CN101929954A - Method for monitoring resin curing process in real time - Google Patents
Method for monitoring resin curing process in real time Download PDFInfo
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- CN101929954A CN101929954A CN 201010235841 CN201010235841A CN101929954A CN 101929954 A CN101929954 A CN 101929954A CN 201010235841 CN201010235841 CN 201010235841 CN 201010235841 A CN201010235841 A CN 201010235841A CN 101929954 A CN101929954 A CN 101929954A
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Abstract
The invention relates to a novel method for monitoring a thermosetting resin curing process in real time. In the method, a polyurethane resin is taken as an example, the change of the transmittance of a characteristic functional group in an infrared spectrum is monitored by an infrared spectrography variable temperature accessory (Germany Bruker), so a conversion curve reflecting the curing degree of the thermosetting resin is directly obtained, and real-time monitoring of the polyurethane resin curing process is realized at a certain temperature. The method is applied to other thermosetting resins and has wide application prospect.
Description
Technical field
The invention belongs to macromolecular material and paint field, relate to a kind of new method of real-time monitoring thermosetting resin curing process.
Background technology
Thermoset resin refers in heating, adds and depress or under hardening agent, action of ultraviolet light, carry out chemical reaction, and crosslinking curing becomes a big class synthetic resin of insoluble not fusant matter.The molecular structure of thermoset resin is a build, comprises most condensation resin, and the advantage of thermoset resin is the thermotolerance height, and pressurized is not yielding; Shortcoming is that mechanical property is relatively poor.
Thermoset resin commonly used has phenolics, Lauxite, melamine formaldehyde resin, epoxy resin, unsaturated polyester, polyurethane, polyimide etc.Thermoset resin is mainly used in makes reinforced plastic, polyfoam, various electrician with moulding compound, casted article etc., also has a great deal of tackifier and coating of being used for.
In actual applications, monitoring, the research of relevant thermosetting resin curing process, and to the deep understanding of its inherent mechanism, for further improvement naval stores quality, the development new varieties are developed new processing technology, all have great importance.At present, the method for research solidification process has thermal analysis system, dynamic torsional oscillation method, infra-red sepectrometry etc.
Infrared spectrum is mainly used in the fundamental research of molecular structure in chemical field, for example measure bond distance, the bond angle of molecule, and then the analysis of inferring its spatial configuration etc. and chemical composition is the qualitative, quantitative of compound, but wherein most widely used still be the evaluation of compound structure generally.The most outstanding characteristics of infrared spectrum are the characteristics with height, and it is external to remove optical siomerism, and every kind of compound all has the infrared absorption spectrum of oneself.So can be according to peak position, the peak of the infrared absorption spectrum of compound strong and peak shape judge whether there is some functional group in this compound, and and then infer its structure.
Urethane resin is one of typical thermoset resin, and the product that can be made into has kinds such as polyfoam, rubber, coating, bonding agent, fiber, synthetic leather.Wherein, polyurethane coating is widely used in the every field with its excellent comprehensive performance.In the practice, often determine the condition of cure of coating according to the performance behind the film curing, this not only complexity but also not too science, and can't obtain the information of relevant solidification process, promptly can't realize real-time monitoring to state of cure.
Summary of the invention
The present invention is an example with the urethane resin, proposes a kind of new method of real-time monitoring thermosetting resin curing process.Mainly utilize infrared spectrum alternating temperature annex (German Bruker), variation by monitoring feature functional group transmissivity, directly obtain the conversion rate curve of reflect heat thermosetting resin state of cure, realized at a certain temperature real-time monitoring the curable urethane resin process.
For achieving the above object, principle of the present invention and experimental procedure are:
1) principle
Every kind of chemical functional group is because its molecular vibration all has its characteristic absorpting spectrum peak in infrared spectrum, can carry out qualitatively and quantitative analysis according to its characteristic peak.The hardening agent of polyurethane coating is a polyisocyanates, and in solidification process, chemical reaction takes place reactive group isocyano-NCO and hydroxyl-OH, generates ammonia ester bond-NHCOO; Along with deepening continuously of state of cure ,-OH and-the NCO group constantly consumes, when-NCO complete obiteration, paint film is with regard to full solidification.Simultaneously, in the solidification process, the characteristic peak of reactive group-NCO is 2272cm
-1, this zone is subjected to the interference at other peaks little, so just can calculate the state of cure of paint film according to the variation of the transmissivity of the characteristic peak of-NCO.
