 at a grafting rate of 50%.
  • FIG. 4 is an infrared spectrum diagram of Example 1 at a grafting rate of 100%.
  • FIG. 5 is a working curve of absorbance at 1780 cm -1 - grafting rate established in Example 1.
  • FIG. 6 is an infrared spectrum of the GL inner layer window film in Example 1.
  • the present invention provides a method and tool for evaluating the performance of the inner layer adhesive of an aluminum-plastic film, which quantitatively analyzes the grafting rate of the inner layer adhesive of the aluminum-plastic film based on Fourier infrared spectroscopy, and evaluates the performance of the inner layer adhesive of the aluminum-plastic film according to the grafting rate, comprising the following steps:
  • a tool is used to combine one of the polyolefin window sheets with at least one of the modified acid window sheets, and Fourier infrared analysis is performed.
  • the percentage of the sum of the mass of the modified acid coated on all the modified acid window sheets after combination to the mass of the polyolefin coated on the polyolefin window sheet is taken as the expected grafting rate, and different expected
  • the infrared spectrum at the grafting rate is obtained, and an absorbance-grafting rate working curve is established according to the absorbance at 1780 cm -1 in the infrared spectrum.
  • the main agent of the inner layer adhesive of the aluminum-plastic film to be tested is placed in ethyl ester with a mass of 2-5 times that of the main agent of the inner layer adhesive of the aluminum-plastic film to be tested, and after the polymer in the inner layer adhesive of the aluminum-plastic film is fully precipitated, filtering, drying and extraction are performed in sequence to obtain the purified inner layer adhesive;
  • the purified inner layer rubber is prepared into a sample standard solution with the same concentration as the polyolefin standard solution, the sample standard solution is taken on a new treated window, and Fourier infrared analysis is performed after drying, and the main polymer component of the sample to be tested and the absorbance at 1780 cm -1 are confirmed according to the infrared spectrum of the sample to be tested. If the infrared spectrum of the sample to be tested is consistent with the intensity corresponding to the main peaks at 2960-2800 cm -1 , 1460-1440 cm -1 , 1370-1350 cm -1 , etc.
  • the intensity of the main peak is expressed as absorbance or transmittance.
  • the polyolefin window sheet and the modified acid window sheet are combined according to the grafting rate of the sample to be tested, and then Fourier infrared analysis is performed to obtain a verification infrared spectrum; the verification infrared spectrum is compared with the infrared spectrum of the sample to be tested for consistency.
  • the grafting rate of the sample to be tested is the grafting rate value of the inner layer glue of the aluminum-plastic film, and the performance of the inner layer glue of the aluminum-plastic film can be evaluated according to the grafting rate of the sample to be tested; if the verification infrared spectrum and the infrared spectrum of the sample to be tested have the same peak intensities at 2960 cm-1 and 1780 cm-1, then the consistency meets the requirements, and the grafting rate of the sample to be tested is the grafting rate value
  • the ratio of the intensity of the peak at 2960 cm -1 is inconsistent, or the ratio of the intensity of the peak at 1780 cm -1 is consistent but the peak at 1780 cm -1 is When the strength deviation exceeds 10%, it indicates that the working curve is invalid or the raw material is incorrectly selected, and the raw material needs to be reselected to draw the working curve.
  • the prepared polyolefin window sheet and the modified acid window sheet are placed in a tool in different combinations for Fourier infrared analysis to obtain infrared spectra at different grafting rates, and an absorbance-grafting rate working curve is established according to the absorbance at a predetermined wavelength in the infrared spectrum; after the inner layer adhesive of the aluminum-plastic film to be tested is separated and purified, its main polymer component and the absorbance at a predetermined wavelength are confirmed by Fourier infrared analysis, and the grafting rate is calculated by substituting into the working curve.
  • the present invention can quantitatively analyze the grafting rate of different types of aluminum-plastic film inner layer adhesives, more truly and accurately reflects the performance of the main agent of the aluminum-plastic film inner layer adhesive, and is convenient for horizontal comparison of different types of aluminum-plastic film inner layer adhesives.
  • the window piece is round or square, the diameter of the round window piece is 10-18 mm, and the side length of the square window piece is 10-18 mm.
  • the polyolefin includes one or more of polypropylene (PP) (binary/ternary copolymer), polyethylene (PE), and polyolefin elastomer (POE).
  • PP polypropylene
  • PE polyethylene
  • POE polyolefin elastomer
  • the coating amount is controlled to maintain the same thickness as the polymer coating, including thickness control using a pipette gun or a sample preparation device.
  • the modifying acid comprises maleic anhydride or acrylic acid.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • This embodiment provides a method for evaluating the performance of the inner layer adhesive of the aluminum-plastic film, which specifically includes the following steps:
  • the potassium bromide window is selected to be square with a side length of 14mm.
  • Preparation of standard solution sample 1g of polyolefin elastomer particles, dilute to 100mL with xylene, stir and heat to 135°C and condense and reflux for about 1h until the particles are completely dissolved, cool and redilute to 100mL to obtain a polyolefin elastomer standard solution with a concentration of 10g/L; take 1g of maleic anhydride, dilute to 100mL with anhydrous ethanol and fully dissolve to obtain a 10g/L maleic anhydride standard solution, take 10mL of the 10g/L maleic anhydride standard solution, redilute to 100mL, repeat twice to obtain 1g/L and 0.1g/L maleic anhydride standard solutions;
  • Preparation of standard sample windows of different specifications take 50 ⁇ L of polyolefin elastomer standard solution on a potassium bromide window with good light transmittance and treated and spread it evenly, place it in an 85°C oven and bake for 30-90 minutes until the solvent is completely evaporated (based on the absence of solvent peaks in infrared detection), calculate the coating thickness and polymer mass m according to the coating area and record them, which is the polyolefin elastomer window of specification m; take another potassium bromide window of the same specification and treat it, and according to the recorded m value, apply maleic anhydride standard solution at 100% m, 50% m, 25% m, 10% m, 5% m, 3% m, 1% m and other data respectively, and control the coating amount to keep the same thickness as the polyolefin elastomer coating, place the coated maleic anhydride window in a 60°C oven until completely dried, and obtain maleic anhydride windows of different specifications.
  • the absorbance A ratio is equivalent to the test substance concentration C ratio, that is, the absorbance A ratio is equivalent to the grafting rate ratio in this embodiment, thereby an absorbance-grafting rate working curve can be established.
  • the absorbance values at grafting rates of 50%, 25%, etc. were obtained under different combinations of maleic anhydride windows. By testing multiple points, the absorbance-grafting rate working curve shown in FIG. 5 was established.
  • the inner layer glue of the aluminum-plastic film to be tested is the GL inner layer glue.
  • the solid content of the GL inner layer glue sampled and tested is 12% (mass).
  • 8.33g of the GL inner layer glue is weighed in a beaker, and ethyl ester of 2-5 times its mass is added to precipitate the polymer. After sufficient filtration and drying, the obtained solid polymer is wrapped with a filter cloth and placed in a Soxhlet extractor. The ethyl ester solvent is used for repeated extraction for 2-4h to ensure that the free acid and small molecules in the GL inner layer glue are completely removed.
  • the purified GL inner layer glue is placed in a 100mL volumetric flask and calibrated with xylene (AR).
  • the concentration of the GL inner layer glue solution is tested to be 10.21g/L.
  • 50 ⁇ L of the GL inner layer glue solution is transferred with a pipette gun and smeared on a disposable potassium bromide window with a side length of 14mm (the coating area is consistent and the concentration is similar, which is regarded as the same film thickness).
  • the grafting rate of 5.2% is rounded off and 5% is taken as the value to be verified in this embodiment 1.
  • a polyolefin elastomer window sheet with a specification of m is combined with a maleic anhydride window sheet with a specification of 5%m, and then Fourier infrared analysis is performed to obtain an infrared spectrum for verification; by comparison, it is found that the peak intensities of the infrared spectrum for verification and the infrared spectrum of the GL inner layer rubber at 2960cm -1 and 1780cm -1 are consistent, that is, the grafting rate obtained is successfully verified, and 5.2% is the grafting rate of the GL inner layer rubber. If the verification is unsuccessful, it is necessary to re-select new polyolefin elastomer particles and maleic anhydride raw materials or other types of polyolefin particles and modified acid raw materials to draw the working curve.
  • Embodiments 2 to 4 respectively provide a method for evaluating the performance of the inner layer adhesive of the aluminum-plastic film. Compared with Example 1, the only difference is the type of inner layer glue tested.
  • the types of inner layer glue of aluminum-plastic film tested in Examples 2 to 4 are Vk118 inner layer glue, Vk318 inner layer glue, and JP-PMA inner layer glue, respectively. The testing methods are consistent with the examples and will not be repeated here.
  • the evaluation test method for the performance of the inner layer glue of the aluminum-plastic film can accurately quantitatively analyze the inner layer glue of the aluminum-plastic film, and can perform a horizontal comparative analysis of different types of inner layer glue.
  • the performance of the inner layer glue of the aluminum-plastic film can be evaluated according to the obtained grafting rate.
  • the evaluation standard is: the higher the grafting rate, the stronger the affinity of the inner layer glue with the aluminum layer, and the weaker the affinity with the PP layer.
  • a low grafting rate inner layer glue needs to be selected.
  • testing the grafting rate as the number of effective functional groups can indicate the amount of curing agent used in the inner layer glue of the aluminum-plastic film to avoid insufficient or excessive curing agent.

