CN109297997B - Method for measuring crystallinity, mesomorphism and amorphous degree of polymer - Google Patents
Method for measuring crystallinity, mesomorphism and amorphous degree of polymer Download PDFInfo
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Abstract
The invention discloses a method for measuring crystallinity, mesomorphism and amorphous degree of a polymer. The method comprises the following steps: (1) determining the crystallinity of the polymer; (2) determining the (crystalline + mesogenic) degree of the polymer; (3) and (3) calculating the following data according to the data in the step (1) and the step (2): mesomorphism degree ═ C of polymerJunction and medium％‑CKnotPercent; amorphous degree of polymer 1-CJunction and medium％‑CKnot% of the total weight of the composition. The invention changes the history that the traditional methods such as DSC, WAXD and the like can only measure the crystallinity of the crystalline polymer. The results in combination with DMTA can give results not only for crystallinity but also for mesocrystallinity. It is also shown that the crystallization of natural rubber and gutta percha is controlled by a vulcanization crosslinking process, and the damaged crystalline region is first converted into a mesomorphic region and then converted into an amorphous region.
Description
Technical Field
The invention relates to the technical field of high molecular materials, and further relates to a method for determining the crystallinity, mesocrystallinity and amorphous degree of a polymer.
Background
The crystallization characteristic of the polymer plays a key role in the application performance of the polymer, the traditional two-phase crystallization model theory considers that the polymer is composed of a crystalline phase and an amorphous phase, and the crystallinity is a very important thermodynamic parameter for characterizing the crystallization performance of the polymer. Conventional crystallinity is measured based on the structural characteristics of the crystal itself or the physical changes occurring during the crystal transition, for example, WAXD is used to measure the crystal diffraction peak and amorphous peak of the crystalline polymer to calculate the crystallinity, and DSC is used to calculate the crystallinity by measuring the enthalpy of fusion of the polymer.
With the progress of scientific technology, it has been found that polymers are composed not only of crystalline and amorphous phases but also include a mesogenic phase having a structure intermediate between the crystalline and amorphous states. It is clear that the mesophase itself is also very critical for the polymer application properties. Since the mesomorphic phase has neither perfect regularity of the crystalline phase nor random coil state of the amorphous state, there is no way to determine the presence of the mesomorphic phase.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for measuring the crystallinity, mesocrystallinity and amorphous degree of a polymer. The principle is that in the process of glass transition of the polymer, the motion state of a free chain segment can be characterized by using DMTA, and the motion degree is controlled by crystallization and mesomorphism. The tan peak area of the crystalline polymer determined using DMTA thus represents the number of free motor segments remaining after crystallization and mesogenic control. Therefore, if the tan peak area of the polymer in the 100% amorphous state is known again, the sum of the crystallinity and mesocrystallinity of the polymer can be known by subtracting the tan peak areas. Whereas WAXD and DSC measure only the crystallinity of the polymer. Thus, the crystallinity, mesocrystallinity and amorphousness of the polymer can be obtained by subtracting the results of WAXD or DSC from the results of DMTA.
The invention aims to provide a method for determining the crystallinity, the mesocrystallinity and the amorphous degree of a polymer. The method comprises the following steps:
(1) determining the crystallinity of the polymer;
(2) determining the (crystalline + mesogenic) degree of the polymer;
the tan peak area of the glass transition region in the 100% amorphous state of the polymer was determined using ArCharacterizing; then, the tan peak area of the glass transition region in the crystalline state of the polymer was determined using AaCharacterizing; according to the theory of a two-phase model of a polymer consisting of a crystalline phase and an amorphous phase, the (crystalline + mesogenic) degree of the polymer is:
in the step (2), the heating rate is 1-10 ℃/min, and the testing frequency is 1-20 Hz.
In the step (2), the polymer with 100% amorphous state is obtained by a mode of liquid nitrogen rapid cooling quenching or a mode of cross-linking inhibition crystallization.
The crosslinking is carried out by means of sulfur vulcanization, peroxide vulcanization and irradiation vulcanization.
