CN106483209A - Method for measuring silicone sealant - Google Patents
Method for measuring silicone sealant Download PDFInfo
- Publication number
- CN106483209A CN106483209A CN201610803782.1A CN201610803782A CN106483209A CN 106483209 A CN106483209 A CN 106483209A CN 201610803782 A CN201610803782 A CN 201610803782A CN 106483209 A CN106483209 A CN 106483209A
- Authority
- CN
- China
- Prior art keywords
- white oil
- silicone sealant
- assay method
- temperature
- gas chromatography
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention relates to a method for identifying whether a silicone sealant contains white oil by using a gas chromatography-mass spectrometer, which comprises the specific steps of performing a swelling or extraction test on the silicone sealant to obtain a swelling solution or an extraction solution, performing gas chromatography-mass spectrometer characterization on the swelling solution or the extraction solution, and judging that the silicone sealant contains the white oil if more low-paraffin proton peaks appear within the range of 30-40 minutes. The method is beneficial to more accurately identifying the white oil content in the silicone sealant, can accurately identify the white oil with extremely small content in the silicone sealant, and can accurately identify the sealant which can not be identified by detecting volatile matters and smelling odor by using the method.
Description
Technical field
The present invention relates to a kind of Quality Identification of silicone sealant and in particular to identified a kind of using gas chromatography mass spectrometry chromatograph
The method of white oil-doped silicone sealant.
Background technology
Since 20th century the eighties, with the rapid development of China's economy, building industry also fast development therewith, especially various
The high building having characteristic, rises sheer from level ground like the mushrooms after rain, and these high buildings are because employing glass curtain wall as external decoration
More Friends grace sb.'s house with their presence to make it.Near during the last ten years, constantly carry with the requirement to the energy-saving and environmental protection of building, the performance such as attractive in appearance for the country
Height, and the promulgation of national energy-saving mandatory standard, glass curtain wall has obtained more being widely applied in building industry.
Before more than 20 year, China has used for reference American-European glass curtain wall technology, and glass curtain wall is introduced China, but at that time as main
Want the silicone sealant but import to be completely dependent on of fabricated material.For the needs of state's Curtain Wall industry development, country fosters energetically
Silicone adhesive manufacturing enterprise, has emerged in large numbers the enterprise that a collection of technology is really up to the mark, quality is really up to the mark, and its product yield increases sharply.
But in recent years, the aggravation of the raising with enterprise's production capacity and competition among enterprises, the operation of enterprise and existence are subject to
Unprecedented pressure and test are arrived.Construction market intensified competition, spreads the tendency of price lightweight emphatically, for reduces cost,
Some producers add white oil plasticizer in silicone weatherproof sealant production process.However, the silicone weather resistant that with the addition of white oil is close
Sealing (hereinafter referred to as " white oil fluid sealant ") although after curable adhesive layer glue-line brightness improve, its weatherability, mechanical property with
And be all greatly affected with the compatibility of butyl rubber in double glazing etc., this is by the safety, resistance to building glass curtain wall
Property hides some dangers for long.
Cause very big injury to the quality of glue and in use after being mixed with white oil in silicone adhesive, white oil is contained
Measure high silicone adhesive to identify by the method for abnormal smells from the patient, survey fugitive constituent, for the Quality Identification of silicone sealant,
GB16776-2005 (structural silicone sealant for building) regulation carries out fugitive constituent mensure it is stipulated that not under conditions of 70 ± 2 DEG C
Silicone adhesive more than 10% is qualified products.Fugitive constituent both included harmful components, such as white oil, also included necessarily leading in formula
Composition to product quality no adverse effect, only cannot effectively be distinguished by thermogravimetry.
Content of the invention
It is an object of the invention to provide a kind of method measuring white oil-doped silicone sealant, in order to detect in silicone sealant
Whether contain white oil.
