JP5437831B2 - Degradation evaluation method for polyether-containing polymers - Google Patents

Description

  The present invention relates to a method for evaluating the degree of deterioration of a polymer containing a polyether, such as a polyether-based polyurethane.

  Polymers containing polyethers such as polyether-based polyurethane in the polymer chain (hereinafter referred to as polyether-containing polymers) are excellent in mechanical properties and workability. The “sealing material” is used as a main component of an amorphous wet sealing material unless otherwise specified, and is often used particularly in the construction field. Architectural sealants are often used under harsh conditions such as outdoors, which are exposed to high temperatures, and high weather resistance is required. However, problems such as systematic maintenance and rain leaks are required. In order to prevent this, it is necessary to accurately evaluate the degree of deterioration in an actual use environment.

  As an item for judging the degree of deterioration of the sealing material, there is a method of inspecting the appearance of peeling of the sealing material from the exterior material, breakage, breakage, deformation, etc. of the sealing material itself. However, when deterioration that can be seen from the appearance inspection has occurred, the sealing material itself has often already deteriorated (Non-Patent Document 1). Therefore, there has been a need for a deterioration degree evaluation method that can evaluate the deterioration degree of the sealing material even at a stage where deterioration is not known from the appearance.

  Furthermore, when diagnosing the deterioration of sealing materials in buildings (aged buildings) that have been built for more than a few years, it was required that the sampling of the sealing materials be kept to a minimum and that repairs can be made easily on site. . Moreover, it is difficult to analyze a sealing material once applied after being dissolved in a solvent, and it has been necessary to analyze the sealing material in a solid state.

  Conventionally, as a method for evaluating deterioration of such a polyurethane-based sealant, Patent Document 1 proposes a method for evaluating the degree of deterioration by measuring the elution amount of a urethane component and the amount of a plasticizer. However, in this method, the amount of sample necessary for measurement is large, sampling from an aged building or the like is difficult, and the substance that is an indicator of deterioration is unknown, so it is difficult to quantitatively evaluate deterioration. Met.

  Further, Patent Document 2 discloses a method for determining the acid anhydride generated by degradation of polybutylene terephthalate using pyrolysis gas chromatography in the presence of alkali by pyrolysis gas chromatography / mass spectrometry. A method for evaluating the degree of deterioration of butylene terephthalate has been proposed. However, in this method, it is already known that the substance generated by the deterioration of polybutylene terephthalate is an acid anhydride, and the deterioration is evaluated using pyrolysis gas chromatography / mass spectrometry. Thus, polyether-containing polymers such as polyether-based polyurethanes cannot be employed because substances that are indicators of deterioration are not known.

JP 2004-137383 A JP 2001-356116 A

Waterproof Journal, Vol. 17, No. 3, pp. 65-72, 1986

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for evaluating the degree of deterioration of a polyether-containing polymer that can at least partially eliminate the above-mentioned problems.
In particular, an object of the present invention is to provide a method for evaluating the degree of deterioration of a polyether-containing polymer, which can be implemented with a very small amount of sample and can evaluate the deterioration state of the polyether-containing polymer with high accuracy.

According to the first invention, a polyether characterized in that the degree of degradation of the polyether-containing polymer is evaluated by measuring a change in the amount of thermal decomposition products derived from the polyether portion of the polyether-containing polymer. A method for evaluating the degree of degradation of a containing polymer , wherein the polyether part of the polyether-containing polymer contains a polyether triol, and diisopropyl ether is quantified as a thermal decomposition product derived from the polyether part. A method for evaluating the degree of deterioration of a polyether-containing polymer is provided.
According to the second invention, in the first invention, there is provided a method for evaluating the degree of deterioration of a polyether-containing polymer, wherein the polyether-containing polymer is a polyether-based polyurethane.
According to a third invention, in the first or second invention, the change in the amount of pyrolysis products derived from the polyether portion of the polyether-containing polymer is measured by pyrolysis gas chromatography. A method for evaluating the degree of deterioration of a polyether-containing polymer is provided.
According to the fourth invention, in the first or second invention, the change in the amount of pyrolysis products derived from the polyether portion of the polyether-containing polymer is measured by pyrolysis gas chromatography and mass spectrometry. A method for evaluating the deterioration degree of a polyether-containing polymer is provided .

