CN-121994861-A - Multichannel confocal rapid phase diagram instrument and application and polymer solution system phase diagram drawing method

CN121994861ACN 121994861 ACN121994861 ACN 121994861ACN-121994861-A

Abstract

The invention belongs to the field of high molecular polymers, and relates to a multichannel confocal rapid phase diagram instrument and an application and polymer solution system phase diagram drawing method. The multichannel confocal fast phase diagram instrument comprises a laser light source, a laser beam expander, a first lens, a multichannel accurate temperature control sample cell system and a detection system which are sequentially arranged, wherein the detection system comprises a small-angle copolymerization Jiao Erji pipe detection system, the small-angle copolymerization Jiao Erji pipe detection system comprises a second lens with a first collimation system and a photodiode with a second collimation system, and the first lens and the second lens form a double-lens 2f-2f confocal optical system. The device and the method can monitor the phase transition rule of a plurality of polymer solution systems in the heating process at the same time, and provide theoretical guidance and regulation basis for regulating the structure or performance of the polymer by regulating the solvent property, phase transition, temperature and the like in the solution polymerization process and the solution processing process.

Inventors

DU WENJIE
WU QI
LI JUAN
ZHANG JIAHUI
QIAO JINLIANG
GONG XIANGJUN
ZHANG LONGGUI
ZHENG JUNPENG
LUO CHUNXIA
GAO FEIFEI

Assignees

中国石油化工股份有限公司
中石化(北京)化工研究院有限公司

Dates

Publication Date: 20260508
Application Date: 20241106

Claims (17)