In order to realize foregoing invention purpose, the technical scheme is that：
A kind of assay method of white oil-doped silicone sealant it is characterised in that determination step is as follows,
Swelling or extraction test is carried out to silicone sealant, obtains swelling solution or extract, then to swelling solution or extracting
Liquid carries out gas chromatography mass spectrometry chromatograph sign, and experimental condition and process are as follows：
Testing equipment：Gas chromatography mass spectrometry chromatograph Varian 450-GC and Varian 220-MS；
Testing column：6% fine propyl phenyl/94% polydimethylsiloxane capillary column；
Injector temperature：250℃；
Detector：FID, 260 DEG C of temperature；
Column temperature：80 DEG C of holding 1min of temperature programming, then rise to 230 DEG C of holding 15min with 10 DEG C/min；
Split ratio：Split sampling, split ratio is adjustable；
Sample size：1.0μL；
Test procedure：Take the silicone adhesive sample after 10g solidification, be dissolved in the closed glass jar filling 20ml toluene solution,
Room temperature places 24h, takes 10 μ L toluene solutions, and 1.0 μ L are to gas chromatography mass spectrometry chromatograph for injection,
If concentrating in special time period and more low alkane proton peak occurring,
Then judge to contain white oil in described silicone sealant.
Preferably, the solvent used by described swell test is any one in toluene, acetone, oxolane or hexamethylene
Kind.
Preferably, comprehensive gas chromatography mass spectrometry colour scale seeks peace thermogravimetric two kinds of characterization results of sign to white oil-doped silicone sealant
It is measured.
Preferably, the method that described thermogravimetric characterizes is from 20～50 DEG C of liters with 20 DEG C/min under conditions of nitrogen atmosphere
It is raised to 200～220 DEG C in warm scope, and keep 5 minutes at this temperature, then with the liter of 20 DEG C/min in the atmosphere of oxygen
Warm speed is raised to 800～900 DEG C.
Preferably, the size of described capillary column is 60mX0.32mmX1.0 μm.
Preferably, described split ratio is 20:1.
Preferably, the chromatographic carrier gas flux of described gas chromatography mass spectrometry is：1.0ml/min, total flow is 24.0ml/min.
Preferably, described special time period is 30-40 minute.
By the authentication method of the present invention, silicone sealant is identified, when the white oil content in silicone sealant is little
When also can accurately determine in this silicone sealant and contain white oil, and simple to operation.The present invention can make we
Using during silicone sealant, quick, accurate identification is carried out to those glue inferior, unqualified glue.The present invention can be right
Accurately identified containing minimal amount of white oil in silicone sealant, for the sealing surveying fugitive constituent, smelling the odour can not be identified
Glue can accurately be identified using the method.
Brief description
Fig. 1 is no white oil fluid sealant mass spectrogram；
Fig. 2 is the mass spectrogram of white oil fluid sealant；
Fig. 3 is the TGA curve comparison figure of white oil fluid sealant and no white oil fluid sealant.
Specific embodiment
In an embodiment of the present invention, it is made whether the mensure containing white oil, specifically after selecting silicone sealant sample
Determination step is as follows：
Swelling or extraction test is carried out to silicone sealant, obtains swelling solution or extract, used by described swell test
Solvent is any one in toluene, acetone, oxolane or hexamethylene；Then gas chromatography mass spectrometry is carried out to swelling solution or extract
Chromatograph characterizes,
Testing equipment：Gas chromatography mass spectrometry chromatograph Varian 450-GC and Varian 220-MS；
Testing column：6% fine propyl phenyl/94% polydimethylsiloxane capillary column, the concrete size of capillary column is preferred
For 60mX0.32mmX1.0 μm；
Injector temperature：250℃；
Detector：FID, 260 DEG C of temperature；
Column temperature：Temperature programming, from the beginning of 80 DEG C, keeps 1min, then rises to 230 DEG C of holding 15min with 10 DEG C/min；
Split ratio：Split sampling, split ratio is adjustable；Preferably, split ratio is chosen as 20:1
Sample size：1.0μL；
Carrier gas flux is：1.0ml/min, total flow is 24.0ml/min.