  In addition to the above invention, a method for evaluating the degree of deterioration of a sealing material containing a polyether-containing polymer such as polyether-based polyurethane, preferably a change in the amount of thermal decomposition products derived from the polyether portion of the polyether-containing polymer Provides a method for evaluating the degree of deterioration of a sealing material, characterized by evaluating the degree of deterioration of the sealing material by measuring by pyrolysis gas chromatography or preferably by pyrolysis gas chromatography and mass spectrometry Here, in one embodiment, the polyether part of a polyether-containing polymer such as polyether-based polyurethane contains polyether triol, and diisopropyl ether is quantified as a thermal decomposition product derived from the polyether part.

  According to the present invention, it is possible to evaluate the degree of deterioration with high accuracy using a trace amount of a polyether-containing polymer sample.

It is the schematic of the thermal decomposition gas chromatography mass spectrometer which can be used in order to implement the degradation degree evaluation method concerning one Embodiment of this invention. The pyrograms (retention time: 0 minutes to 10 minutes) of the sealing material sample before the accelerated deterioration test (0 hour) and the sealing material sample after the accelerated deterioration test of 10,000 hours are shown. In the figure, peak 1 is diisopropyl ether and peak 2 is 4-isopropoxy-2-butanone. Samples of the sealing material before the accelerated deterioration test (0 hour) and the sealing material samples after the accelerated deterioration test of 2000 hours, 4000 hours, 6000 hours, 8000 hours, and 10,000 hours were measured by pyrolysis gas chromatography. Then, the area ratio of each peak of diisopropyl ether and 4-isopropoxy-2-butanone to the area of all peaks in the sample was calculated, and diisopropyl ether and 4-isopropoxy-2- The change of the area ratio of each peak in butanone is shown. Using a sealing material of the same composition as the one subjected to the accelerated deterioration test, the sealing material collected from the south surface of the building that has passed 5 years, 6 years, 11 years, 14 years has been measured by pyrolysis gas chromatography, The area ratio of each peak of diisopropyl ether and 4-isopropoxy-2-butanone to the area of all the peaks in the sealing material sample was calculated, and diisopropyl ether and 4-isopropoxy-2-butanone when the pre-deterioration was assumed to be 1 The change of the area ratio of each peak in is shown.

  The inventors of the present invention have found that the degree of change in the composition of specific components of the polyether-containing polymer indicates the degree of deterioration, not a method for evaluating the appearance or physical shape of the sealing material. That is, the present inventors succeeded in estimating the degree of deterioration of the polyether-containing polymer by measuring the thermal decomposition product derived from the polyether part of the polyether-containing polymer. Further, it has been found that it is preferable to use pyrolysis gas chromatography or pyrolysis gas chromatography and mass spectrometry in order to measure the pyrolysis product derived from the polyether moiety of the polyether-containing polymer.

  In other words, conventionally, polyether-containing polymers such as polyether-based polyurethane used for sealing materials for outdoor buildings have a three-dimensional cross-linking structure, the composition is extremely complicated, and various types of additives. Therefore, it was considered extremely difficult to analyze the deteriorated sealing material itself and evaluate the degree of deterioration of the polyether-containing polymer. However, as a result of diligent research, the present inventors have determined that a specific pyrolysis derived from the polyether part of the polyether-containing polymer, regardless of the additives contained in the sealing material, etc. It has been found that a product is produced and that the amount of pyrolysis product increases approximately in proportion to the degradation of the polyether-containing polymer.

  Therefore, in the degradation degree evaluation method according to an embodiment of the present invention, pyrolysis gas chromatography is used, and the amount of pyrolysis products derived from the polyether portion of the polyether-containing polymer, in one example, the composition ratio of the gas chromatogram. Is used to estimate the degree of degradation of the polyether-containing polymer. According to this method, the deteriorated polyether-containing polymer can be directly applied to the analysis sample as it is without being pretreated, so that it is possible to evaluate the degree of deterioration with high accuracy.