Landscapes

  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Laminated Bodies (AREA)

Abstract

A method and tool for evaluating and testing the performance of an inner layer adhesive for an aluminum-plastic film, relating to the field of soft packing of lithium batteries. The method comprises: preparing polyolefin window sheets and modified acid window sheets as standard samples, performing Fourier infrared analysis on the polyolefin window sheets and the modified acid window sheets in different combination modes by using a tool to obtain infrared spectrums under different grafting rates, and establishing an absorbance-grafting rate working curve according to the absorbance at predetermined wavelengths in the infrared spectrums; and separating and purifying an inner layer adhesive for an aluminum-plastic film to be tested, confirming components of a main polymer of the inner layer adhesive and the absorbance at the predetermined wavelengths by means of Fourier infrared analysis, substituting the absorbance into the working curve to obtain the grafting rates, and verifying the obtained grafting rates. The grafting rates of different types of inner layer adhesives for aluminum-plastic films can be quantitatively analyzed, the performance of main agent bodies of the inner layer adhesives for aluminum-plastic films can be reflected more truly and accurately, and transverse comparison of different types of inner layer adhesives for aluminum-plastic films is facilitated.

Description

针对铝塑膜内层胶性能的评估测试方法及其工具Evaluation and testing methods and tools for the performance of inner adhesive of aluminum-plastic film 技术领域Technical Field
本发明涉及锂电池软包技术领域，尤其涉及一种针对铝塑膜内层胶性能的评估测试方法及其工具。The present invention relates to the technical field of lithium battery soft packs, and in particular to an evaluation and testing method for the performance of an inner layer adhesive of an aluminum-plastic film and a tool thereof.
背景技术Background technique
随着锂离子电池行业的不断发展与壮大，尤其是软包锂电池市场的拓展，其主要材料铝塑膜的使用量迅速增加。对于市面上的铝塑膜而言，其性能主要源自直接接触电解液的PP层。由于PP成膜技术发展水平较高，铝箔本身工艺较为先进，因此铝塑膜性能的关键表现为PP层与铝箔层粘接剂的性能。即行业内常说的铝塑膜内层胶的性能。With the continuous development and growth of the lithium-ion battery industry, especially the expansion of the soft-pack lithium battery market, the use of aluminum-plastic film, its main material, has increased rapidly. For the aluminum-plastic film on the market, its performance mainly comes from the PP layer that is in direct contact with the electrolyte. Due to the high level of development of PP film-forming technology and the advanced process of aluminum foil itself, the key to the performance of aluminum-plastic film is the performance of the adhesive between the PP layer and the aluminum foil layer. This is what the industry often calls the performance of the inner layer glue of the aluminum-plastic film.
市面上的铝塑膜内层胶多如繁星，关于如何评价不同内胶的优劣，目前市面上常用的方法主要是直接法，即使用胶水，以胶水在标准样条上产生剥离力的多少进行对比，以直接生产铝塑膜的方式进行验证与评估。直接法测试铝塑膜内层胶的优势在于直观明了，能够直接通过剥离力、耐电解液、热封性能等方面直接反馈该内层胶在铝塑膜制造上是否合适。There are numerous inner layer glues for aluminum-plastic films on the market. As for how to evaluate the advantages and disadvantages of different inner glues, the commonly used method on the market is mainly the direct method, that is, using glue to compare the peeling force generated by the glue on the standard sample, and verifying and evaluating it by directly producing aluminum-plastic films. The advantage of the direct method for testing the inner layer glue of aluminum-plastic films is that it is intuitive and clear, and can directly feedback whether the inner layer glue is suitable for aluminum-plastic film manufacturing through peeling force, electrolyte resistance, heat sealing performance, etc.
但铝塑膜内层胶作为一种双组分胶黏剂，固化剂的使用比例、固化条件、涂布浓度等参数将会影响内层胶的具体性能，这就导致使用直接法进行测试时，能且仅能对某一特定参数下的内层胶性能进行分析。在此之上使用直接法测试铝塑膜内层胶需要消耗铝材及其它耗材，实验成本较高。最重要的一点，使用直接法对内层胶进行分析，分析结果为内层AB胶在配比后性能的差异，未切实针对主剂本体进行分析，直接将直接法测试结果等效为内层胶主体的性能有失偏颇。However, as a two-component adhesive, the inner layer glue of aluminum-plastic film will be affected by parameters such as the proportion of curing agent used, curing conditions, and coating concentration, which will affect the specific performance of the inner layer glue. This means that when using the direct method for testing, the performance of the inner layer glue can only be analyzed under certain specific parameters. In addition, using the direct method to test the inner layer glue of aluminum-plastic film requires the consumption of aluminum and other consumables, and the experimental cost is relatively high. The most important point is that the direct method is used to analyze the inner layer glue, and the analysis results are the difference in performance of the inner layer AB glue after proportioning. The main agent itself is not actually analyzed, and it is biased to directly equate the direct method test results to the performance of the inner layer glue body.
以铝塑膜内层胶而言，其主体成分为酸改性聚烯烃类材料，主体为聚丙 烯基类材料，但依据不同使用情况，有采用乙烯基共聚，丁烯段共聚等不同衍生物存在。改性酸一般为马来酸酐，偶有丙烯酸，其它酸类几乎不使用。因此如能精确判断酸改性聚烯烃的酸性基团接枝率，即可有效表征内层胶主剂的活性基团比例与极性程度，进而表征其作为内层胶性能潜力水平。As for the inner layer of aluminum-plastic film, its main component is acid-modified polyolefin material, the main component is polypropylene Olefin materials, but according to different usage conditions, there are different derivatives such as vinyl copolymerization and butene copolymerization. The modified acid is generally maleic anhydride, occasionally acrylic acid, and other acids are almost not used. Therefore, if the acid group grafting rate of acid-modified polyolefin can be accurately determined, the active group ratio and polarity of the main agent of the inner layer glue can be effectively characterized, and then its performance potential level as an inner layer glue can be characterized.
目前学术界表征酸改性接枝率的主要方法为滴定法，这种方法的优势在于，对于酸改性产品，其定量精确，所需仪器较少。但对于铝塑膜内层胶而言，由于其主体使用的聚丙烯基类材料不同，使用滴定法只能对同一种胶的不同批次进行检验，对于不同公司提供的不同类型的胶，缺乏横向比较能力。而另一种方法，使用傅里叶红外光谱法进行接枝率分析，又由于胶膜厚度，测试胶量以及均匀性控制等问题，通常只使用在官能表征方向，即定性而不定量分析。而使用ATR法进行此分析，由于反射吸收偏弱，在差异较小时工作曲线偏移较大，仍旧会存在失真问题。At present, the main method used in academia to characterize the acid-modified grafting rate is titration. The advantage of this method is that for acid-modified products, it is quantitatively accurate and requires fewer instruments. However, for the inner layer glue of aluminum-plastic film, due to the different polypropylene-based materials used in its main body, the titration method can only be used to test different batches of the same glue, and lacks the ability to compare different types of glue provided by different companies. Another method, Fourier transform infrared spectroscopy, is used for grafting rate analysis. However, due to problems such as film thickness, test glue quantity, and uniformity control, it is usually only used in the direction of functional characterization, that is, qualitative rather than quantitative analysis. When using the ATR method for this analysis, due to weak reflection absorption, the working curve shifts greatly when the difference is small, and there will still be distortion problems.
发明内容Summary of the invention
针对上述现有技术的缺陷，本发明的目的在于提供一种针对铝塑膜内层胶性能的评估测试方法及其工具，基于傅里叶红外光谱法定量分析铝塑膜内层胶接枝率，根据接枝率对铝塑膜内层胶性能进行评估。In view of the defects of the above-mentioned prior art, the purpose of the present invention is to provide a testing method and tool for evaluating the performance of the inner layer glue of aluminum-plastic film, quantitatively analyze the grafting rate of the inner layer glue of aluminum-plastic film based on Fourier transform infrared spectroscopy, and evaluate the performance of the inner layer glue of aluminum-plastic film according to the grafting rate.
为实现上述目的，本发明提供了一种针对铝塑膜内层胶性能的评估测试方法，包括如下步骤：To achieve the above object, the present invention provides a method for evaluating the performance of the inner layer adhesive of an aluminum-plastic film, comprising the following steps:
(1)制备不同规格的标准样窗片(1) Preparation of standard sample windows of different specifications
配制预定浓度的聚烯烃标准溶液和改性酸标准溶液；将预定体积的所述聚烯烃标准溶液均匀涂布于处理好的窗片上，烘干后得到聚烯烃窗片；按照与所述聚烯烃标准溶液相同的涂布厚度将不同质量的所述改性酸标准溶液分别涂布于不同的处理好的窗片上，烘干后得到不同规格的改性酸窗片；所述改性酸窗片上涂布的改性酸的质量占所述聚烯烃窗片上涂布的聚烯烃的质量的1-100％；Prepare a polyolefin standard solution and a modified acid standard solution of a predetermined concentration; evenly apply a predetermined volume of the polyolefin standard solution on the treated window sheet, and obtain the polyolefin window sheet after drying; apply different masses of the modified acid standard solution on different treated window sheets according to the same coating thickness as the polyolefin standard solution, and obtain modified acid windows of different specifications after drying; the mass of the modified acid coated on the modified acid window sheet accounts for 1-100% of the mass of the polyolefin coated on the polyolefin window sheet;