As the A component, isocyanate curing agent (740D) is as the B component with the thermosetting acrylic resin (BS-965) of Sanmu Group Co., Ltd., Jiangsu.Because each measurement point, therefore need not be sought a characteristic peak that does not participate in the functional group of reacting all at same position as the reference peak, only needs the characteristic peak 2272cm of record-NCO
-1Variation get final product.
The computing formula of conversion ratio (extent of reaction) is as follows:
R
I＝[(T
2272?I-T?
2272?0)/T?
2272?0]×100
In the formula, R
I---the extent of reaction (%) of solidification process;
T
2272 I---the 2272cm in the solidification process
-1Transmissivity;
T
2,272 0---the 2272cm in the uncured process
-1Transmissivity.
The curing reaction formula of thermosetting acrylic resin and isocyanate curing agent is as follows:
2) experimental procedure
A. potassium bromide (KBr) window that will place sample is installed on " infrared spectrum alternating temperature annex " (hereinafter to be referred as " annex ");
B. " annex " integral body is placed infrared spectrum sample chamber light path;
C. regulate attemperating unit, potassium bromide (KBr) window temperature is risen to design temperature;
D. according to preset proportion, accurately take by weighing A, B component, mix immediately, stir with electronic balance;
E. get an amount of mixing back resin, be applied on potassium bromide (KBr) window in " annex ";
F. begin Infrared spectrum scanning, can set sweep interval;
E. according to 2272cm
-1Transmission change, calculate and obtain reflecting the conversion rate curve of state of cure.
The invention has the advantages that:
1) do not destroy sample in the test process, analysis speed is fast, and amount of samples is few.
2) in the test process, monitor the regional constant of sample solidifies, self-consistentency does not need the reference peak.
3) only need record 2272cm
-1The variation of transmissivity is simplified method.
4) can set sweep interval as required, realize monitoring in real time.
5) method is simple, and is workable.
Description of drawings
(the A/B=3: infrared spectrogram 1) of sample when Fig. 1 solidification temperature is 120 ℃
Illustrate: under fixed temperature, 5 minutes run-downs, along with the carrying out of curing reaction, characteristic peak 2272cm
-1Transmissivity increase gradually, promptly absorb and reduce, functional group content reduces.
(the A/B=3: conversion rate curve figure 1) of sample when Fig. 2 solidification temperature is 120 ℃
Illustrate: under fixed temperature, 5 minutes run-downs, along with the carrying out of curing reaction, characteristic peak 2272cm
-1Transmission change obvious, calculate the conversion rate curve figure of sample.
Embodiment
Embodiment 1: monitor thermosetting resin curing process in real time and obtain according to following method:
1. potassium bromide (KBr) window that will place polyurethane samples is installed on " infrared spectrum alternating temperature annex ", then " annex " integral body is placed infrared spectrum sample chamber light path, regulates attemperating unit, and potassium bromide (KBr) window regional temperature is risen to 120 ℃.
2. according to mass ratio A/B=3: 1, accurately take by weighing A, the B component of polyurethane samples with electronic balance, mix immediately, stir; Get an amount of mixing back resin then, be applied on potassium bromide (KBr) window in " annex ".
3. begin Infrared spectrum scanning, 5 minutes run-downs are according to 2272cm
-1Transmission change, calculate and obtain reflecting the conversion rate curve of state of cure.
Embodiment 2: it is 110 ℃ that temperature is set, and all the other are with embodiment 1.
Embodiment 3: it is 130 ℃ that temperature is set, and all the other are with embodiment 1.
Embodiment 4: A, B constituent mass ratio that polyurethane samples is set are 2: 1, and all the other are with embodiment 1.
Embodiment 5: A, B constituent mass ratio that polyurethane samples is set are 1: 1, and all the other are with embodiment 1.
Embodiment 6: it is 4 minutes that sweep interval is set, and all the other are with embodiment 1.
Embodiment 7: it is 3 minutes that sweep interval is set, and all the other are with embodiment 1.
Claims (6)
1. the method for a monitoring resin curing process in real time, it is characterized in that: this method can obtain according to the following step:
1. potassium bromide (KBr) window that will place polyurethane samples is installed on " infrared spectrum alternating temperature annex ", then " annex " integral body is placed infrared spectrum sample chamber light path, regulates attemperating unit, and potassium bromide (KBr) window regional temperature is risen to design temperature.