  Furthermore, in the degradation degree evaluation method according to another embodiment of the present invention, the pyrolysis gas chromatography mass spectrometry (pyrolysis) can be performed even if the types of the monomer components and additives constituting the polyether-containing polymer are not known. After performing qualitative analysis by an analysis method in which gas chromatography and mass spectrometry are continuously performed) or at the same time, quantitative degradation analysis is possible. Furthermore, in the present invention, it is possible to estimate the degree of deterioration even with a small amount of sample of several mg or less, and it is possible to overcome the problem in the conventional method of damaging a building when sampling from an aged building. In addition, the degree of deterioration of the polyether-containing polymer can be evaluated.

  Here, the “polyether-containing polymer” of the present invention is used as a sealing material for indoors and outdoors such as buildings. Therefore, in one aspect, the method for evaluating the degree of deterioration of the polyether-containing polymer of the present invention is a method for evaluating the degree of deterioration of the sealing material. Such a sealant usually contains a plasticizer in addition to the polyether-containing polymer, and further includes a heat stabilizer, an ultraviolet absorber, a light stabilizer, an antioxidant, an algaeproof agent, an antifungal agent, and an antifoaming agent. Further, a thickener, a dispersant, a filler, a pigment, and the like are appropriately contained.

  The polyether-containing polymer of the present invention may contain a polyether in the main chain or as a pendant chain as long as it contains a polyether in the molecule. Examples of the material include polyether-based polyurethane, polyether-modified silicone, polyether-modified polysulfide, particularly polyether-based polyurethane.

  Hereinafter, a typical polyether-based polyurethane will be described. This is obtained by a reaction between a curing agent having at least two isocyanate groups and a polyol compound having at least two hydroxyl groups.

The one-component polyether-based polyurethane is, for example, cured by reacting with moisture in the air using a prepolymer obtained by reaction of diisocyanate with polyether diol and polytriol as a raw material. The two-component polyether polyurethane is cured by reacting a prepolymer obtained by reaction of diisocyanate with polyether diol and polytriol and a polyol or polyamine as a curing agent.
Examples of the above-mentioned isocyanate include toluene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate.

  The above-mentioned polyol has two or more hydroxyl groups per molecule, and the number average molecular weight is preferably in the range of 400 to 7000. Examples of the diol include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and an ethylene oxide / propylene oxide copolymer. Examples of the triol include polyoxyethylene triol, polyoxypropylene triol, polyoxytetramethylene triol, and polyoxyhexamethylene triol. It is also preferable to use a mixture of triol and diol as appropriate.

  As the plasticizer, polymer plasticizers such as phthalate ester compounds, polyesters or aliphatic polyurethanes can be used alone or in combination. Typical examples of the heat stabilizer include a hindered phenol compound, the ultraviolet absorber includes a benzotriazole compound or a hydroxyphenyl triazine compound, and the light stabilizer includes a hindered amine compound.

  Pyrolysis gas chromatography (PyGC) is a separation / analysis method that instantly pyrolyzes a small amount of sample, introduces and separates the pyrolysis products into a gas chromatograph, and obtains a pyrogram (Koji Hiroshi, 2002). Hokkaido Industrial Research Institute Technical Information, Vol. 24, No. 4, p. 11). Thermal decomposition of samples such as black rubber, which was difficult with thermal analysis methods such as infrared spectroscopy and differential scanning calorimetry, and polymers with no melting point such as rubber and thermosetting resins Gas chromatography is applicable.

  Mass spectrometry (MS) is an analytical method used when determining the mass-to-charge ratio (value obtained by dividing mass by the number of charges) of a sample. In the method of the present invention, electron impact ionization, chemical ionization, field ionization, or fast atom bombardment ionization method can be used, and a single focusing magnetic field deflection type, a quadrupole type, an ion trap type, a double focusing type, or an ion cyclotron. A type of mass spectrometer can be used, but is not limited thereto.

  The degree of deterioration of the polyether-containing polymer or sealing material is determined by gas chromatogram of pyrolysis products derived from the polyether portion of the polyether-containing polymer by pyrolysis gas chromatography on the sampled polyether-containing polymer or sealing material. The composition ratio is calculated and evaluated by observing the change with time of the numerical value. Estimating the degree of degradation of a polyether-containing polymer by using the phenomenon that the composition ratio of the thermal decomposition products derived from the polyether portion in the polyether-containing polymer increases with the deterioration of the polyether-containing polymer. Is.