(2)建立吸光度-接枝率工作曲线(2) Establishing the absorbance-grafting rate working curve
使用工具将1枚所述聚烯烃窗片与至少1枚所述改性酸窗片组合，进行傅 里叶红外分析，以组合后所有改性酸窗片上涂布的改性酸质量之和占所述聚烯烃窗片上涂布的聚烯烃的质量的百分数作为预期接枝率，得到不同预期接枝率下的标准样的红外光谱，并根据所述红外光谱中预定波长处的吸光度建立吸光度-接枝率工作曲线；Use a tool to combine one of the polyolefin window sheets with at least one of the modified acid window sheets, and perform Infrared analysis is performed to obtain the expected grafting rate by taking the percentage of the sum of the mass of the modified acid coated on all the modified acid windows after combination to the mass of the polyolefin coated on the polyolefin window, obtaining infrared spectra of standard samples under different expected grafting rates, and establishing an absorbance-grafting rate working curve according to the absorbance at a predetermined wavelength in the infrared spectrum;
(3)待测样分离提纯、测试及验证(3) Separation, purification, testing and verification of samples
取待测铝塑膜内层胶主剂置于预定量的乙酯中，待所述铝塑膜内层胶中的聚合物充分析出后，依次进行过滤、干燥与萃取，得到提纯后的内层胶；The main agent of the inner layer adhesive of the aluminum-plastic film to be tested is placed in a predetermined amount of ethyl ester, and after the polymer in the inner layer adhesive of the aluminum-plastic film is fully precipitated, filtering, drying and extraction are performed in sequence to obtain the purified inner layer adhesive;
依照配制所述聚烯烃标准溶液的方法，将所述提纯后的内层胶配制为与所述聚烯烃标准溶液浓度一致的待测样标准溶液，取所述待测样标准溶液于新的处理好的窗片上，烘干后进行傅里叶红外分析，根据待测样的红外光谱确认待测样主体聚合物组分和预定波长处的吸光度，再根据所述工作曲线计算出待测样的接枝率；According to the method for preparing the polyolefin standard solution, the purified inner layer rubber is prepared into a sample standard solution having the same concentration as the polyolefin standard solution, the sample standard solution is placed on a newly treated window, and after drying, Fourier infrared analysis is performed, the main polymer component of the sample to be tested and the absorbance at a predetermined wavelength are confirmed according to the infrared spectrum of the sample to be tested, and then the grafting rate of the sample to be tested is calculated according to the working curve;
将所述聚烯烃窗片与所述改性酸窗片按照所述待测样的接枝率进行组合，随后进行傅里叶红外分析，得到验证用红外光谱；将所述验证用红外光谱与所述待测样的红外光谱进行一致性对比，若一致性符合要求，则根据所述待测样的接枝率对所述铝塑膜内层胶的性能进行评估；若一致性不符合要求，则表明所述工作曲线失效或选用原料有误，需重新选用原料绘制工作曲线。进一步地，步骤(1)中所述聚烯烃包括聚丙烯、聚乙烯、聚烯烃弹性体中的一种或几种；所述预定浓度的聚烯烃标准溶液的浓度为10g/L；所述聚烯烃标准溶液的预定浓度为1-10g/L；所述预定体积为10-100μL。The polyolefin window and the modified acid window are combined according to the grafting rate of the sample to be tested, and then Fourier infrared analysis is performed to obtain a verification infrared spectrum; the verification infrared spectrum is compared with the infrared spectrum of the sample to be tested for consistency. If the consistency meets the requirements, the performance of the inner layer glue of the aluminum-plastic film is evaluated according to the grafting rate of the sample to be tested; if the consistency does not meet the requirements, it indicates that the working curve is invalid or the raw material is incorrectly selected, and the raw material needs to be reselected to draw the working curve. Further, the polyolefin in step (1) includes one or more of polypropylene, polyethylene, and polyolefin elastomer; the concentration of the predetermined concentration of the polyolefin standard solution is 10g/L; the predetermined concentration of the polyolefin standard solution is 1-10g/L; the predetermined volume is 10-100μL.
进一步地，步骤(1)中所述改性酸包括马来酸酐、丙烯酸；所述改性酸标准溶液的预定浓度为0.1-1g/L。Furthermore, the modified acid in step (1) includes maleic anhydride and acrylic acid; and the predetermined concentration of the modified acid standard solution is 0.1-1 g/L.
进一步地，步骤(1)中制备所述聚烯烃窗片时，将涂布有所述聚烯烃标准溶液的窗片置于60-90℃烘箱中烘烤30-90min至溶剂完全挥发。Furthermore, when preparing the polyolefin window in step (1), the window coated with the polyolefin standard solution is placed in an oven at 60-90° C. and baked for 30-90 min until the solvent is completely volatilized.
进一步地，步骤(1)中所述窗片为溴化钾窗片；所述窗片为圆形或方形，圆形窗片直径为10-18mm，方形窗片边长为10-18mm；所述处理好的窗片的处理过程为：将表面发白发雾窗片置于加有异丙醇混合液的1200-2000目金相砂纸 上摩擦至表面均匀，若窗片无发雾，则略过此步；然后将处理后窗片擦干，再次滴加异丙醇混合液于窗片表面，用丝绒金相抛光布进行抛光Furthermore, the window in step (1) is a potassium bromide window; the window is round or square, the diameter of the round window is 10-18 mm, and the side length of the square window is 10-18 mm; the treatment process of the treated window is: placing the white and foggy window on a 1200-2000 mesh metallographic sandpaper with an isopropyl alcohol mixture Rub until the surface is even. If the window is not foggy, skip this step. Then wipe the treated window dry, add isopropyl alcohol mixture to the window surface again, and polish with velvet metallographic polishing cloth.
进一步地，所述异丙醇混合液由异丙醇和蒸馏水按预定的体积比混合而成，所述异丙醇混合溶液中异丙醇的体积占比为85-95％。Furthermore, the isopropanol mixed solution is prepared by mixing isopropanol and distilled water in a predetermined volume ratio, and the volume proportion of isopropanol in the isopropanol mixed solution is 85-95%.
进一步地，步骤(2)中所述预定波长处的吸光度为1780cm-1处的吸光度。Furthermore, the absorbance at the predetermined wavelength in step (2) is the absorbance at 1780 cm -1 .
进一步地，步骤(3)中所述预定量的乙酯的质量为所述待测铝塑膜内层胶主剂的2-5倍。Furthermore, the mass of the predetermined amount of ethyl ester in step (3) is 2-5 times that of the main agent of the inner layer adhesive of the aluminum-plastic film to be tested.
进一步地，在步骤(3)中，根据工作曲线计算接枝率时，若所述待测样的红外光谱与所述标准样的红外光谱中主峰对应的吸光度一致，则将1780cm-1处峰的吸光度代入所述工作曲线求出待测样的接枝率；若所述主峰对应的吸光度不一致，则以2960cm-1处峰为基准，依照接枝率＝(1780cm-1处计算的接枝率*待测样的红外谱图在2960cm-1处峰强度/标准样的红外谱图在2960cm-1处峰强度)进行修正，即得到铝塑膜内层胶接枝率数值。Furthermore, in step (3), when the grafting rate is calculated according to the working curve, if the infrared spectrum of the sample to be tested is consistent with the absorbance corresponding to the main peak in the infrared spectrum of the standard sample, the absorbance of the peak at 1780 cm -1 is substituted into the working curve to calculate the grafting rate of the sample to be tested; if the absorbance corresponding to the main peak is inconsistent, the peak at 2960 cm -1 is used as a reference, and correction is made according to grafting rate = (grafting rate calculated at 1780 cm -1 * peak intensity of infrared spectrum of sample to be tested at 2960 cm -1 / peak intensity of infrared spectrum of standard sample at 2960 cm -1 ), so as to obtain the grafting rate value of the inner layer adhesive of the aluminum-plastic film.
进一步地，在步骤(3)中进行所述一致性对比时，若所述验证用红外光谱和所述待测样的红外光谱在2960cm-1与1780cm-1处峰的强度一致，或者所述验证用红外光谱和所述待测样的红外光谱在所述1780cm-1处峰的强度偏差不超过10％且所述验证用红外光谱和所述待测样的红外光谱在所述2960cm-1与1780cm-1处峰的强度的比例关系一致，则一致性符合要求；若所述验证用红外光谱和所述待测样的红外光谱在所述2960cm-1与1780cm-1处峰的强度的比例关系不一致，或者在所述2960cm-1与1780cm-1处峰的强度的比例关系一致但在所述1780cm-1处峰的强度偏差超过10％时，则一致性不符合要求。Furthermore, when the consistency comparison is performed in step (3), if the peak intensities of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 2960 cm -1 and 1780 cm -1 are consistent, or the peak intensity deviation of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 1780 cm -1 does not exceed 10% and the ratio of the peak intensities of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 2960 cm - 1 and 1780 cm -1 is consistent, then the consistency meets the requirements; if the ratio of the peak intensities of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 2960 cm -1 and 1780 cm -1 is inconsistent, or the ratio of the peak intensities at 2960 cm -1 and 1780 cm -1 is consistent but the peak intensity deviation at 1780 cm -1 exceeds 10%, then the consistency does not meet the requirements.
为实现上述目的，本发明还提供了一种针对铝塑膜内层胶性能的评估测试工具，该工具沿垂直于红外光照射的方向平行设置有若干个插槽，用于放置以不同形式组合的聚烯烃窗片和改性酸窗片。To achieve the above objectives, the present invention also provides an evaluation and testing tool for the performance of the inner layer adhesive of aluminum-plastic film, which has a plurality of slots arranged in parallel along a direction perpendicular to the infrared light irradiation for placing polyolefin windows and modified acid windows in different combinations.
本发明的有益效果是：The beneficial effects of the present invention are:
1、本发明提供的针对铝塑膜内层胶性能的评估测试方法，基于傅里叶红外 光谱法原理定量分析铝塑膜内层胶接枝率，并根据接枝率对铝塑膜内层胶的性能进行评估。以此便可方便快捷地评估不同铝塑膜内层胶性能。与现有技术采用的直接法相比，本发明不仅降低了所需的实验耗材，而且解除了以往仅能分析特定参数下内层胶性能的限制，并提高了对混合胶分析的准确性。1. The present invention provides a method for evaluating the performance of the inner layer adhesive of the aluminum-plastic film based on Fourier infrared The principle of spectral method quantitatively analyzes the grafting rate of the inner layer glue of the aluminum-plastic film, and evaluates the performance of the inner layer glue of the aluminum-plastic film according to the grafting rate. In this way, the performance of the inner layer glue of different aluminum-plastic films can be conveniently and quickly evaluated. Compared with the direct method used in the prior art, the present invention not only reduces the required experimental consumables, but also removes the previous limitation of only being able to analyze the performance of the inner layer glue under specific parameters, and improves the accuracy of mixed glue analysis.