2. according to setting the mass ratio A/B of resin (A), accurately take by weighing A, B component, mix immediately, stir with electronic balance with hardening agent (B); Get an amount of mixing back resin then, be applied on potassium bromide (KBr) window in " annex ".
3. begin Infrared spectrum scanning, according to setting-up time interval scan once, according to 2272cm
-1Transmission change, calculate and obtain reflecting the conversion rate curve of state of cure.
2. the method for a kind of monitoring resin curing process in real time according to claim 1, it is characterized in that: the resin system that is suitable for is phenolics, Lauxite, melamine formaldehyde resin, epoxy resin, unsaturated polyester, polyurethane, polyimide.
3. the method for a kind of monitoring resin curing process in real time according to claim 1, it is characterized in that: equipment therefor is " infrared spectrum alternating temperature annex " and potassium bromide (KBr) window.
4. the method for a kind of monitoring resin curing process in real time according to claim 1, it is characterized in that: solidification temperature can be set at 100,110,120,130,140 ℃.
5. the method for a kind of monitoring resin curing process in real time according to claim 1 is characterized in that: the time interval of beginning Infrared spectrum scanning can be set at 2,3,4,5 minutes/time.
6. the method for a kind of monitoring resin curing process in real time according to claim 1 is characterized in that: according to 2272cm
-1Transmission change, calculate the reflection state of cure conversion rate curve, computing formula is:
R
I＝[(T
2272?I-T
?2272?0)/T
2272?0]×100
In the formula, R
I---the extent of reaction (%) of solidification process;
T
2272 I---the 2272cm in the solidification process
-1Transmissivity;
T
2,272 0---the 2272cm in the uncured process
-1Transmissivity.
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| CN 201010235841 CN101929954A (en) | 2010-07-26 | 2010-07-26 | Method for monitoring resin curing process in real time |
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| CN 201010235841 CN101929954A (en) | 2010-07-26 | 2010-07-26 | Method for monitoring resin curing process in real time |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102967579A (en) * | 2012-11-19 | 2013-03-13 | 深圳大学 | Method for representing polyurethane curing reaction by in-situ diffuse reflection infrared spectrum |
| CN103901183A (en) * | 2014-03-19 | 2014-07-02 | 肇庆理士电源技术有限公司 | Testing method for hardening of glue |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4798954A (en) * | 1987-02-03 | 1989-01-17 | Foster-Miller, Inc. | Monitoring technology |
| CN101038282A (en) * | 2006-03-15 | 2007-09-19 | 欧姆龙株式会社 | A state estimate method of ultraviolet rays curing resin |
| CN101435772A (en) * | 2008-12-12 | 2009-05-20 | 三星高新电机（天津）有限公司 | Epoxide-resin glue curing degree and hardness detecting and analyzing method |
-
2010
- 2010-07-26 CN CN 201010235841 patent/CN101929954A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4798954A (en) * | 1987-02-03 | 1989-01-17 | Foster-Miller, Inc. | Monitoring technology |
| CN101038282A (en) * | 2006-03-15 | 2007-09-19 | 欧姆龙株式会社 | A state estimate method of ultraviolet rays curing resin |
| CN101435772A (en) * | 2008-12-12 | 2009-05-20 | 三星高新电机（天津）有限公司 | Epoxide-resin glue curing degree and hardness detecting and analyzing method |
Non-Patent Citations (2)
| Title |
|---|
| 《功能材料》 20070731 邓朝霞等 环氧树脂改性水性聚氨酯的合成研究 期刊第1132-1135页 1-6 第38卷, 第7期 2 * |
| 《高分子材料科学与工程》 20030131 文庆珍等 FT-IR法研究聚氨酯的固化行为 参见期刊108页正文第3段至109页右栏第1段、图1 1-6 第19卷, 第1期 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102967579A (en) * | 2012-11-19 | 2013-03-13 | 深圳大学 | Method for representing polyurethane curing reaction by in-situ diffuse reflection infrared spectrum |
| CN102967579B (en) * | 2012-11-19 | 2015-08-19 | 深圳大学 | A kind of Energetic Materials by In-Situ Diffuse Reflection characterizes the method for urethane cures reaction |
| CN103901183A (en) * | 2014-03-19 | 2014-07-02 | 肇庆理士电源技术有限公司 | Testing method for hardening of glue |
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Open date: 20101229 |