WO2004017056A1 - Determination des caracteristiques mecaniques de produits polymeres par spectroscopie raman - Google Patents

Determination des caracteristiques mecaniques de produits polymeres par spectroscopie raman Download PDF

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Publication number
WO2004017056A1
WO2004017056A1 PCT/EP2003/008904 EP0308904W WO2004017056A1 WO 2004017056 A1 WO2004017056 A1 WO 2004017056A1 EP 0308904 W EP0308904 W EP 0308904W WO 2004017056 A1 WO2004017056 A1 WO 2004017056A1
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WIPO (PCT)
Prior art keywords
polymer
mechanical property
polymer product
determined
reactors
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Application number
PCT/EP2003/008904
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English (en)
Inventor
Dieter Lilge
Claus Gabriel
Original Assignee
Basell Polyolefine Gmbh
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
Priority claimed from DE2002137394 external-priority patent/DE10237394A1/de
Application filed by Basell Polyolefine Gmbh filed Critical Basell Polyolefine Gmbh
Priority to AU2003255419A priority Critical patent/AU2003255419A1/en
Publication of WO2004017056A1 publication Critical patent/WO2004017056A1/fr

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    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering

Definitions

  • the invention relates to a process for determining mechanical properties of polymer products with the aid of Raman spectroscopy. 5
  • Claims 2 to 18 contain preferred embodiments of the process according to the invention.
  • the invention is based on the fact that the mechanical properties of polymers may be determined with the aid of Raman spectroscopy. To this end, a Raman spectrum of the at least one polymer product is recorded and the at least one mechanical property of the polymer product is determined from it.
  • Useful comonomers are again C 2 -C 20 1- alkenes, in particular ethene, propene, 1-butene or 1-hexene, but the process is also applicable to other copolymers such as EPDM, EVA, etc. These may be random or else block or graft copolymers.
  • Blends and compounds of different polymers or polymers provided with colorants and fillers can also be mechanically characterized in a rapid and simple fashion by the method described.
  • the process is applicable to HDPE, LDPE and LLDPE, but also to polyamides and other semicrystalline polymers, copolymers thereof and blends thereof.
  • the applicability of the process substantially depends only on the mechanical properties in the polymer being reflected in some manner in the Raman-active molecular vibrations, so that a correlation results between the change in the spectrum and the mechanical property.
  • the Raman spectrum of the polymer products may in principle be recorded in liquid or solid form.
  • the sample form is variable within a wide range so that working the samples up before recording the Raman spectra is normally unnecessary.
  • preference is accordingly also given to granules, lumps, meal or powder.
  • Mechanical properties of the polymer product may be any property of the polymer product which characterizes its macroscopic-mechanical behavior and can be determined with the aid of mechanical measuring methods. These include in particular the elastic and inelastic deformability and also the rheological properties of the polymer product.
  • Preferred mechanical properties are the modulus of elasticity, the tensile strength, the yield stress, the flexural modulus, the flexural strength and the impact strength, although the process would not be restricted to the properties mentioned. Rather, any mechanical property of the polymer product which is known to those skilled in the art and can be determined from the Raman spectrum can be used. Particularly preferred mechanical properties are the modulus of elasticity and the yield stress.
  • the process according to the invention also makes it possible to realize in a relatively simple manner the online determination of the mechanical properties of a polymer product during an operating polymerization process, whether it be on the laboratory, pilot plant or industrial scale.
  • samples may be continuously withdrawn from the reactor and their mechanical properties may be investigated with the aid of Raman spectroscopy. Changes in the mechanical properties of the polymer product during the production process may thus be quickly detected and appropriate corrective measures may be taken.
  • the process according to the invention is particularly effective when the mechanical property is determined for an array of a multiplicity of polymer products.
  • many Raman spectra of different polymer products may be recorded in direct succession which allows the combination with a high throughput reactor system which delivers a large number of polymers having varying properties.
  • This is true in particular when the multiplicity of polymer products differs in the desired and determined mechanical properties.
  • the polymer products may be arrayed as a series or preferably as a two-dimensional field. However, any other array is conceivable in principle, as long as only the polymers to be investigated can be physically assigned to the array. In the simplest case, a microtiter plate may be used. It is normally possible to determine more than one different mechanical property of the polymer product from one spectrum.