2、本发明提供的针对铝塑膜内层胶性能的评估测试方法，通过将聚烯烃窗片和改性酸窗片以不同组合方式进行傅里叶红外分析，能够得到不同接枝率下的红外光谱，建立吸光度-接枝率工作曲线；在此基础上，通过对待测铝塑膜内层胶进行分离提纯后确认其主体聚合物组分和预定波长处的吸光度，代入工作曲线便可求得接枝率，实现了基于傅里叶红外光谱法的接枝率定量分析。与现有技术采用的滴定法相比，本发明提供的测试方法解除了以往仅能对同一种胶的不同批次进行测试的限制，扩宽了适用范围，并能对不同类型铝塑膜内层胶进行横向比较。2. The present invention provides an evaluation test method for the performance of the inner layer adhesive of aluminum-plastic film. By performing Fourier infrared analysis on polyolefin windows and modified acid windows in different combinations, infrared spectra under different grafting rates can be obtained, and an absorbance-grafting rate working curve can be established. On this basis, the main polymer components and the absorbance at a predetermined wavelength are confirmed after separation and purification of the inner layer adhesive of the aluminum-plastic film to be tested, and the grafting rate can be obtained by substituting into the working curve, thus realizing the quantitative analysis of the grafting rate based on Fourier infrared spectroscopy. Compared with the titration method used in the prior art, the test method provided by the present invention removes the previous limitation that only different batches of the same adhesive can be tested, broadens the scope of application, and can make a horizontal comparison of different types of inner layer adhesives of aluminum-plastic film.
3、本发明提供的针对铝塑膜内层胶性能的评估测试工具，通过开设若干个槽，可以将聚烯烃窗片和改性酸窗片以多种不同组合方式进行傅里叶红外分析，便于建立吸光度-接枝率工作曲线，并简便、快捷的求得铝塑膜内层胶的接枝率。3. The evaluation and testing tool for the performance of the inner layer adhesive of the aluminum-plastic film provided by the present invention can perform Fourier transform infrared analysis on the polyolefin window and the modified acid window in a variety of different combinations by opening a plurality of slots, so as to facilitate the establishment of an absorbance-grafting rate working curve and to obtain the grafting rate of the inner layer adhesive of the aluminum-plastic film simply and quickly.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明提供的针对铝塑膜内层胶性能的评估测试工具的结构示意图。FIG. 1 is a schematic diagram of the structure of a test tool for evaluating the performance of the inner adhesive layer of an aluminum-plastic film provided by the present invention.
图2为实施例1中0％接枝率下的红外光谱谱图。FIG. 2 is an infrared spectrum diagram of Example 1 at a grafting rate of 0%.
图3为实施例1中50％接枝率下的红外光谱谱图。FIG. 3 is an infrared spectrum diagram of Example 1 at a grafting rate of 50%.
图4为实施例1中100％接枝率下的红外光谱谱图。FIG. 4 is an infrared spectrum diagram of Example 1 at a grafting rate of 100%.
图5为实施例1中建立的1780cm-1处的吸光度-接枝率工作曲线。FIG. 5 is a working curve of absorbance at 1780 cm -1 - grafting rate established in Example 1.
图6为实施例1中GL内层胶窗片的红外光谱谱图。FIG. 6 is an infrared spectrum of the GL inner layer window film in Example 1.
具体实施方式Detailed ways
为了使本发明的目的、技术方案和优点更加清楚，下面结合附图和具体 实施例对本发明进行详细描述。In order to make the purpose, technical solutions and advantages of the present invention more clear, the following is a detailed description of the present invention with reference to the accompanying drawings and specific The present invention is described in detail with reference to Examples.
在此，还需要说明的是，为了避免因不必要的细节而模糊了本发明，在附图中仅仅示出了与本发明的方案密切相关的结构和/或处理步骤，而省略了与本发明关系不大的其他细节。It should also be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to the scheme of the present invention are shown in the drawings, while other details that are not closely related to the present invention are omitted.
另外，还需要说明的是，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。In addition, it should be noted that the terms "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or apparatus.
本发明提供一种针对铝塑膜内层胶性能的评估测试方法及其工具，基于傅里叶红外光谱法定量分析铝塑膜内层胶接枝率，根据接枝率对铝塑膜内层胶性能进行评估，包括以下步骤：The present invention provides a method and tool for evaluating the performance of the inner layer adhesive of an aluminum-plastic film, which quantitatively analyzes the grafting rate of the inner layer adhesive of the aluminum-plastic film based on Fourier infrared spectroscopy, and evaluates the performance of the inner layer adhesive of the aluminum-plastic film according to the grafting rate, comprising the following steps:
(1)制备不同规格的标准样窗片(1) Preparation of standard sample windows of different specifications
配制浓度为10g/L的聚烯烃标准溶液和浓度为0.1-1g/L的改性酸标准溶液；取10-100μL的所述聚烯烃标准溶液均匀涂布于处理好的溴化钾窗片上，置于60-90℃烘箱中烘烤30-90min至溶剂完全挥发后，得到不同规格的聚烯烃窗片；按照与所述聚烯烃标准溶液相同的涂布厚度将不同质量的所述改性酸标准溶液分别涂布于不同的处理好的窗片上，烘干后得到不同规格的改性酸窗片；所述改性酸窗片上涂布的改性酸的质量占所述聚烯烃窗片上涂布的聚烯烃的质量的1-100％；所述处理好的窗片的处理过程为：将表面发白发雾窗片置于加有异丙醇混合液的1200-2000目金相砂纸上摩擦至表面均匀，若窗片无发雾，则略过此步；然后将处理后窗片擦干，再次滴加异丙醇混合液于窗片表面，用金相抛光布进行抛光；所述异丙醇混合液由体积占比为85-95％的异丙醇和蒸馏水混合而成。Prepare a polyolefin standard solution with a concentration of 10 g/L and a modified acid standard solution with a concentration of 0.1-1 g/L; take 10-100 μL of the polyolefin standard solution and evenly apply it on the treated potassium bromide window, place it in a 60-90 ° C oven and bake for 30-90 minutes until the solvent is completely volatilized, and obtain polyolefin windows of different specifications; according to the same coating thickness as the polyolefin standard solution, apply different masses of the modified acid standard solution on different treated windows, and obtain modified acid windows of different specifications after drying; The mass of the modified acid coated on the modified acid window sheet accounts for 1-100% of the mass of the polyolefin coated on the polyolefin window sheet; the processing process of the treated window sheet is: placing the window sheet with a white and foggy surface on a 1200-2000 mesh metallographic sandpaper added with an isopropyl alcohol mixture and rubbing it until the surface is uniform, if the window sheet is not foggy, this step is skipped; then the treated window sheet is wiped dry, the isopropyl alcohol mixture is dripped on the surface of the window sheet again, and polished with a metallographic polishing cloth; the isopropyl alcohol mixture is a mixture of isopropyl alcohol and distilled water with a volume ratio of 85-95%.
(2)建立吸光度-接枝率工作曲线(2) Establishing the absorbance-grafting rate working curve
使用工具将1枚所述聚烯烃窗片与至少1枚所述改性酸窗片组合，进行傅里叶红外分析，以组合后所有改性酸窗片上涂布的改性酸质量之和占所述聚烯烃窗片上涂布的聚烯烃的质量的百分数作为预期接枝率，得到不同预期 接枝率下的红外光谱，并根据所述红外光谱中1780cm-1处的吸光度建立吸光度-接枝率工作曲线。A tool is used to combine one of the polyolefin window sheets with at least one of the modified acid window sheets, and Fourier infrared analysis is performed. The percentage of the sum of the mass of the modified acid coated on all the modified acid window sheets after combination to the mass of the polyolefin coated on the polyolefin window sheet is taken as the expected grafting rate, and different expected The infrared spectrum at the grafting rate is obtained, and an absorbance-grafting rate working curve is established according to the absorbance at 1780 cm -1 in the infrared spectrum.
(3)待测样分离提纯、测试及验证(3) Separation, purification, testing and verification of samples
取待测铝塑膜内层胶主剂置于所述待测铝塑膜内层胶主剂质量的2-5倍的乙酯中，待所述铝塑膜内层胶中的聚合物充分析出后，依次进行过滤、干燥与萃取，得到提纯后的内层胶；The main agent of the inner layer adhesive of the aluminum-plastic film to be tested is placed in ethyl ester with a mass of 2-5 times that of the main agent of the inner layer adhesive of the aluminum-plastic film to be tested, and after the polymer in the inner layer adhesive of the aluminum-plastic film is fully precipitated, filtering, drying and extraction are performed in sequence to obtain the purified inner layer adhesive;
依照配制所述聚烯烃标准溶液的方法，将所述提纯后的内层胶配制为与所述聚烯烃标准溶液浓度一致的待测样标准溶液，取所述待测样标准溶液于新的处理好的窗片上，烘干后进行傅里叶红外分析，根据待测样的红外光谱确认待测样主体聚合物组分和1780cm-1处的吸光度，若所述待测样的红外光谱与所述标准样的红外光谱中2960-2800cm-1、1460-1440cm-1、1370-1350cm-1等处主峰对应的强度一致，则将所述1780cm-1处的吸光度代入所述工作曲线求出待测样的接枝率；若所述主峰对应的强度不一致，则以2960cm-1处峰为基准，依照接枝率＝(1780cm-1处计算的接枝率*待测样的红外光谱在2960cm-1处峰强度/标准样的红外光谱在2960cm-1处峰强度)进行修正，即求出待测样的接枝率。其中，主峰的强度以吸光度或透过率进行表示。According to the method for preparing the polyolefin standard solution, the purified inner layer rubber is prepared into a sample standard solution with the same concentration as the polyolefin standard solution, the sample standard solution is taken on a new treated window, and Fourier infrared analysis is performed after drying, and the main polymer component of the sample to be tested and the absorbance at 1780 cm -1 are confirmed according to the infrared spectrum of the sample to be tested. If the infrared spectrum of the sample to be tested is consistent with the intensity corresponding to the main peaks at 2960-2800 cm -1 , 1460-1440 cm -1 , 1370-1350 cm -1 , etc. in the infrared spectrum of the standard sample, the absorbance at 1780 cm -1 is substituted into the working curve to obtain the grafting rate of the sample to be tested; if the intensity corresponding to the main peak is inconsistent, the peak at 2960 cm -1 is used as a reference, and the grafting rate is calculated according to the formula: grafting rate = (grafting rate calculated at 1780 cm -1 * peak intensity of the infrared spectrum of the sample to be tested at 2960 cm -1 / peak intensity of the infrared spectrum of the standard sample at 2960 cm-1 -1 ) to correct the grafting rate of the sample to be tested. The intensity of the main peak is expressed as absorbance or transmittance.