  Here, the “composition ratio of the thermal decomposition product derived from the polyether part in the polyether-containing polymer” means that it originates from the polyether part relative to the total thermal decomposition product generated by pyrolyzing the polyether-containing polymer. It means the content ratio of a specific thermal decomposition product. This content ratio can be estimated from the peak area ratio of the chromatogram.

  Further, the “thermal decomposition product derived from the polyether part” is alcohol, ether or ketone produced by the thermal decomposition of the polyether part. The thermal decomposition products when polyoxypropylene triol is used as the polyol are diisopropyl ether and 4-isopropoxy-2-butanone. In particular, diisopropyl ether has high sensitivity to deterioration, which is advantageous in determining the degree of deterioration.

  In the method of the present invention, the sample for evaluating the degree of deterioration of the polyether-containing polymer may be several mg, for example, and at least about 0.01 mg can be evaluated. Therefore, even when diagnosing the deterioration of the sealing material of an aged building, the sample can be easily collected with minimal damage to the building, for example, 0.01 to 1.0 mg is accurately weighed, It can use for a measurement sample. Therefore, in order to improve the reproducibility of the measurement, it is preferable to use the same amount of sample each time in the range of 0.3 to 0.5 mg.

  In addition, in the sealing material, in addition to a plasticizer, usually a heat stabilizer, an ultraviolet absorber, a light stabilizer, an antioxidant, an algae-proofing agent, an antifungal agent, an antifoaming agent, a thickener, a dispersant, Various additives such as fillers and pigments are included, but even if they are present, there is no problem in the evaluation of the deterioration degree of the sealing material.

  In the method of the present invention, since pyrolysis gas chromatography is used as an analysis method, it is possible to perform highly sensitive and highly accurate measurement even in a solid state sample. In the measurement, the gas generated by heating the sample is separated by a column to perform qualitative and quantitative measurement. Here, the heating temperature can be changed depending on the kind of the polyether-containing polymer, and is usually preferably 400 ° C. to 700 ° C. If the temperature is lower than 400 ° C., the decomposition of the polyether-containing polymer hardly occurs, so component analysis cannot be performed. When the temperature is higher than 700 ° C., the decomposition of the polyether-containing polymer and additives proceeds so much that a large amount of unnecessary components are produced, making it difficult to quantify. The heating conditions are preferably performed in a short time of 0.1 to 2 seconds uniformly over the entire sample. This is because when the heating time is prolonged, a side reaction occurs and a component different from the decomposition product is generated. In addition, by raising the temperature during heating, the polyether-containing polymer and the additive can be identified and analyzed.

  As a method for thermally decomposing a sample, a filament type, induction heating type, or heating furnace type pyrolysis apparatus is used, and an optimum one may be selected depending on the sample to be measured. The gas chromatograph apparatus may be a general apparatus, and the column stationary phase may be selected according to the sample to be measured. Regarding the detector, there are a flame ionization detector, a thermal conductivity detector, an electron capture detector, and the like, which can be selected as necessary.

  Moreover, when the component obtained by separating by pyrolysis gas chromatography is unknown, each component can be identified by performing mass spectrometry. It is preferable to use pyrolysis gas chromatography mass spectrometry (PyGC-MS) mass spectrometry using a series of apparatuses in which a pyrolysis gas chromatograph apparatus and a mass spectrometer are directly connected.

  FIG. 1 is a schematic view of a pyrolysis gas chromatography mass spectrometer. The polyether-containing polymer sample to be analyzed is put into the sample injection unit 2. When the temperature of the thermal decomposition apparatus 3 reaches a predetermined value, the input sample is supplied into the thermal decomposition apparatus 3 and rapidly heated to be decomposed. The gas generated by heating and decomposing the polyether-containing polymer sample is introduced into the column 4 by the carrier gas 1. When performing a gas chromatograph analysis, it is analyzed by the detector 6 through the splitter 5. When mass analysis is necessary, it is introduced into the interface 7 through the splitter 5 and then introduced into the mass spectrometer 8 to perform mass analysis. A double shot pyrolyzer PY-1020D manufactured by Frontier Laboratories can be used for the thermal decomposition section (thermal decomposition apparatus 3). Agilent's P-6890 can be used for the gas chromatograph part (detector 6). For the mass spectrometer (mass spectrometer 8), AutoMass-II manufactured by JEOL can be used.