  • the calibration spectrum is determined by analyzing polymers of known mechanical properties. The known statistical methods may be used here. Calibration makes it possible to forecast the mechanical product properties which have been determined by standard testing methods.
  • the polymer samples of known composition and known mechanical properties which have been previously determined with the aid of conventional methods are placed in the Raman spectrometer under the conditions under which the polymer products to be characterized are subsequently analyzed and at least one Raman spectrum of each is recorded.
  • the mechanical properties to be determined within the polymers are varied within a very wide range, at least within the range to be expected for the analysis of unknown samples, it is also important that the magnitude ratios of the mechanical properties relative to each other are varied to a very large extent in order to avoid redundancies and facilitate very accurate forecasts.
  • the wavelength range used for the calibration is in the range from 560 to 1980 cm "1 , a preferred range for polyethylene is from 1000 to 1500 cm "1 , and a preferred range for polypropylene is from 750 to 1550 cm "1 .
  • Preference is given to generating the calibration spectra by interpolating the crude spectra recorded in wavelength steps of 2 cm “1 , and the resolution of the analytical instrument is 1.4 cm “1 .
  • the calibration spectra may be compared with the sample spectra by assuming a linear relationship between scattering intensity and the mechanical property in a similar manner to the Beer-Lambert law for characteristic Raman bands, as described, for example, in Journal of Polymer Science, Polymer Physics Edition Vol. 16 (1978), 1181 for determining the crystallinity.
  • chemometric methods are generally known to those skilled in the art and is described, for example, in Matthias Otto: Chemometrics, Wiley-VCH, 1999. This combines the advantages of ILS and CLS and delivers optimal results for the application according to the invention.
  • ILS Inverse Least Squares
  • CLS Classical Least Squares
  • PCR Principal Component Regression
  • Principal Component Regression involves calibrating selected regions of the Raman spectrum with the aid of polymer products of known mechanical properties and then carrying out a regression of the selected spectral region on the mechanical property using this calibration.
  • preference is given to using two further partial least squares methods PLS1 and PLS2 for the chemometric analysis which are provided by the program used.
  • the regression may be carried out with the aid of commercial programs.
  • the PCR was carried out using the program Spectrum Quant ⁇ (Version 4-1) from Perkin Elmer.
  • the calibration is carried out with or without cross-validation, preferably with cross-validation. Criteria taken into account for the quality of the calibration include the number of principal components, the variance and the standard forecast error and also the application of the regression to the predefined and estimated values.
  • the process according to the invention can be particularly advantageously applied to optimize the preparative process of a polymer product with reference to at least one mechanical property by converting one or more reactants to a polymer product in a multiplicity of reactors under polymerization conditions, then analyzing at least one mechanical property of the polymer products resulting from each reactor according to the above-described processes with the aid of Raman spectroscopy and finally selecting the polymer products from the individual reactors with reference to the at least one mechanical property.
  • Variation of the reactant concentrations or the reaction parameters allows a polymer product to be tailored exactly to a predefined mechanical property or property combination, or a combinatorial database to be constructed with which it is possible to systematically select the reactants, catalysts and reaction conditions.
  • a reactant is any chemical material which can be converted with or without a catalyst to one or more polymer products. These also include auxiliaries and additives.
  • the process is applicable irrespective of whether the reactant is a gas, a liquid or a solid.
  • the reactant only has to be present in fluid form, i.e. it has to be possible to supply it to the reactor. It may be necessary to dissolve, suspend or disperse the reactant in a fluid carrier stream in order to be able to supply it to the reactor.
  • a polymer product is any polymer resulting from the reaction, irrespective of its chemical or physical properties. Preference is also given here to using C 2 to C 2 o alkenes and mixtures thereof as reactants.
  • one of the reactants may itself also be a polymer which is reactively grafted with the a further low molecular weight component, for example maleic anhydride, or an oligomeric or polymeric component.
  • the process according to the invention may further be applied to selecting from a multiplicity of catalysts for preparing a polymer product in a high throughput screening and thus optimizing the reactants, additives, preparative processes and processing methods used. In such a screening, a multiplicity of catalysts for preparing a polymer product is first introduced into an array of reactors and one or more reactants is or are added to each individual reactor and contacted with the catalysts under predefined reaction conditions.