将所述聚烯烃窗片与所述改性酸窗片按照所述待测样的接枝率进行组合，随后进行傅里叶红外分析，得到验证用红外光谱；将所述验证用红外光谱与所述待测样的红外光谱进行一致性对比，若所述验证用红外光谱和所述待测样的红外光谱在2960cm-1与1780cm-1处峰的强度一致，或者所述验证用红外光谱和所述待测样的红外光谱在所述1780cm-1处峰的强度偏差不超过10％且所述验证用红外光谱和所述待测样的红外光谱在所述2960cm-1与1780cm-1处峰的强度的比例关系一致，则一致性符合要求，求出的待测样的接枝率即为铝塑膜内层胶接枝率数值，则可根据所述待测样的接枝率对所述铝塑膜内层胶的性能进行评估；若所述验证用红外光谱和所述待测样的红外光谱在所述2960cm-1与1780cm-1处峰的强度的比例关系不一致，或者在所述2960cm-1与1780cm-1处峰的强度的比例关系一致但在所述1780cm-1处峰 的强度偏差超过10％时，则表明所述工作曲线失效或选用原料有误，需重新选用原料绘制工作曲线。The polyolefin window sheet and the modified acid window sheet are combined according to the grafting rate of the sample to be tested, and then Fourier infrared analysis is performed to obtain a verification infrared spectrum; the verification infrared spectrum is compared with the infrared spectrum of the sample to be tested for consistency. If the peak intensities of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 2960 cm -1 and 1780 cm -1 are consistent, or the peak intensity deviation of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 1780 cm -1 does not exceed 10% and the ratio of the peak intensities of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 2960 cm -1 and 1780 cm -1 is consistent, then the consistency meets the requirements, and the grafting rate of the sample to be tested is the grafting rate value of the inner layer glue of the aluminum-plastic film, and the performance of the inner layer glue of the aluminum-plastic film can be evaluated according to the grafting rate of the sample to be tested; if the verification infrared spectrum and the infrared spectrum of the sample to be tested have the same peak intensities at 2960 cm-1 and 1780 cm-1, then the consistency meets the requirements, and the grafting rate of the sample to be tested is the grafting rate value of the inner layer glue of the aluminum-plastic film, then the performance of the inner layer glue of the aluminum - plastic film can be evaluated according to the grafting rate of the sample to be tested. The ratio of the intensity of the peak at 2960 cm -1 is inconsistent, or the ratio of the intensity of the peak at 1780 cm -1 is consistent but the peak at 1780 cm -1 is When the strength deviation exceeds 10%, it indicates that the working curve is invalid or the raw material is incorrectly selected, and the raw material needs to be reselected to draw the working curve.
上述实施例将制备的聚烯烃窗片和改性酸窗片以不同组合方式置于工具进行傅里叶红外分析，得到不同接枝率下的红外光谱，并根据红外光谱中预定波长处的吸光度建立吸光度-接枝率工作曲线；对待测铝塑膜内层胶进行分离提纯后，通过傅里叶红外分析确认其主体聚合物组分和预定波长处的吸光度，代入工作曲线求出接枝率，本发明能够对不同类型的铝塑膜内层胶接枝率进行定量分析，更加真实准确地反映了铝塑膜内层胶主剂本体的性能，且便于对不同类型的铝塑膜内层胶进行横向比较。In the above-mentioned embodiment, the prepared polyolefin window sheet and the modified acid window sheet are placed in a tool in different combinations for Fourier infrared analysis to obtain infrared spectra at different grafting rates, and an absorbance-grafting rate working curve is established according to the absorbance at a predetermined wavelength in the infrared spectrum; after the inner layer adhesive of the aluminum-plastic film to be tested is separated and purified, its main polymer component and the absorbance at a predetermined wavelength are confirmed by Fourier infrared analysis, and the grafting rate is calculated by substituting into the working curve. The present invention can quantitatively analyze the grafting rate of different types of aluminum-plastic film inner layer adhesives, more truly and accurately reflects the performance of the main agent of the aluminum-plastic film inner layer adhesive, and is convenient for horizontal comparison of different types of aluminum-plastic film inner layer adhesives.
优选地，所述窗片为圆形或方形，圆形窗片直径为10-18mm，方形窗片边长为10-18mm。Preferably, the window piece is round or square, the diameter of the round window piece is 10-18 mm, and the side length of the square window piece is 10-18 mm.
优选地，所述聚烯烃包括聚丙烯(PP)(二元/三元共聚)、聚乙烯(PE)、聚烯烃弹性体(POE)中的一种或几种。Preferably, the polyolefin includes one or more of polypropylene (PP) (binary/ternary copolymer), polyethylene (PE), and polyolefin elastomer (POE).
优选地，所述控制涂布量保持与聚合物涂布同样厚度，包括用移液枪、制样器进行厚度控制。Preferably, the coating amount is controlled to maintain the same thickness as the polymer coating, including thickness control using a pipette gun or a sample preparation device.
优选地，所述改性酸包括马来酸酐、丙烯酸。Preferably, the modifying acid comprises maleic anhydride or acrylic acid.
下面结合实施例对本发明提供的针对铝塑膜内层胶性能的评估测试方法及其工具进行具体说明。The evaluation test method and tool for the performance of the inner layer adhesive of the aluminum-plastic film provided by the present invention are described in detail below in conjunction with the embodiments.
实施例1：Embodiment 1:
本实施例提供了一种针对铝塑膜内层胶性能的评估测试方法，具体包括如下步骤：This embodiment provides a method for evaluating the performance of the inner layer adhesive of the aluminum-plastic film, which specifically includes the following steps:
(1)制备不同规格的标准样窗片(1) Preparation of standard sample windows of different specifications
取90mL异丙醇(AR)与10mL蒸馏水充分混合均匀制得异丙醇混合溶液。对于表面发白发雾溴化钾窗片，滴加约1mL所述异丙醇混合液于2000目金相砂纸上，并将发雾面置于砂纸上来回轻轻摩擦至表面均匀，若窗片无发雾，则略过此步；将处理后的溴化钾窗片擦干，再次滴加所述混合液一滴于所述溴化钾窗片表面，使用3μm金相抛光布摩擦，随后使用1μm金相抛 光布擦拭干净，反复数次，直至表面透明度良好视为该面抛光完成。对溴化钾窗片两面均处理完成后待用；其中所述溴化钾窗片选择方形边长为14mm。Take 90mL of isopropanol (AR) and 10mL of distilled water and mix them thoroughly to make an isopropanol mixed solution. For potassium bromide windows with white and foggy surfaces, add about 1mL of the isopropanol mixed solution onto 2000-grit metallographic sandpaper, and gently rub the foggy surface back and forth on the sandpaper until the surface is uniform. If the window is not foggy, skip this step; wipe the treated potassium bromide window dry, add a drop of the mixed solution onto the surface of the potassium bromide window again, rub it with a 3μm metallographic polishing cloth, and then use a 1μm metallographic polishing cloth to polish it. Wipe clean with a clean cloth, repeat several times until the surface transparency is good, and the polishing of the surface is considered complete. After both sides of the potassium bromide window are processed, it is ready for use; wherein the potassium bromide window is selected to be square with a side length of 14mm.
配制标准溶液：取样聚烯烃弹性体颗粒1g，用二甲苯定容至100mL，搅拌加热至135℃并冷凝回流约1h至颗粒完全溶解，冷却后重新定容至100mL，制得浓度为10g/L的聚烯烃弹性体标准溶液；取1g马来酸酐，用无水乙醇定容至100mL后充分溶解后得到10g/L的马来酸酐标准溶液，取所述10g/L的马来酸酐标准溶液10mL，重新定容至100mL，重复两次，得到1g/L与0.1g/L马来酸酐标准溶液；Preparation of standard solution: sample 1g of polyolefin elastomer particles, dilute to 100mL with xylene, stir and heat to 135°C and condense and reflux for about 1h until the particles are completely dissolved, cool and redilute to 100mL to obtain a polyolefin elastomer standard solution with a concentration of 10g/L; take 1g of maleic anhydride, dilute to 100mL with anhydrous ethanol and fully dissolve to obtain a 10g/L maleic anhydride standard solution, take 10mL of the 10g/L maleic anhydride standard solution, redilute to 100mL, repeat twice to obtain 1g/L and 0.1g/L maleic anhydride standard solutions;
制备不同规格标准样窗片：取50μL聚烯烃弹性体标准溶液于透光性良好并处理好的溴化钾窗片上并将其均匀摊开，置于85℃烘箱中烘烤30-90min至溶剂完全挥发(以红外检测不出现溶剂峰为准)，根据涂布面积，计算涂布厚度及聚合物质量m并记录，即为规格为m的聚烯烃弹性体窗片；另取同样规格处理好的溴化钾窗片，根据记录m值，以100％m、50％m、25％m、10％m、5％m、3％m、1％m等数据分别进行马来酸酐标准溶液涂布，并控制涂布量，使其保持与聚烯烃弹性体涂布同样厚度，将涂布完成的马来酸酐窗片至于60℃烘箱中至完全干燥，即得到不同规格的马来酸酐窗片。Preparation of standard sample windows of different specifications: take 50 μL of polyolefin elastomer standard solution on a potassium bromide window with good light transmittance and treated and spread it evenly, place it in an 85°C oven and bake for 30-90 minutes until the solvent is completely evaporated (based on the absence of solvent peaks in infrared detection), calculate the coating thickness and polymer mass m according to the coating area and record them, which is the polyolefin elastomer window of specification m; take another potassium bromide window of the same specification and treat it, and according to the recorded m value, apply maleic anhydride standard solution at 100% m, 50% m, 25% m, 10% m, 5% m, 3% m, 1% m and other data respectively, and control the coating amount to keep the same thickness as the polyolefin elastomer coating, place the coated maleic anhydride window in a 60°C oven until completely dried, and obtain maleic anhydride windows of different specifications.