  Such pyrolysis gas chromatography mass spectrometry enables qualitative analysis of samples, not only polyether-containing polymers, but also plasticizers, hindered phenol thermal stabilizers, hindered amine light stabilizers (HALS) and UV absorption. Qualitative and quantitative determination of additives such as an agent (UVA) becomes possible. Therefore, it is possible to know the remaining amount of hindered phenol heat stabilizer, HALS and UVA of the deteriorated polyether-containing polymer. The effect of stabilizing agents, HALS and UVA, or the effect of such additives on the weather resistance of polyether-containing polymers can be confirmed.

  In summary, according to the present invention, a polyether-containing polymer is characterized in that the degree of deterioration is estimated by measuring a change in the amount of thermal decomposition products derived from the polyether moiety in the polyether-containing polymer. A degradation degree evaluation method is provided. Rather than a method for evaluating appearance and physical shape, the degree of deterioration is objectively evaluated compared to conventional methods by measuring changes in the amount of components that form polyether-containing polymers and the amount of pyrolysis products derived from the polyether part. The accuracy of the degradation degree evaluation is excellent.

  In one embodiment, the polyether-containing polymer is characterized in that the degree of deterioration is estimated by measuring a change in the amount of pyrolysis products derived from the polyether portion in the polyether-containing polymer by pyrolysis gas chromatography. Since a method for evaluating the degree of degradation of a polymer is provided, it can be directly applied to an analysis sample in the form of a solid without pretreatment of the degraded polyether-containing polymer, and the accuracy of the degradation level evaluation is excellent. . In addition, it is possible to estimate the degree of deterioration even with a small amount of sample of several mg or less, and it is not affected by the color and melting point of the sample much like spectroscopic analysis methods such as infrared spectroscopic analysis and differential scanning calorimetry. There are advantages.

  Furthermore, in one embodiment, the degree of deterioration is estimated by measuring a change in the amount of pyrolysis products derived from the polyether portion in the polyether-containing polymer by pyrolysis gas chromatography and mass spectrometry. A method for evaluating the degree of deterioration of a polyether-containing polymer is provided. Even if the type of the polyether-containing polymer and the additive is not known, after qualitative analysis by pyrolysis gas chromatography and mass spectrometry, or At the same time, quantitative analysis can be performed. Therefore, since it can be used even when the types of the polyether-containing polymer and the additive are unknown, it is excellent in that a wide range of polyether-containing polymers that can be evaluated for the degree of deterioration. Moreover, even if many additives, such as a heat stabilizer and a ultraviolet absorber, are contained, it is excellent also in that they are not affected by them.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable. For example, in the above, an example in which the deterioration degree of a sealing material containing a polyether-containing polymer was evaluated was shown. However, when the polyether-containing polymer is used for purposes other than a sealing material (for example, with a gasket or the like) As long as the composition change of the pyrolysis product of the polyether-containing polymer correlates with deterioration, the method of the present invention can be applied to the so-called fixed dry sealant, adhesive, and synthetic fibers that require stretchability. it can.

In addition, the deterioration degree evaluation method according to the present invention can be used not only for deterioration diagnosis of sealing materials for aged buildings, but also for evaluating the weather resistance of the sealing materials at the design and construction stage of a building. Therefore, in one embodiment, a sealing material containing a polyether-containing polymer is deteriorated by an accelerated deterioration test, and the degree of deterioration of the sealing material whose deterioration is accelerated can be evaluated by the method according to the present invention. As a result, it is possible to create a rational and planned maintenance plan and calculate the life cycle cost with high accuracy at the stage before construction.
Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1
<Creation of sealing material>
10% by weight of polyoxypropylene triol having a weight average molecular weight of 5000, 50% by weight of polyoxypropylene glycol having a weight average molecular weight of 2000 and 29% by weight of di-2-ethylhexyl phthalate are placed in a reaction vessel, and the pressure is reduced at 110 ° C. and 50 mmHg for 2 hours. Dehydrated. Thereafter, the reaction product was cooled to 80 ° C., and 11% by weight of 4,4-diphenylmethane diisocyanate was added and stirred. It was made to react at 80 degreeC for 30 hours, and the isocyanate containing urethane prepolymer was obtained.