  • the catalyst may also be in any form and any aggregate state, as long as it can be secured in the reactor.
  • catalysts also include catalyst mixtures or catalysts activated by cocatalysts.
  • the process according to the invention is suitable for selecting metallocene catalysts, chromium catalysts or Ziegler-Natta catalysts for polymerizing polyolefins. Such catalysts are often used in polymer production and generally known to those skilled in the art.
  • reactants or catalysts used in the individual reactors differ in at least one chemical and/or physical property. It is also possible to vary reactant properties and catalyst properties in combination.
  • the chemical property may consist in any molecular property such as constitution, configuration or conformation. This also include enantiomeric forms of catalysts.
  • Examples of physical properties include the particle shape and size of the catalyst or catalyst support chosen, its surface, the average pore volume and the pore volume distribution.
  • physical parameters include any physical quantity which has an influence on the course of polymerization to form the polymer product. These include in particular temperature, pressure, reactant or product concentrations and distributions, introduction and withdrawal of reactants and products, fixed or fluidized bed methods, reaction time or residence time, etc., without the process according to the invention being restricted to the parameters mentioned. Preference is given to a temperature range of from -80 to 200°C, r ⁇ ore preferably from 0 to 100°C, and a pressure range of from 10 "4 to 10 2 MPa, more preferably from 10 "2 to 6 MPa.
  • the process according to the invention may exhibit its particular strength when the reaction conditions in each individual reactor during the polymerization process differ in exactly one reaction parameter.
  • the optimum variation of the reaction conditions may be planned using the generally known principles of the combinatorial approach, in particular of combinatorial chemistry.
  • a preferred embodiment of the process according to the invention involves recording the Raman spectrum of the at least one polymer product immediately within each individual reactor which had previously been used to carry out the polymerization.
  • the advantage of Raman spectroscopy of working with visible light and obtaining the information from the vibrations via the shifting ofthe wavelength of the scattered light has the great advantage that simple optical elements of glass or quartz may be used to inject the analytical beam into the reactor and that analysis without transferring the samples to separate analytical holders is realized in a simple manner.
  • IR-transparent windows with which each of the reactors would have to have been equipped are superfluous. When reactors of glass or quartz are used, injection windows may even be omitted entirely.
  • this variant even opens the possibility of following the mechanical properties of the polymer product on-line during the progress of the polymerization reaction when Raman spectra of the reaction mixture are recorded continuously during it and then converted into the desired mechanical properties.
  • the reactors are operated continuously under the polymerization conditions, in particular when the catalysts are supported and may be used in a fluidized bed.
  • fluid reactants this may be achieved by the reactant or reactants themselves generating a sufficient flow through the reactor to perform the reaction in a suitable manner.
  • an inert carrier fluid may be admixed to the reactant stream.
  • batchwise operation is likewise suitable.
  • a number of reactors used in the array is chosen depending on the use. For a rapid screening to preselect suitable catalysts, a relatively large number of relatively small parallel reactors is used to very quickly limit the number of suitable catalysts. In this case, the polymerization conditions are varied only to a limited extent. In this case, preference is given to using 8, 16, 24, 32, 48, 64, 96 and 112 reactors which have a volume from 1 to 50 cm 3 , preferably from 5 to 20 cm 3 , more preferably from 10 to 15 cm 3 . Preference is likewise given to combining the reactors into blocks which more preferably each consist of 4 or 16 reactors.
  • the reaction parameters can be set separately for each block. The size, the type, the material and other reactor properties are selected according to the reaction to be investigated and in such a manner that comparability with processes on the pilot plant or industrial scale is as easy as possible.
  • the array of reactors described also allows only one catalyst to be used and an exclusive optimization of the activation and reaction conditions to be carried out with increased analytical precision.
  • preference is given to using 4, 8 or 16 reactors arranged in parallel which in one embodiment customarily have a larger volume than in the rapid screening, preferably from 30 to 200 cm 3 , more preferably from 60 to 90 cm 3 .
  • the mechanical properties of unknown polyethylene samples were determined by polymerizing them in a high throughput reactor system from Chemspeed Ltd, Switzerland, which comprises from 4 to 112 parallel reactors.