(2)建立吸光度-接枝率工作曲线(2) Establishing the absorbance-grafting rate working curve
使用如图1所示的工具将1枚所述聚烯烃弹性体窗片与1-3枚所述马来酸酐窗片组合，进行傅里叶红外分析后，以组合后所有改性酸窗片上涂布的改性酸质量之和占所述聚烯烃弹性体窗片上涂布的聚烯烃弹性体的质量百分数作为预期接枝率，得到如图2-4所示的不同预期接枝率(质量百分数)下的红外光谱，以1780cm-1处马来酸酐C＝O特征峰作为参考对象，依据朗博比尔定律A＝εLC，对于同一物质，吸光系数ε一致，L厚度一致，则吸光度A比值等效于测试物质浓度C比值，即吸光度A比值等效于本实施例中的接枝率比值，由此可以建立吸光度-接枝率工作曲线。Use the tool as shown in Figure 1 to combine one of the polyolefin elastomer windows with one to three of the maleic anhydride windows, perform Fourier infrared analysis, and take the sum of the mass of the modified acid coated on all the modified acid windows after combination as the mass percentage of the polyolefin elastomer coated on the polyolefin elastomer window as the expected grafting rate, and obtain infrared spectra at different expected grafting rates (mass percentages) as shown in Figures 2-4, and take the maleic anhydride C=O characteristic peak at 1780cm -1 as the reference object. According to the Lambert-Beer law A=εLC, for the same substance, the absorption coefficient ε is consistent, the thickness L is consistent, then the absorbance A ratio is equivalent to the test substance concentration C ratio, that is, the absorbance A ratio is equivalent to the grafting rate ratio in this embodiment, thereby an absorbance-grafting rate working curve can be established.
在本实施例中，将装载有100％m马来酸酐窗片与聚烯烃弹性体窗片组合，以1780cm-1处C＝O特征峰此时吸光度作为100％接枝率下的吸光度，在 不同马来酸酐窗片组合下得到50％、25％等接枝率下吸光度值，测试多个点即建立如图5所示的吸光度-接枝率工作曲线。In this embodiment, a window sheet loaded with 100% m maleic anhydride is combined with a polyolefin elastomer window sheet, and the absorbance of the C=O characteristic peak at 1780 cm -1 is taken as the absorbance at 100% grafting rate. The absorbance values at grafting rates of 50%, 25%, etc. were obtained under different combinations of maleic anhydride windows. By testing multiple points, the absorbance-grafting rate working curve shown in FIG. 5 was established.
(3)待测物分离提纯、测试及验证(3) Separation, purification, testing and verification of the analytes
本实施例中待测的铝塑膜内层胶为GL内层胶，取样测试GL内层胶固含量为12％(质量)，称量8.33gGL内层胶于烧杯中，并添加其2-5倍质量的乙酯，使聚合物析出，充分过滤并干燥后，使用滤布将得到的固体聚合物包裹，置于索氏抽提器中，使用乙酯溶剂进行2-4h反复萃取，以保证GL内层胶中的游离酸和小分子全部除净。将提纯后的GL内层胶置于100mL容量瓶中用二甲苯(AR)标定，标定完成后测试GL内层胶溶液浓度为10.21g/L，用移液枪移取50μLGL内层胶溶液涂抹至边长为14mm一次性溴化钾窗片上(涂膜面积一致，浓度相近，视为胶膜厚度一致)。于85℃烘箱烘烤至GL内层胶溶液挥发完全后，对其进行傅里叶红外光谱分析，得到如图6所示的GL内层胶窗片的红外光谱，分析结果为，1780cm-1处吸光度为0.0102，但其在2960cm-1处峰的强度(本实施例中峰强度以吸光度表示)与图2所示的0％接枝率下的红外光谱中对应主峰的强度并不一致，则以2960cm-1处峰为基准进行修正，测得GL内层胶窗片的红外光谱在2960cm-1处峰的吸光度为0.489，标准样的红外光谱在2960cm-1处峰的吸光度为0.556，结合工作曲线计算接枝率如下，接枝率＝(3.5348*0.0102+0.0231)*(0.489/0.556)＝5.2％。In this embodiment, the inner layer glue of the aluminum-plastic film to be tested is the GL inner layer glue. The solid content of the GL inner layer glue sampled and tested is 12% (mass). 8.33g of the GL inner layer glue is weighed in a beaker, and ethyl ester of 2-5 times its mass is added to precipitate the polymer. After sufficient filtration and drying, the obtained solid polymer is wrapped with a filter cloth and placed in a Soxhlet extractor. The ethyl ester solvent is used for repeated extraction for 2-4h to ensure that the free acid and small molecules in the GL inner layer glue are completely removed. The purified GL inner layer glue is placed in a 100mL volumetric flask and calibrated with xylene (AR). After the calibration, the concentration of the GL inner layer glue solution is tested to be 10.21g/L. 50μL of the GL inner layer glue solution is transferred with a pipette gun and smeared on a disposable potassium bromide window with a side length of 14mm (the coating area is consistent and the concentration is similar, which is regarded as the same film thickness). After baking in an oven at 85°C until the GL inner layer glue solution is completely evaporated, it is subjected to Fourier infrared spectroscopy analysis to obtain the infrared spectrum of the GL inner layer glue window piece as shown in Figure 6. The analysis result shows that the absorbance at 1780cm -1 is 0.0102, but the intensity of the peak at 2960cm -1 (the peak intensity in this embodiment is expressed as absorbance) is inconsistent with the intensity of the corresponding main peak in the infrared spectrum at 0% grafting rate shown in Figure 2. Then, correction is made based on the peak at 2960cm -1 . It is measured that the absorbance of the infrared spectrum of the GL inner layer glue window piece at the peak at 2960cm -1 is 0.489, and the absorbance of the infrared spectrum of the standard sample at the peak at 2960cm -1 is 0.556. The grafting rate is calculated in combination with the working curve as follows: grafting rate = (3.5348*0.0102+0.0231)*(0.489/0.556) = 5.2%.
为了验证该接枝率是否符合实际情况，将求得的接枝率5.2％四舍五入取整后，以5％为本实施例1需要进行验证的值，将1枚规格为m的聚烯烃弹性体窗片与1枚规格为5％m的马来酸酐窗片组合，随后进行傅里叶红外分析，得到验证用红外光谱；对比发现验证用红外光谱与GL内层胶的红外光谱在2960cm-1与1780cm-1处峰的强度一致，即验证求得的接枝率成功，5.2％为GL内层胶的接枝率。若验证不成功，则需重新选用新的聚烯烃弹性体颗粒和马来酸酐原料或其他种类的聚烯烃颗粒和改性酸原料绘制工作曲线。In order to verify whether the grafting rate is in line with the actual situation, the grafting rate of 5.2% is rounded off and 5% is taken as the value to be verified in this embodiment 1. A polyolefin elastomer window sheet with a specification of m is combined with a maleic anhydride window sheet with a specification of 5%m, and then Fourier infrared analysis is performed to obtain an infrared spectrum for verification; by comparison, it is found that the peak intensities of the infrared spectrum for verification and the infrared spectrum of the GL inner layer rubber at 2960cm -1 and 1780cm -1 are consistent, that is, the grafting rate obtained is successfully verified, and 5.2% is the grafting rate of the GL inner layer rubber. If the verification is unsuccessful, it is necessary to re-select new polyolefin elastomer particles and maleic anhydride raw materials or other types of polyolefin particles and modified acid raw materials to draw the working curve.
实施例2～4Embodiments 2 to 4
实施例2～4分别提供了一种针对针对铝塑膜内层胶性能的评估测试方法， 与实施例1相比，区别仅在于测试的内层胶的类型不同，实施例2～4测试的铝塑膜内层胶的类型分别为Vk118内层胶、Vk318内层胶、JP-PMA内层胶，其测试方法均与实施例一致，在此不在赘述。Embodiments 2 to 4 respectively provide a method for evaluating the performance of the inner layer adhesive of the aluminum-plastic film. Compared with Example 1, the only difference is the type of inner layer glue tested. The types of inner layer glue of aluminum-plastic film tested in Examples 2 to 4 are Vk118 inner layer glue, Vk318 inner layer glue, and JP-PMA inner layer glue, respectively. The testing methods are consistent with the examples and will not be repeated here.
实施例1～4的具体测试结果如表1所示。The specific test results of Examples 1 to 4 are shown in Table 1.
表1不同待测试样品的实施例结果图表
Table 1 Example results of different samples to be tested
根据表1可以看出，本发明提供的针对铝塑膜内层胶性能的评估测试方法可以对铝塑膜内层胶进行准确的定量分析，且能对不同类型的内层胶进行横向对比分析。在此基础上，根据求得的接枝率即可对铝塑膜内层胶的性能进行评估，评估标准为：接枝率越高，内层胶与铝层亲和力越强，与PP层亲和力越弱，通过在实际测试铝塑膜剥离力时剥离界面的表现可以确认需要提升哪方面性能，若胶从铝层脱落，则提示需要选用高接枝率内层胶，若胶从PP层脱落，则提示需要选用低接枝率内层胶。此外，测试接枝率作为有效官能团数量能够提示铝塑膜内层胶使用固化剂的量，避免固化剂不足或过剩。It can be seen from Table 1 that the evaluation test method for the performance of the inner layer glue of the aluminum-plastic film provided by the present invention can accurately quantitatively analyze the inner layer glue of the aluminum-plastic film, and can perform a horizontal comparative analysis of different types of inner layer glue. On this basis, the performance of the inner layer glue of the aluminum-plastic film can be evaluated according to the obtained grafting rate. The evaluation standard is: the higher the grafting rate, the stronger the affinity of the inner layer glue with the aluminum layer, and the weaker the affinity with the PP layer. By actually testing the peeling force of the aluminum-plastic film, the performance that needs to be improved can be confirmed. If the glue falls off from the aluminum layer, it is suggested that a high grafting rate inner layer glue needs to be selected. If the glue falls off from the PP layer, it is suggested that a low grafting rate inner layer glue needs to be selected. In addition, testing the grafting rate as the number of effective functional groups can indicate the amount of curing agent used in the inner layer glue of the aluminum-plastic film to avoid insufficient or excessive curing agent.
以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发 明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围。 The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be described in detail. The technical solution of the present invention can be modified or replaced by equivalents without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