60% by weight of the isocyanate-containing urethane prepolymer obtained above is placed in a kneading vessel filled with dry nitrogen gas, and further, 25% by weight of calcium carbonate, 5% by weight of silica, and 10% of xylene as a solvent as fillers. % By weight and kneaded in a stirrer to obtain a urethane-based sealing composition. The urethane-based sealing composition thus obtained was prepared into a sheet having a thickness of 2 mm, and was cured for 4 weeks at 23 ° C. and 50% relative humidity.
The following test was performed using the test body cut out from the above sample.

<Accelerated deterioration test>
As an accelerated deterioration test, both sides of the prepared sheet were sandwiched between 1 mm thick cellulose-based non-woven sheets adsorbing oil components, pressurized at 0.5 g / cm ² , and exposed to constant temperature and humidity. Moreover, this cellulose nonwoven fabric sheet was replaced every 2000 hours. The conditions of the accelerated deterioration test were a temperature of 80 ° C. and a humidity of 5% RH, and the accelerated deterioration test time was 2000 hours, 4000 hours, 6000 hours, 8000 hours, and 10,000 hours. Each sheet subjected to each accelerated deterioration test was taken out of the thermo-hygrostat after the test, and used for analysis. A 0.5 mg sample for analysis was obtained from the inside (near the center) of the sheet before and after the accelerated deterioration test, and used for pyrolysis gas chromatography mass spectrometry.

<Pyrolysis gas chromatography mass spectrometry>
Thermal decomposition was performed at a thermal decomposition temperature of 600 ° C. using a thermal decomposition apparatus (Double Shot Pyrolyzer PY-1020D manufactured by Frontier Laboratories). The column used in the gas chromatography was Durabond DB-1 (inner diameter: 0.25 mm, length: 30 m, film thickness: 0.25 μm), and a detector (P-6890) manufactured by Agilent was used. The temperature conditions were maintained at 50 ° C. for 5 minutes, heated from 50 ° C. to 320 ° C. (temperature increase rate: 10 ° C./minute), and maintained at 320 ° C. for 8 minutes. For mass spectrometry, AutoMass-II manufactured by JEOL was used. The mass spectrometric measurement conditions are an electron impact ionization method and a mass measurement range: m / z = 10 to 700 (m: mass, z: charge).

  The sealant sample before the accelerated deterioration test was analyzed by pyrolysis gas chromatography to obtain a pyrogram (0 hr in FIG. 2). Furthermore, about the sealing material sample before implementation of an accelerated deterioration test, each component was qualitatively acquired by acquiring the mass spectrometry spectrum of each component isolate | separated with the gas chromatograph. As a result, diisopropyl ether was detected at a retention time of 6.1 minutes, 1,2,4-trimethylcyclopentane (a peak unique to the sealing material) was detected at 6.3 minutes, and 4 minutes at 6.5 minutes. -Isopropoxy-2-butanone was detected. Moreover, 4,4-diphenylmethane diisocyanate and di-2-ethylhexyl phthalate could be detected in the portion with a long retention time.

In addition, pyrolysis gas chromatography analysis was performed in the same manner as described above for the sealing samples subjected to the accelerated degradation test at 80 ° C., 5% RH, 2000 hours, 4000 hours, 6000 hours, 8000 hours, and 10,000 hours. Thus, a pyrogram was obtained for each sample (only a sealing sample subjected to a 10,000 hour accelerated deterioration test is shown in FIG. 2).
Comparing the pyrogram obtained from the sealing material sample before the accelerated deterioration test (0 hour) with the pyrogram obtained from the sealing material sample subjected to the accelerated deterioration test for each deterioration test time, the accelerated deterioration test time increases. As a result, the peak area ratio of diisopropyl ether and 4-isopropoxy-2-butanone increased, and the correlation with the accelerated deterioration test time was high. On the other hand, for 1,2,4-trimethylcyclopentane, the area ratio decreased with the accelerated deterioration test time, and the correlation was not so high.