  • the reactors are combined in blocks of 4 or 16 reactors which can be heated independently and to which pressure can be applied.
  • the reactors of a 16-block have a volume of 13 cm 3 , those of a 4-block 75 cm 3 .
  • the samples which were present as a powder, meal, lumps or granules, or as a liquid and required no further workup, were introduced into a microtiter plate for 24, 48 or 96 samples. The filling was carried out by hand, although automatic withdrawal is also contemplated. The filled microtiter plate was then introduced into the Raman spectrometer (Multiwell, Jobin Yvon Horiba, Bensheim, 532 nm, 150 mW output, spectral range from 560 to 1980 cm “1 , resolution 1.4 cm “1 , CCD detector with single grating, scattered light suppression by filter).
  • Raman spectrometer Multiwell, Jobin Yvon Horiba, Bensheim, 532 nm, 150 mW output, spectral range from 560 to 1980 cm "1 , resolution 1.4 cm “1 , CCD detector with single grating, scattered light suppression by filter).
  • the number of measurements per polymer sample and the measuring duration were input, and the number of measurements was customarily from 1 to 10, preferably from 3 to 5, and the measuring duration was in the range from 1 s to 60 s, preferably 5-15 s. In this case, the measurements were carried out at room temperature. Using a heating table, it is possible to analyze up to about 200°C. After the type of microtiter plate was input, the Raman spectra of each sample were recorded in succession. To this end, the sample table on which the microtiter plate is disposed is automatically movable in the horizontal x and y directions.
  • the laser beam of the Raman spectrometer in this case the second harmonic of an Nd:YAG laser (532 nm), was initially prefocused manually on the polymer surface by moving the objective in the vertical direction and observing the "light spot" resulting from the focus on a monitor.
  • the focus was preadjusted using a microtiter plate well which has the average filling height of the polymer samples. Focusing during the measurement was then effected automatically by the Raman spectrometer within a tolerance range of 2.5 mm.
  • the measurements themselves were made by moving to the center of the appropriate wells of the microtiter plate having the samples. This is effected for each well until the entire microtiter plate has been covered and at least one Raman spectrum of each sample has been recorded. In the present example, one spectrum was recorded per well.
  • the measurements were then stored automatically on an electronic medium and transferred to a computer for chemometric evaluation.
  • the spectra may be processed. Although it is possible to scale and smooth the spectra, this was not done in the present case. If, however, this had been done, it would have been effected with the aid of a reference band at 1300 cm "1 . Normalization and baseline correction were likewise not carried out. If, however, normalization or baseline correction had been carried out, they would have been effected with the aid of the 1st derivative and smoothing over 5 points.
  • the number of PCA factors used was initially defined, which may be varied from one to the number of spectra used. Preference is given to using a maximum of 5 PCA factors.
  • the mechanical property against which the regression is to be effected is then chosen. Preference is given to regression against the modulus of elasticity, the yield stress, the impact strength or the flexural strength, and particular preference to carrying out regression against more than one mechanical property with the aid of one spectrum.
  • the spectra used for the regression are selected while discarding by hand or automatically those having noticeable errors, significant noise, etc., and not using them for the regression.
  • the characteristic mechanical values modulus of elasticity E and yield stress ⁇ y were taken from the polyethylene product portfolio of Basell. Polyethylenes of highly differing density were used for the investigations (metallocene and Ziegler-Natta LLDPE, LDPE, MDPE, HOPE)
  • the characteristic mechanical values were used to calibrate the Raman spectra measured on the individual polyethylenes with the aid of Principal Component Regression (PCR) as the chemometric method.
  • Figures 1 and 2 show that Raman spectra allow good values to be determined both for the modulus of elasticity and for the yield stress.
  • the moduli of elasticity determined from the Raman spectra are plotted against the moduli of elasticity determined by conventional tensile tests. This results in a linear dependence with a variance of 98.3% and a standard forecast error of 117 MPa. The quality of the correlations is sufficient for the forecasting of mechanical properties of polyethylene from high throughput screening.
  • the characteristic mechanical value modulus of elasticity E were taken from propylene (co)polymers produced by the Novolen gas phase process. Either metallocene or Ziegler-Natta catalysts were used. The content of ethylene in the propylene homo- and copolymers were in the range from 0 to about 20 % by weight. The melt flow rates MFR (230 °C / 2,16 kg) according to ISO 1133 of the products were in the range from about 0.5 to 80 g/10 min.
  • Table 2 shows that the deviations between predicted and measured moduli of eleasticity are in the range of ⁇ 10%. Only in excepted cases deviations up to 20 % were found. A prediction is possible for a wide range of copolymer content.