(3) And (3) calculating the following data according to the data in the step (1) and the step (2):
mesomorphism degree ═ C of polymerJunction and medium％-CKnot％
Amorphous degree of polymer 1-CJunction and medium％-CKnot％。
Among them, preferred is
In the step (1), the crystallinity of the polymer can be determined by one of the following two methods;
a, measuring a wide-angle X-ray diffraction curve of the polymer, obtaining a characteristic crystallization peak and an amorphous diffraction peak of the polymer by a peak separation technology, and respectively using WcAnd WaCharacterizing; the crystallinity of the polymer, as determined using WAXD, is then:
b, measuring the temperature-rising melting curve of the polymer to obtain the melting peak of the polymer, obtaining the melting enthalpy of the polymer by integration, and using delta HfCharacterizing; knowing the enthalpy of fusion of the polymer at 100% crystalline state, using Δ Hf100％Characterizing; the polymer has a crystallinity, as determined by DSC, of:
wherein the heating rate is 1-10 ℃/min.
The invention can adopt the following technical scheme:
the method requires the use of three test devices, Dynamic Mechanical analysis (DMTA) and Differential Scanning Calibration (DSC) and Wide Angle X-ray diffraction (WAXD). The crystallinity, mesogenicity and amorphousness of the polymer can be determined by DMTA and DSC complexation. The crystallinity, mesogenicity and amorphousness of the polymer can also be determined by DMTA and WAXD complexation.
Determination of the tan Peak surface of the glass transition region of the Polymer in the 100% amorphous State Using DMTALong Zhu, use ArAnd (5) characterizing. Then measuring the tan peak area of the glass transition region in the polymer crystallization state by using DMTA, and using AaAnd (5) characterizing. The testing temperature is set according to the glass transition temperature of the polymer, the heating rate is 1-10 ℃/min, and the testing frequency is 1-20 Hz. According to the theory of a two-phase model of a polymer consisting of a crystalline phase and an amorphous phase, the polymer has a crystallinity + mesomorphism, measured with DMTA, of:
measuring the temperature-rising melting curve of the polymer by using DSC to obtain the melting peak of the polymer, obtaining the melting enthalpy of the polymer by integration, and using Delta HfAnd (5) characterizing. Knowing the enthalpy of fusion of the polymer at 100% crystalline state, using Δ Hf100％And (5) characterizing. The testing temperature is set according to the crystallization melting temperature of the polymer, and the heating rate is 1-10 ℃/min. The crystallinity of the polymer, determined using DSC, was:
according to the theory of a three-phase model in which a polymer is composed of a crystalline phase, a mesomorphic phase, and an amorphous phase, the crystallinity determined by DMTA contains not only a crystalline portion but also a mesomorphic portion. Whereas the crystallinity determined by DSC contains only crystalline portions. Thus, the crystallinity, mesogenicity and amorphousness of the polymer can be determined using DMTA in combination with DSC as follows:
degree of crystallinity ═ CDSC％
Degree of mesomorphism ═ CDMTA％-CDSC％
Amorphous degree ═ 1-CDMTA％-CDSC％
The wide-angle X-ray diffraction curve of the polymer is measured by WAXD, the characteristic crystallization peak and amorphous diffraction peak of the polymer can be obtained by the peak separation technology, and W is used respectivelycAnd WaAnd (5) characterizing. The test conditions are specifically set according to the crystallization characteristics of the polymer. Use of the polymer WAThe crystallinity determined in XD was:
for the same reason, the mesomorphism degree and the amorphous degree of the polymer are as follows:
degree of mesomorphism ═ CDMTA％-CWAXD％
Amorphous degree ═ 1-CDMTA％-CWAXD％
The polymer in 100% amorphous state can be obtained by means of rapid quenching with liquid nitrogen. The polymer in 100% amorphous state can also be obtained by cross-linking means such as sulfur vulcanization, peroxide vulcanization and irradiation vulcanization, and then the tan peak area of the crystalline polymer in 100% amorphous state at different cross-linking densities is deduced back from the linear relationship between cross-linking density and tan peak area.