  Diisopropyl ether and 4 for the area of all peaks in the sealant sample before the accelerated degradation test (0 hour) and the sealant samples subjected to the accelerated degradation test for 2000 hours, 4000 hours, 6000 hours, 8000 hours, and 10,000 hours. -The area ratio of each peak of isopropoxy-2-butanone was calculated, and the increase / decrease ratio of each peak area of diisopropyl ether and 4-isopropoxy-2-butanone when the pre-accelerated deterioration was set to 1 was obtained. Indicated. As can be seen from this result, the accelerated deterioration test time increased, and the increase / decrease ratio of diisopropyl ether and 4-isopropoxy-2-butanone increased. That is, it was found that the degree of deterioration of the sealing material can be estimated from the value of the increase / decrease ratio of each peak area of diisopropyl ether and 4-isopropoxy-2-butanone. It was also found that the initial deterioration state has a good correlation with the accelerated deterioration time, and the initial deterioration state can be grasped. In particular, diisopropyl ether has high sensitivity to deterioration, and is considered more suitable as an indicator of deterioration.

Example 2
<Evaluation of degradation level of actual exposed paint film>
Sampling the sealant from the south of a building that has been used for 5 years, 6 years, 11 years, and 14 years after completion using a sealant with the same composition as the one subjected to accelerated deterioration test, and pyrolysis gas chromatography mass spectrometry It was used for. Perform the same analysis as above, calculate the area ratio of each peak of diisopropyl ether and 4-isopropoxy-2-butanone to the area of all the peaks in the sealing material sample, and diisopropyl ether peak when 1 before deterioration And the increase / decrease ratio of each peak area of 4-isopropoxy-2-butanone was calculated | required and it showed in FIG. As a result, it was found that the peak area ratio had a good correlation with the actual exposure time even in the actual exposure test.

  3 and 4, in the case of diisopropyl ether, the accelerated deterioration test time is 400 hours, which corresponds to almost one year of actual exposure (exposure by actual aged buildings). In the case of 4-isopropoxy-2-butanone The accelerated degradation test time of 420 hours was found to correspond to almost one year of actual exposure (exposure over actual aged buildings). As a result, it was found that the degree of deterioration can be accurately evaluated by quantifying the thermal decomposition product derived from the polyether part, and can be applied to deterioration diagnosis.

  As described above, the method for evaluating deterioration of a polyether-containing polymer according to the present invention can evaluate the degree of deterioration of a polyether-containing polymer with a small amount of sample with high accuracy, and can be evaluated. Since the range of is wide, it is useful for a method for evaluating the degree of deterioration of a sealing material for aged buildings and for deterioration diagnosis using the method.

DESCRIPTION OF SYMBOLS 1 Carrier gas supply 2 Sample injection part 3 Pyrolysis apparatus 4 Column 5 Splitter 6 Gas chromatograph detector 7 Interface 8 Mass spectrometer

Claims (4)

A method for evaluating the degree of deterioration of a polyether-containing polymer, wherein the degree of deterioration of the polyether-containing polymer is evaluated by measuring a change in the amount of thermal decomposition products derived from the polyether portion of the polyether-containing polymer. The polyether-containing polymer deterioration characterized in that the polyether part of the polyether-containing polymer contains polyether triol, and diisopropyl ether is quantified as a thermal decomposition product derived from the polyether part. Degree evaluation method.   The method for evaluating the degree of deterioration of a polyether-containing polymer according to claim 1, wherein the polyether-containing polymer is a polyether-based polyurethane. The degradation degree evaluation of the polyether-containing polymer according to claim 1 or 2, wherein a change in the amount of pyrolysis products derived from the polyether portion of the polyether-containing polymer is measured by pyrolysis gas chromatography. Method. The change in the amount of pyrolysis products derived from the polyether portion of the polyether-containing polymer is measured by pyrolysis gas chromatography and mass spectrometry. Degradation evaluation method.

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