Abstract

L'invention concerne un procédé permettant de déterminer les propriétés mécaniques des produits polymères. Ce procédé consiste à enregistrer le spectre Raman d'au moins un produit polymère, et à calculer au moins une propriété mécanique de ce produit polymère à partir du spectre Raman du produit. Ce procédé rapide, non effractif et reproductible qui ne requiert pas la préparation d'un échantillon, peut servir à la caractérisation mécanique de produits polymères et convient pour les processus de criblage à haut débit.
PCT/EP2003/008904 2002-08-12 2003-08-11 Determination des caracteristiques mecaniques de produits polymeres par spectroscopie raman WO2004017056A1 (fr)

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Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10237394.9 2002-08-12
DE2002137394 DE10237394A1 (de) 2002-08-12 2002-08-12 Verfahren zur Bestimmung mechanischer Eigenschaften von Polymerprodukten
US40819502P 2002-09-04 2002-09-04
DE60/408,195 2002-09-04

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007018739A1 (fr) * 2005-07-22 2007-02-15 Exxonmobil Chemical Patents Inc. Analyse de proprietes in situ d'un polymere fondu par spectroscopie raman pour le controle d'un dispositif de melange
US7874723B2 (en) 2006-11-27 2011-01-25 Basell Polyolefine Gmbh Method of rapidly determining the MFR in the high-pressure polymerization ethylene
CN104132929A (zh) * 2014-07-28 2014-11-05 浙江大学 一种重金属浓酸液体中深铬黄浓度的检测方法
CN104132923A (zh) * 2014-07-28 2014-11-05 浙江大学 一种重金属浓酸液体中浅铬黄浓度的检测方法
CN104132922A (zh) * 2014-07-28 2014-11-05 浙江大学 一种重金属浓碱液体中桔铬黄浓度的检测方法
WO2019195737A1 (fr) 2018-04-06 2019-10-10 Braskem America, Inc. Spectroscopie raman et apprentissage automatique de contrôle de qualité

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WO2002033388A1 (fr) * 2000-10-19 2002-04-25 General Electric Company Analyse in situ de carbonate de diphenyle (dpc) et de bisphenol a (bpa) dans du polycarbonate par spectroscopie raman
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US5999255A (en) * 1997-10-09 1999-12-07 Solutia Inc. Method and apparatus for measuring Raman spectra and physical properties in-situ
WO2000049395A1 (fr) * 1999-02-18 2000-08-24 Rhodia Chimie Procede de preparation de latex par (co)polymerisation en emulsion de monomeres ethyleniquement insatures, avec suivi direct en ligne par spectroscopie raman
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WO2002033388A1 (fr) * 2000-10-19 2002-04-25 General Electric Company Analyse in situ de carbonate de diphenyle (dpc) et de bisphenol a (bpa) dans du polycarbonate par spectroscopie raman
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007018739A1 (fr) * 2005-07-22 2007-02-15 Exxonmobil Chemical Patents Inc. Analyse de proprietes in situ d'un polymere fondu par spectroscopie raman pour le controle d'un dispositif de melange
US7874723B2 (en) 2006-11-27 2011-01-25 Basell Polyolefine Gmbh Method of rapidly determining the MFR in the high-pressure polymerization ethylene
CN104132929A (zh) * 2014-07-28 2014-11-05 浙江大学 一种重金属浓酸液体中深铬黄浓度的检测方法
CN104132923A (zh) * 2014-07-28 2014-11-05 浙江大学 一种重金属浓酸液体中浅铬黄浓度的检测方法
CN104132922A (zh) * 2014-07-28 2014-11-05 浙江大学 一种重金属浓碱液体中桔铬黄浓度的检测方法
CN104132923B (zh) * 2014-07-28 2016-09-14 浙江大学 一种重金属浓酸液体中浅铬黄浓度的检测方法
CN104132929B (zh) * 2014-07-28 2016-09-14 浙江大学 一种重金属浓酸液体中深铬黄浓度的检测方法
WO2019195737A1 (fr) 2018-04-06 2019-10-10 Braskem America, Inc. Spectroscopie raman et apprentissage automatique de contrôle de qualité
EP3775759A4 (fr) * 2018-04-06 2022-04-27 Braskem America, Inc. Spectroscopie raman et apprentissage automatique de contrôle de qualité

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