The invention relates to a method for measuring the crystallinity, mesomorphism and amorphous degree of a polymer, which changes the history that only the crystallinity of a crystalline polymer can be measured by the traditional methods such as DSC, WAXD and the like. The results in combination with DMTA can give results not only for crystallinity but also for mesocrystallinity. It is also shown that the crystallization of natural rubber and gutta percha is controlled by a vulcanization crosslinking process, and the damaged crystalline region is first converted into a mesomorphic region and then converted into an amorphous region.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The crystallinity, mesocrystallinity and amorphousness of the high density polyethylene were measured. The sample size of the polyethylene was 25mm × 6mm × 2 mm. The tan-temperature curve of the crystalline polyethylene was measured in a drawing mode. And (3) testing conditions are as follows: the heating rate is 1 ℃/min, the testing frequency is 1Hz, the testing temperature is-150 to-140 ℃, the tan-temperature curve of the crystalline polyethylene is obtained at this time, and then the tan peak area of the polyethylene at the glass transition temperature is calculated through integration. The temperature of 140 ℃ is kept constant, the temperature is above the melting point temperature (130 ℃) and not more than 15 ℃, the polyethylene crystals are melted at the moment, but in a softened state, and the shape of a sample strip can be still maintained. And then rapidly introducing liquid nitrogen to quench the softened polyethylene sample strips, so that the polyethylene sample strips are in a 100% amorphous state. The tan-temperature curve of the amorphous polyethylene was determined using the draw mode. And (3) testing conditions are as follows: the heating rate is 1 ℃/min, the testing frequency is 1Hz, the testing temperature is-150 to-140 ℃, the tan-temperature curve of the amorphous polyethylene is obtained at this time, and then the tan peak area of the amorphous polyethylene at the glass transition temperature is calculated through integration. The crystallinity of the DMTA test was then calculated according to the formula provided in claim 2.
The temperature-rising melting curve of the crystalline polyethylene was measured by DSC. The heating rate is 1 ℃/min, and the temperature range is from normal temperature to 200 ℃. The crystallinity of the DSC test was then calculated using the formula shown in claim 3.
Finally, the crystallinity (C%), mesocrystallinity (M%) and amorphousness (A%) of the high density polyethylene are settled according to the formula indicated in the claims, see Table 1.
TABLE 1 crystallinity, mesocrystallinity and amorphousness of high density polyethylene
Example 2
The crystallinity, mesocrystallinity and amorphousness of the low temperature crystallized natural rubber were determined. The sample size of the natural rubber was 25mm × 6mm × 2 mm. Firstly, DMTA is utilized to induce the crystallization of the natural rubber at low temperature (-25 ℃) for 0, 1, 2, 4 and 12 hours. And measuring the tan-temperature curve of the natural rubber under different crystallization time by adopting a stretching mode. And (3) testing conditions are as follows: the heating rate is 3 ℃/min, and the testing frequency is 3 Hz. The area of the tan peak of the natural rubber at the glass transition temperature was then calculated by integration and the degree of crystallinity of the DMTA test was then calculated according to the disclosure provided in claim 2.
The crystallization of natural rubber was induced by DSC at low temperature (-25 ℃) for 0, 1, 2, 4, 12 hours and then their temperature-rising melting curves were measured, respectively. The heating rate is 1 ℃/min, and the temperature range is from-80 ℃ to 120 ℃. The crystallinity of the DSC test was then calculated using the formula shown in claim 3.
Finally, the crystallinity (C%), mesocrystallinity (M%) and amorphousness (A%) of the natural rubber are settled according to the formula indicated in the claims, see Table 2.
TABLE 2 Low temperature induced crystallinity, Mesogenic and amorphous degree of Natural rubber
Example 3
And (3) determining the crystallinity, the mesocrystallinity and the amorphous degree of the natural rubber under different crosslinking densities by low-temperature crystallization. The sample size of the natural rubber was 25mm × 6mm × 2 mm. Firstly, preparing natural rubber samples under different crosslinking densities by using a traditional rubber processing technology, wherein the crosslinking agent is sulfur, and the parts are 0, 0.25, 0.5, 0.75, 1, 1.5 and 2. The natural rubber is induced to crystallize for 4 hours at low temperature (-25 ℃) by utilizing DMTA. And then measuring the tan-temperature curve of the natural rubber under different crosslinking densities by adopting a stretching mode. And (3) testing conditions are as follows: the heating rate is 5 ℃/min, and the testing frequency is 10 Hz. The area of the tan peak of the natural rubber at the glass transition temperature was then calculated by integration and the degree of crystallinity of the DMTA test was then calculated according to the disclosure provided in claim 2. The tan peak area of the crystalline natural rubber in a 100% amorphous state at different crosslink densities can be extrapolated from the relationship between tan peak area and crosslink density.
The natural rubbers at the above different crosslinking densities were induced to crystallize for 4 hours at a low temperature (-25 ℃) by DSC, and then their temperature-rising melting curves were measured, respectively. The heating rate is 1 ℃/min, and the temperature range is from-80 ℃ to 120 ℃. The crystallinity of the DSC test was then calculated using the formula shown in claim 3.
Finally, the crystallinity (C%), mesocrystallinity (M%) and amorphousness (A%) of the natural rubber are settled according to the formula indicated in the claims, see Table 3.