  1. 一种针对铝塑膜内层胶性能的评估测试方法，其特征在于，包括以下步骤：A method for evaluating the performance of the inner layer adhesive of an aluminum-plastic film, characterized in that it comprises the following steps:
    (1)制备不同规格的标准样窗片(1) Preparation of standard sample windows of different specifications
    配制预定浓度的聚烯烃标准溶液和改性酸标准溶液；将预定体积的所述聚烯烃标准溶液均匀涂布于处理好的窗片上，烘干后得到聚烯烃窗片；按照与所述聚烯烃标准溶液相同的涂布厚度将不同质量的所述改性酸标准溶液分别涂布于不同的处理好的窗片上，烘干后得到不同规格的改性酸窗片；所述改性酸窗片上涂布的改性酸的质量占所述聚烯烃窗片上涂布的聚烯烃的质量的1％-100％；Prepare a polyolefin standard solution and a modified acid standard solution of a predetermined concentration; evenly apply a predetermined volume of the polyolefin standard solution on the treated window sheet, and obtain the polyolefin window sheet after drying; apply different masses of the modified acid standard solution on different treated window sheets according to the same coating thickness as the polyolefin standard solution, and obtain modified acid windows of different specifications after drying; the mass of the modified acid coated on the modified acid window sheet accounts for 1%-100% of the mass of the polyolefin coated on the polyolefin window sheet;
    (2)建立吸光度-接枝率工作曲线(2) Establishing the absorbance-grafting rate working curve
    使用工具将1枚所述聚烯烃窗片与至少1枚所述改性酸窗片组合，进行傅里叶红外分析，以组合后所有改性酸窗片上涂布的改性酸质量之和占所述聚烯烃窗片上涂布的聚烯烃的质量的百分数作为预期接枝率，得到不同预期接枝率下的标准样的红外光谱，并根据所述红外光谱中预定波长处的吸光度建立吸光度-接枝率工作曲线；Using a tool to combine one of the polyolefin window sheets with at least one of the modified acid window sheets, and performing Fourier infrared analysis, taking the percentage of the sum of the mass of the modified acid coated on all the modified acid window sheets after combination to the mass of the polyolefin coated on the polyolefin window sheet as the expected grafting rate, obtaining infrared spectra of standard samples under different expected grafting rates, and establishing an absorbance-grafting rate working curve according to the absorbance at a predetermined wavelength in the infrared spectrum;
    (3)待测样分离提纯、测试及验证(3) Separation, purification, testing and verification of samples
    取待测铝塑膜内层胶主剂置于预定量的乙酯中，待所述铝塑膜内层胶中的聚合物充分析出后，依次进行过滤、干燥与萃取，得到提纯后的内层胶；The main agent of the inner layer adhesive of the aluminum-plastic film to be tested is placed in a predetermined amount of ethyl ester, and after the polymer in the inner layer adhesive of the aluminum-plastic film is fully precipitated, filtering, drying and extraction are performed in sequence to obtain the purified inner layer adhesive;
    依照配制所述聚烯烃标准溶液的方法，将所述提纯后的内层胶配制为与所述聚烯烃标准溶液浓度一致的待测样标准溶液，取所述待测样标准溶液于新的处理好的窗片上，烘干后进行傅里叶红外分析，根据待测样的红外光谱确认待测样主体聚合物组分和预定波长处的吸光度，再根据所述工作曲线计算出待测样的接枝率；According to the method for preparing the polyolefin standard solution, the purified inner layer rubber is prepared into a sample standard solution having the same concentration as the polyolefin standard solution, the sample standard solution is placed on a newly treated window, and after drying, Fourier infrared analysis is performed, the main polymer component of the sample to be tested and the absorbance at a predetermined wavelength are confirmed according to the infrared spectrum of the sample to be tested, and then the grafting rate of the sample to be tested is calculated according to the working curve;
    将所述聚烯烃窗片与所述改性酸窗片按照所述待测样的接枝率进行组合，随后进行傅里叶红外分析，得到验证用红外光谱；将所述验证用红外光谱与所述待测样的红外光谱进行一致性对比，若一致性符合要求，则根据所述待测样 的接枝率对所述铝塑膜内层胶的性能进行评估；若一致性不符合要求，则表明所述工作曲线失效或选用原料有误，需重新选用原料绘制工作曲线。The polyolefin window and the modified acid window are combined according to the grafting rate of the sample to be tested, and then Fourier infrared analysis is performed to obtain an infrared spectrum for verification; the infrared spectrum for verification is compared with the infrared spectrum of the sample to be tested for consistency. If the consistency meets the requirements, the sample to be tested is tested according to the method described in the embodiment of the present invention. The grafting rate is used to evaluate the performance of the inner layer adhesive of the aluminum-plastic film; if the consistency does not meet the requirements, it indicates that the working curve is invalid or the raw material is incorrectly selected, and the raw material needs to be re-selected to draw the working curve.
  2. 根据权利要求1所述的针对铝塑膜内层胶性能的评估测试方法，其特征在于：所述聚烯烃包括聚丙烯、聚乙烯、聚烯烃弹性体中的一种或几种；所述聚烯烃标准溶液的预定浓度为1-10g/L；所述预定体积为10μL-100μL。The evaluation and testing method for the inner layer adhesive performance of aluminum-plastic film according to claim 1 is characterized in that: the polyolefin includes one or more of polypropylene, polyethylene, and polyolefin elastomer; the predetermined concentration of the polyolefin standard solution is 1-10g/L; and the predetermined volume is 10μL-100μL.
  3. 根据权利要求1所述的针对铝塑膜内层胶性能的评估测试方法，其特征在于：所述改性酸包括马来酸酐或丙烯酸；所述改性酸标准溶液的预定浓度为0.1-1g/L。The evaluation and testing method for the performance of the inner layer adhesive of the aluminum-plastic film according to claim 1 is characterized in that: the modified acid includes maleic anhydride or acrylic acid; and the predetermined concentration of the modified acid standard solution is 0.1-1g/L.
  4. 根据权利要求1所述的针对铝塑膜内层胶性能的评估测试方法，其特征在于：制备所述聚烯烃窗片时，将涂布有所述聚烯烃标准溶液的窗片置于60-90℃烘箱中烘烤30-90min至溶剂完全挥发。The evaluation and testing method for the performance of the inner layer adhesive of the aluminum-plastic film according to claim 1 is characterized in that: when preparing the polyolefin window sheet, the window sheet coated with the polyolefin standard solution is placed in a 60-90°C oven and baked for 30-90 minutes until the solvent is completely volatilized.
  5. 根据权利要求1所述的针对铝塑膜内层胶性能的评估测试方法，其特征在于：所述窗片为溴化钾窗片；所述窗片为圆形或方形，圆形窗片直径为10-18mm，方形窗片边长为10-18mm；所述处理好的窗片的处理过程为：将表面发白发雾窗片置于加有异丙醇混合液的1200-2000目金相砂纸上摩擦至表面均匀，若窗片无发雾，则略过此步；然后将处理后窗片擦干，再次滴加异丙醇混合液于窗片表面，用丝绒金相抛光布进行抛光；所述异丙醇混合液由异丙醇和蒸馏水按预定的体积比混合而成，所述异丙醇混合溶液中异丙醇的体积占比为85-95％。According to claim 1, the evaluation and testing method for the inner layer adhesive performance of the aluminum-plastic film is characterized in that: the window is a potassium bromide window; the window is round or square, the diameter of the round window is 10-18 mm, and the side length of the square window is 10-18 mm; the processing process of the treated window is: the window with a whitish and foggy surface is placed on a 1200-2000 mesh metallographic sandpaper added with an isopropyl alcohol mixture and rubbed until the surface is uniform. If the window is not foggy, this step is skipped; then the treated window is wiped dry, the isopropyl alcohol mixture is dripped on the surface of the window again, and polished with a velvet metallographic polishing cloth; the isopropyl alcohol mixture is prepared by mixing isopropyl alcohol and distilled water in a predetermined volume ratio, and the volume proportion of isopropyl alcohol in the isopropyl alcohol mixed solution is 85-95%.
  6. 根据权利要求1所述的针对铝塑膜内层胶性能的评估测试方法，其特征在于：在步骤(2)中，所述预定波长处的吸光度为1780cm-1处的吸光度。The evaluation and testing method for the performance of the inner layer adhesive of the aluminum-plastic film according to claim 1 is characterized in that: in step (2), the absorbance at the predetermined wavelength is the absorbance at 1780 cm -1 .
  7. 根据权利要求1所述的针对铝塑膜内层胶性能的评估测试方法，其特征在于：在步骤(3)中，所述预定量的乙酯的质量为所述待测铝塑膜内层胶主剂的2-5倍。The evaluation and testing method for the performance of the inner layer adhesive of the aluminum-plastic film according to claim 1 is characterized in that: in step (3), the mass of the predetermined amount of ethyl ester is 2-5 times the mass of the main agent of the inner layer adhesive of the aluminum-plastic film to be tested.
  8. 根据权利要求6所述的针对铝塑膜内层胶性能的评估测试方法，其特征在于：在步骤(3)中，根据工作曲线计算接枝率时，若所述待测样的红外光谱与所述标准样的红外光谱中主峰强度一致，则将1780cm-1处峰的吸光度代入所 述工作曲线求出待测样的接枝率；若所述待测样的红外光谱与所述标准样的红外光谱中主峰强度不一致，则以2960cm-1处峰为基准，依照接枝率＝(1780cm-1处计算的接枝率*待测样的红外光谱在2960cm-1处峰强度/标准样的红外光谱在2960cm-1处峰强度)进行修正，即得到铝塑膜内层胶接枝率数值。The method for evaluating the performance of the inner layer adhesive of the aluminum-plastic film according to claim 6 is characterized in that: in step (3), when calculating the grafting rate according to the working curve, if the infrared spectrum of the sample to be tested is consistent with the main peak intensity in the infrared spectrum of the standard sample, the absorbance of the peak at 1780 cm -1 is substituted into the The grafting rate of the sample to be tested is calculated by the working curve; if the main peak intensity in the infrared spectrum of the sample to be tested is inconsistent with that in the infrared spectrum of the standard sample, the peak at 2960 cm -1 is used as the reference, and correction is made according to grafting rate = (grafting rate calculated at 1780 cm -1 *peak intensity at 2960 cm -1 of the infrared spectrum of the sample to be tested/peak intensity at 2960 cm -1 of the infrared spectrum of the standard sample), so as to obtain the grafting rate value of the inner layer adhesive of the aluminum-plastic film.
  9. 根据权利要求6所述的针对铝塑膜内层胶性能的评估测试方法，其特征在于：在步骤(3)中，进行所述一致性对比时，若所述验证用红外光谱和所述待测样的红外光谱在2960cm-1与1780cm-1处峰的强度一致，或者所述验证用红外光谱和所述待测样的红外光谱在所述1780cm-1处峰的强度偏差不超过10％且所述验证用红外光谱和所述待测样的红外光谱在所述2960cm-1与1780cm-1处峰的强度的比例关系一致，则一致性符合要求；若所述验证用红外光谱和所述待测样的红外光谱在所述2960cm-1与1780cm-1处峰的强度的比例关系不一致，或者在所述2960cm-1与1780cm-1处峰的强度的比例关系一致但在所述1780cm-1处峰的强度偏差超过10％时，则一致性不符合要求。The evaluation and testing method for the performance of the inner layer adhesive of the aluminum-plastic film according to claim 6 is characterized in that: in step (3), when the consistency comparison is performed, if the peak intensities of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 2960 cm -1 and 1780 cm -1 are consistent, or the peak intensity deviation of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 1780 cm -1 does not exceed 10% and the ratio of the peak intensities of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 2960 cm -1 and 1780 cm -1 is consistent, then the consistency meets the requirements; if the ratio of the peak intensities of the verification infrared spectrum and the infrared spectrum of the sample to be tested at 2960 cm -1 and 1780 cm -1 is inconsistent, or the ratio of the peak intensities at 2960 cm -1 and 1780 cm -1 is consistent but the peak intensity deviation at 1780 cm -1 exceeds 10%, then the consistency does not meet the requirements.
  10. 一种针对铝塑膜内层胶性能的评估测试工具，其特征在于，该工具沿垂直于红外光照射的方向平行设置有若干个插槽，用于放置以不同形式组合的聚烯烃窗片和改性酸窗片。 A tool for evaluating and testing the performance of the inner layer adhesive of an aluminum-plastic film, characterized in that the tool is provided with a plurality of slots in parallel along a direction perpendicular to infrared light irradiation, for placing polyolefin windows and modified acid windows in different combinations.
PCT/CN2023/107183 2022-11-17 2023-07-13 Method and tool for evaluating and testing performance of inner layer adhesive for aluminum-plastic film WO2024103812A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211461524.1A CN116087135B (en) 2022-11-17 2022-11-17 Evaluation test method for performance of inner layer adhesive of aluminum plastic film
CN202211461524.1 2022-11-17