1. The multichannel confocal rapid phase diagram instrument is characterized by comprising a laser light source, a laser beam expander, a first lens, a multichannel accurate temperature control sample cell system and a detection system, wherein the laser light source, the laser beam expander, the first lens, the multichannel accurate temperature control sample cell system and the detection system are sequentially arranged, and the detection system comprises a small-angle copolymerization Jiao Erji tube detection system; the small-angle copolymerization Jiao Erji pipe detection system comprises a second lens with a first collimation system and a photodiode with the second collimation system, wherein the first lens and the second lens form a double-lens 2f-2f confocal optical system.
2. The multichannel confocal fast phase diagram apparatus of claim 1, wherein the laser light source is a helium-neon laser red light source and/or a 532nm green light source having a wavelength of 632.8nm for providing an incident signal to the system.
3. The multi-channel confocal fast phase diagram apparatus of claim 1, wherein the multi-channel precision temperature-controlled sample cell system comprises a sample cell, a multi-channel constant temperature heater, and a temperature control assembly; the sample pool is used for containing a solution sample to be tested; the multichannel constant temperature heater is used as a solid medium for controlling the temperature of a sample and provides a laser detection path; The temperature control component is used for accurately controlling the temperature of the multichannel constant-temperature heater.
4. A multichannel confocal fast phase diagram according to claim 3, wherein the sample cell is an optical-grade quartz sealed bottle or a quartz capillary.
5. A multi-channel confocal fast phase diagram according to claim 3, wherein, The multichannel constant temperature heater is vertically arranged with the light path, each channel is a through light hole in parallel with the direction of the light path, and is a non-through hole in the vertical direction and is provided with a sample groove for placing a sample cell, and the size of the sample groove is such that the sample cell is closely attached to the inner wall of the sample groove; the inside of the multichannel constant temperature heater is provided with a plurality of communicated flow channels, the inlets and the outlets of the flow channels are respectively positioned at two sides of the multichannel constant temperature heater, heating medium from the temperature control assembly enters the flow channels from the lower inlet and circulates back to the temperature control assembly from the upper outlet at the other side; The multichannel constant temperature heater is fixed on a precise parallel moving table driven by a computer and a stepping motor, the position of the multichannel constant temperature heater is controlled by the stepping motor, the arrangement position of the multichannel constant temperature heater enables laser to be focused to the center of a solution sample to be tested through a first lens, and the laser is enabled to scan a sample pool in each channel in sequence through repeated reciprocating motion of the multichannel constant temperature heater in the horizontal direction, so that automatic collection of high-flux signals is realized.
6. A multichannel confocal fast phase diagram apparatus according to claim 3, wherein the multichannel thermostatted heater is made of a highly thermally conductive material, preferably stainless steel, copper or aluminium, more preferably brass; The multichannel accurate temperature control sample cell system is also provided with a thermocouple, a heat-resistant pipeline and a heat-insulating sleeve, and fireproof heat-insulating foam cotton is coated outside the multichannel constant-temperature heater; When the thermocouple is used, the temperature sensing port of the thermocouple is immersed in a control group sealed container only containing the pure solvent of the test system, and the thermocouple is used for monitoring the internal temperature of the multichannel constant temperature heater in real time.
7. A multichannel confocal fast phase diagram apparatus according to claim 3, wherein the multichannel constant temperature heater is provided with 3-30 channels, preferably 5-8 channels, for accommodating sample cells.
8. The multichannel confocal fast phase diagram instrument according to claim 3, wherein the temperature control assembly comprises a heating and refrigerating oil bath-constant temperature circulator and a heating medium, the heating range of the heating and refrigerating oil bath-constant temperature circulator is-50-300 ℃, and the temperature control precision is +/-0.01 ℃.
9. The multi-channel confocal fast phase diagram instrument according to claim 1, wherein the second lens is arranged at a position where an included angle of 3-10 degrees is formed between the other side of the multi-channel accurate temperature control sample cell system and the incident light direction, the horizontal distance between the center of the lens and the center of the sample is fixed to be a double focal length, and the photodiode is arranged at the double focal length behind the second lens.
10. The multi-channel confocal fast phase diagram apparatus of claim 1, wherein the first collimating system and the second collimating system are each independently selected from a slit or an aperture.
11. The multichannel confocal rapid phase diagram instrument according to claim 1, wherein the small-angle copolymerization Jiao Erji pipe detection system further comprises a signal and data processing module, and the phase diagram of the high polymer solution system is obtained through software calculation processing by recording the composition and the temperature corresponding to the signal mutation of the phase change point.
12. The multi-channel confocal fast phase diagram apparatus of claim 1, wherein the detection system is a dual detection system, further comprising a small-angle imaging system; the small-angle imaging system is preferably a high-resolution camera, and the setting position of the small-angle imaging system forms an included angle of 3-10 degrees with the incident light direction and is used for collecting laser signal images.
13. The multi-channel confocal fast phase diagram apparatus of claim 1 wherein the center of the heights of each component on the laser path is at the same level.
14. Use of a multichannel confocal fast phase diagram apparatus according to any one of claims 1-13 for characterizing a phase diagram of a polymer solution system.
15. A method for drawing a phase diagram of a polymer solution system by using the multichannel confocal fast phase diagram apparatus according to any one of claims 1 to 13, comprising the following steps: (1) Placing one or more sample cells containing a polymer solution in a sample cell of a multichannel precision temperature controlled sample cell system; (2) The starting device is used for focusing laser to the center position of the sample cell through the laser beam expander and the first lens, the incident laser is focused again by the second lens through the first collimating system after being scattered by the sample, and finally enters the photodiode through the second collimating system to acquire and process data; (3) And controlling the temperature in the test process, collecting scattered light signals of each sample at each temperature, obtaining phase transition temperature parameters of each sample, and fitting the phase transition temperature parameters and the composition parameters to obtain a phase diagram.
16. The method of phase patterning a polymer solution system according to claim 15, wherein when testing a plurality of samples, the method further comprises controlling the precision translation stage such that the laser scans the samples in each channel in turn.
17. The method for drawing a phase diagram of a polymer solution system according to claim 15, wherein the method for obtaining the phase transition temperature parameter of each sample is to plot a temperature-dependent scattered light signal intensity variation curve and take the measured temperature corresponding to the moment when the scattered light signal intensity is suddenly changed as the phase transition temperature of the polymer solution sample under the composition.