TABLE 3 Low temperature induced crystallinity, Mesogenic and amorphous degree of Natural rubber
Example 4
And (3) measuring the crystallinity, the mesomorphism and the amorphous degree of the gutta percha under different crosslinking densities at normal temperature. The sample size of gutta-percha was 25mm × 6mm × 2 mm. Firstly, preparing natural rubber samples under different crosslinking densities by using a traditional rubber processing technology, wherein DCP is used as a crosslinking agent in parts of 0, 1, 2, 4, 6, 8, 10, 12, 14 and parts. And (3) measuring tan-temperature curves of the gutta-percha under different crosslinking densities by using DMTA in a stretching mode. The test conditions, the heating rate of 10 ℃/minute and the test frequency of 20 Hz. The tan peak area of gutta percha at the glass transition temperature was then calculated by integration or the like, and then the degree of crystallinity of the DMTA test was calculated according to the disclosure provided in claim 2. The tan peak area of the 100% amorphous state of the crystallized gutta-percha at different crosslinking densities can be obtained by extrapolation from the relationship between tan peak area and crosslinking density.
Their diffraction patterns were tested by WAXD. The scan angle range is 5 ° <2 θ <30 °, scan speed 5 °/min. The crystallinity of the WAXD test is then calculated using the formula shown in claim 5.
Finally, the crystallinity (C%), mesocrystallinity (M%) and amorphousness (A%) of the natural rubber are settled according to the formula shown in claim 5, see Table 4.
TABLE 4 Low temperature induced crystallinity, Mesogenic and amorphous degree of Natural rubber
Claims (7)
1. A method for determining the crystallinity, mesocrystallinity and amorphousness of a polymer, characterized in that said method comprises:
(1) determining the crystallinity of the polymer;
the crystallinity of the polymer was determined using Differential Scanning calibration or Wide Angle X-ray Diffraction;
(2) determining the crystallinity and mesocrystallinity of the polymer;
determining the tan peak area of the glass transition region in the 100% amorphous state of the polymer byArCharacterizing; then, the tan peak area of the glass transition region in the crystalline state of the polymer was determined using AaCharacterizing; according to the theory of a three-phase model in which a polymer consists of a crystalline phase and an amorphous phase, the crystallinity and mesocrystallinity of the polymer are:
the crystallinity and mesocrystallinity of the polymer were determined using a Dynamic Mechanical Thermal Analysis;
(3) and (3) calculating the following data according to the data in the step (1) and the step (2):
mesomorphism degree ═ C of polymerJunction and medium％-CKnot％
Amorphous degree of polymer 1-CJunction and medium％-CKnot％。
2. The method for determining the crystallinity, mesocrystallinity and amorphousness of a polymer according to claim 1, wherein:
in the step (1), the crystallinity of the polymer is measured;
measuring wide-angle X-ray diffraction curve of polymer, obtaining characteristic crystalline peak and amorphous diffraction peak of the polymer by peak separation technique, respectively using WcAnd WaCharacterizing; the crystallinity of the polymer is then:
3. the method for determining the crystallinity, mesocrystallinity and amorphousness of a polymer according to claim 1, wherein:
in the step (1), the crystallinity of the polymer is measured;
measuring the temperature-rising melting curve of the polymer to obtain the melting peak of the polymer, obtaining the melting enthalpy of the polymer by integration, and using the delta HfCharacterizing; knowing the enthalpy of fusion of the polymer at 100% crystalline state, using Δ Hf100％Characterizing; the crystallinity of the polymer was:
4. the method for determining the crystallinity, mesocrystallinity and amorphousness of a polymer according to claim 1, wherein:
in the step (2), the heating rate is 1-10 ℃/min, and the testing frequency is 1-20 Hz.
5. The method of determining the crystallinity, mesocrystallinity and amorphousness of a polymer according to claim 3 wherein:
the heating rate is 1-10 ℃/min.
6. The method for determining the crystallinity, mesocrystallinity and amorphousness of a polymer according to claim 1, wherein:
in the step (2), the polymer with 100% amorphous state is obtained by a mode of liquid nitrogen rapid cooling quenching or a mode of cross-linking inhibition crystallization.
7. The method for determining the crystallinity, mesocrystallinity and amorphousness of a polymer according to claim 6, wherein:
the crosslinking is carried out by means of sulfur vulcanization, peroxide vulcanization and irradiation vulcanization.
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