Publications (1)

Publication Number Publication Date
WO2024103812A1 true WO2024103812A1 (en) 2024-05-23

Family

ID=86203279

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/107183 WO2024103812A1 (en) 2022-11-17 2023-07-13 Method and tool for evaluating and testing performance of inner layer adhesive for aluminum-plastic film

Country Status (2)

Country Link
CN (1) CN116087135B (en)
WO (1) WO2024103812A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116087135B (en) * 2022-11-17 2024-04-26 广东广麟材耀新能源材料有限公司 Evaluation test method for performance of inner layer adhesive of aluminum plastic film

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019167447A (en) * 2018-03-23 2019-10-03 Ｍｃｐｐイノベーション合同会社 Modified polyethylene composition for adhesive sheet and adhesive sheet
CN110441253A (en) * 2019-07-22 2019-11-12 杭州华聚复合材料有限公司 A kind of method of quick detection PP-g-MAH grafting rate
CN111795942A (en) * 2020-07-08 2020-10-20 上海叶心材料科技有限公司 Method for detecting grafting rate of polyolefin maleic anhydride
CN114235735A (en) * 2021-11-26 2022-03-25 北方华锦化学工业股份有限公司 Method for quantitatively analyzing content of transparent agent in industrial transparent polypropylene by infrared spectroscopy
CN216207976U (en) * 2021-10-18 2022-04-05 惠州市广麟材耀科技有限公司 Infrared detection sample preparation device for adhesive high polymer
CN116087135A (en) * 2022-11-17 2023-05-09 广东广麟材耀新能源材料有限公司 Evaluation test method and tool for performance of inner glue of aluminum plastic film

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010117202A (en) * 2008-11-12 2010-05-27 Sumitomo Electric Ind Ltd Method of forming calibration curve for quantitation assay in infrared spectroscopy and quantity determination method
KR20140047757A (en) * 2012-10-12 2014-04-23 동우 화인켐 주식회사 Evaluating method of hardness of curable material
JP3183194U (en) * 2013-02-18 2013-05-09 株式会社島津製作所 Sample holder for film-like sample transmission measurement in Fourier transform infrared spectrophotometer
CN106324186A (en) * 2016-11-02 2017-01-11 泸州北方化学工业有限公司 Method for determining grafting ratio of maleic anhydride grafting chlorinated polypropylene
US11022548B2 (en) * 2017-05-02 2021-06-01 Ping Lin Sample holder for use in infrared spectroscopy
CN108254334B (en) * 2017-12-29 2020-12-22 黄河三角洲京博化工研究院有限公司 Method for detecting mass content of each component in polyolefin
CN113484271B (en) * 2021-07-06 2023-07-04 绍兴文理学院 Quantitative analysis method for grafting rate of grafted silk
CN114965344A (en) * 2022-05-16 2022-08-30 合肥国轩高科动力能源有限公司 Quantitative analysis method for SEI (solid electrolyte interphase) film of lithium ion battery cathode

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019167447A (en) * 2018-03-23 2019-10-03 Ｍｃｐｐイノベーション合同会社 Modified polyethylene composition for adhesive sheet and adhesive sheet
CN110441253A (en) * 2019-07-22 2019-11-12 杭州华聚复合材料有限公司 A kind of method of quick detection PP-g-MAH grafting rate
CN111795942A (en) * 2020-07-08 2020-10-20 上海叶心材料科技有限公司 Method for detecting grafting rate of polyolefin maleic anhydride
CN216207976U (en) * 2021-10-18 2022-04-05 惠州市广麟材耀科技有限公司 Infrared detection sample preparation device for adhesive high polymer
CN114235735A (en) * 2021-11-26 2022-03-25 北方华锦化学工业股份有限公司 Method for quantitatively analyzing content of transparent agent in industrial transparent polypropylene by infrared spectroscopy
CN116087135A (en) * 2022-11-17 2023-05-09 广东广麟材耀新能源材料有限公司 Evaluation test method and tool for performance of inner glue of aluminum plastic film

Also Published As

Publication number Publication date
CN116087135A (en) 2023-05-09
CN116087135B (en) 2024-04-26

Similar Documents

Publication Publication Date Title
WO2024103812A1 (en) Method and tool for evaluating and testing performance of inner layer adhesive for aluminum-plastic film
Mirabella Jr Internal reflection spectroscopy
WO2022017520A1 (en) Trypsin detection film, preparation method therefor, application thereof, and trypsin detection kit
CN104155302B (en) Method for detecting silicon crystal defects
Mirabella Jr Strength of interaction and penetration of infrared radiation for polymer films in internal reflection spectroscopy
CN1654519A (en) Reaction liquid for modifying polymer film and modifying method
Compton et al. Optimization of data recorded by internal reflectance spectroscopy
CN107661752B (en) Graphene oxide/Prussian blue nanoparticle composite material solid-phase microextraction probe and preparation method and application thereof
CN107991372B (en) Method for detecting lead ions
CN110646344A (en) Characterization method and characterization device for electrode plate bonding performance
JP5399338B2 (en) Porous material density evaluation method and porous material density evaluation system
CN107415273A (en) Prepreg manufacture method
JP4817308B2 (en) Sample surface treatment method for thermophysical property measurement
Gheorghiu et al. Electrochemical behavior of oxazoline‐based plasma polymers for biosensing applications
CN111122516B (en) Method for detecting retroreflection performance of glass beads
CN110658135A (en) Characterization method and characterization device for electrode plate bonding performance
De Witte et al. The use of a PY-GC-MS technique for the analysis of synthetic resins
JP2022167404A (en) Inspection method and processing inspection device for battery electrode material
CN215415074U (en) Test paper strip for rapidly detecting nitrite nitrogen in water
EP4237258A1 (en) Liquid foams of ethylene vinyl acetate resin/s for the restoration of paintings on canvas
CN114034662B (en) High-compatibility portable biological detection device based on gold nanopore array and preparation method and application thereof
CN112798373B (en) Method for detecting blood Benzhou's protein
CN115197463A (en) Preparation method and application of sulfadiazine molecularly imprinted one-dimensional photonic crystal sensor film
DE10215731B4 (en) Measuring cell and method for determining the zeta potential using flow potential and flow current measurements and for determining data using ATR-FTIR spectroscopy
Said et al. Investigation of one-step superglue fuming for visualization of latent fingermarks