Description

Multichannel confocal rapid phase diagram instrument and application and polymer solution system phase diagram drawing method Technical Field The invention belongs to the field of high molecular polymers, and particularly relates to a multichannel confocal rapid phase diagram instrument, application of the multichannel confocal rapid phase diagram instrument in representing a phase diagram of a polymer solution system and a drawing method of the polymer solution system. Background The phase transition of polymer solution is relevant to industrial production, such as in solution polymerization process, solution processing process and material design process, and practical application of regulating the structure or performance of polymer by regulating solvent property, phase transition, temperature and the like is very common. The phase change process of the polymer solution is usually obtained by observing the phase change point of the system by an optical microscope or a light scattering instrument. The optical microscopy is more suitable for monitoring the phase change process of the polymer blending system in the temperature rising and falling process. For the small angle light scattering system, relevant laser light scattering instruments (CN 93202023.2, CN 200510012282.8, CN 201120526103.3) are disclosed in succession at university of Tianjin, academy of sciences of china, university of technology of hunan. The three devices are composed of a laser light source, a beam expander, a sample cell, an image acquisition system and the like, are suitable for a polymer solid system and are used for determining the crystallization structure of a polymer single component or the phase change process of a solid polymer blending system. The system disclosed in the above patent can only test a sample of one component at a time, and is time-consuming, and the temperature control system needs to be further improved. There are few related patents relating to phase separation processes in polymeric solution processes, such as WO2012/156393A1, WO2002/034795A1, WO2011/008955A1, US2012/0277392A1, etc. In US4444922a method is disclosed for producing a two-phase separation by changing the thermodynamic state of the solution, in US 9018328 B2 a method is disclosed for controlling the polymerization process of polyolefin polymers by controlling the solution phase separation process, and in another US10365195 B2 a method and device for determining the degree of phase separation of a polymer solution system. The above patent documents use the principle of solution phase separation but do not relate to an instrument for drawing a complete phase diagram. In Wu Ji yard article Mapping Phase Diagrams of Polymer Solutions by a Combination of Microfluidic Solution Droplets and Laser Light-Scattering Detection(Macromolecules 2014,47,2496-2502), a phase diagram is obtained by combining a microchannel sample cell and utilizing the abrupt change in light scattering signal when phase separation occurs to obtain a series of relationships between the composition and temperature of a polymer solution system. The disadvantage is that the temperature range is limited and cannot be used in high temperature environments. Disclosure of Invention In order to overcome the defects of insufficient temperature range and long test time of the currently disclosed test solution phase diagram device, the invention provides a multi-detector multi-channel small-angle laser rapid phase diagram instrument, the experimental precision and experimental reproducibility of the instrument are better than 0.1 ℃, the test time can be greatly shortened, and the accurate and rapid test of the polymer solution system phase diagram is realized. The invention provides a multichannel confocal rapid phase diagram instrument, which comprises a laser light source, a laser beam expander, a first lens, a multichannel accurate temperature control sample cell system and a detection system, wherein the laser light source, the laser beam expander, the first lens, the multichannel accurate temperature control sample cell system and the detection system are sequentially arranged, and the detection system comprises a small-angle copoly Jiao Erji tube detection system; the small-angle copolymerization Jiao Erji pipe detection system comprises a second lens with a first collimation system and a photodiode with the second collimation system, wherein the first lens and the second lens form a double-lens 2f-2f confocal optical system. A second aspect of the invention provides the use of a multichannel confocal fast phase diagram apparatus as described above for characterizing a phase diagram of a polymer solution system. The third aspect of the invention provides a method for drawing a phase diagram of a polymer solution system, which adopts the multichannel confocal rapid phase diagram instrument and comprises the following steps: (1) Placing one or more sample cells containing a polymer so