Test procedure：Take the silicone adhesive sample after 10g solidification, be dissolved in the closed glass jar filling 20ml toluene solution,
Room temperature places 24h, takes 10 μ L toluene solutions, and 1.0 μ L are to gas chromatography mass spectrometry chromatograph for injection.
Interpretation of result：
First group of silicone sealant sample obtains mass spectrogram as shown in Figure 1, and second group of sealant specimen obtains as Fig. 2
Shown mass spectrogram.As shown in figure 1, within the sign time more than 60 minutes, fragmentary a small amount of proton peak occurs, these
Proton peak is in substantially irregular scattered shape distribution, as shown in Fig. 2 at 30～40 minutes, concentrating and a large amount of proton peak occur,
Other time point is then similar with Fig. 1, occasionally with the presence of fragmentary scattered shape proton peak.From Fig. 1 and Fig. 2 embodied to two groups
The Comparative result that sealant specimen enters makings coupled HPLC sign can be seen that in fig. 2, in 30～40 offices, has more compared with Fig. 1
Substantial amounts of proton peak, through analyzing, these proton peak are corresponding mostly to be low alkane hydrocarbon structure, illustrates that the proton peak herein occurring is white
The characteristic peak of oil mixture, thus, by mass spectral analyses, can easily judge whether silicone sealant contains white oil very much.
In the present invention, above-mentioned two groups of sealant specimen can also be carried out with thermogravimetric sign, the method that thermogravimetric characterizes is in nitrogen
Atmosphere is raised to 200～220 DEG C from 20～50 DEG C of heating rates with 50～160 DEG C/min under conditions of enclosing, and at this temperature
Keep 2～5 minutes, then in the atmosphere of oxygen, be raised to 800～900 DEG C with the heating rate of 50～160 DEG C/min.
Fig. 3 is the TGA curve comparison figure that above-mentioned thermogravimetric characterizes the white oil fluid sealant obtaining and no white oil sealant specimen, such as
Shown in Fig. 3, the curve positioned at bottom is the TGA curve of white oil sealant specimen, and superposed curve is no white oil fluid sealant
The TGA curve of sample.White oil fluid sealant begins with mass loss at 90 DEG C about, and its proportion is about 16%.Subsequently seal
Colloid amount tends towards stability, and begins to decline until 450 DEG C again, first thermal weight loss platform subsequently.No white oil fluid sealant is 450
DEG C start, fluid sealant quality just starts to decrease, the predominantly loss of fluid sealant main quality.Two contrasts from Fig. 3
The fluid sealant thermostability that curve can be seen that admixture white oil is significantly lower than no white oil fluid sealant, and main cause is near 90 DEG C
There occurs mass loss, volatilized and cracked by white oil and lead to.In Practical Project, glass curtain wall under hot weather, for a long time
Stand the irradiation of sunlight, local temperature may be up to 70 DEG C, even more high, therefore if use white oil fluid sealant, its white oil composition
Be easy to shine upon or high-temperature condition under lose, thus fluid sealant volume contraction occurs, colloid cracking etc. phenomenon.
Preferably, can seek peace that to characterize two kinds of characterization results close to white oil-doped silicone for thermogravimetric by comprehensive gas chromatography mass spectrometry colour scale
Sealing is identified.
Contrast to outward appearance before and after the fluid sealant aging of product is it can be deduced that white oil fluid sealant is easier cracking, efflorescence and logical
Cross the test to commercially available prod, find that commercially available cheaper commodity has above-mentioned quality problems；
Before and after aging to fluid sealant, adhesion strength, the contrast surely stretching caking property and analysis, show that white oil glue adhesive property exists
Decline substantially after aging, and colloid cracking phenomena easily occurs；
Mensure to hardness before and after the fluid sealant aging of product, finds that the aging front elasticity of white oil fluid sealant is good, hardness is relatively low, but
With the carrying out of accelerated aging test, white oil fluid sealant setting rate is fast, and firmness change rate is much larger than no white oil fluid sealant product,
It is easier embrittlement, hardening；
Mensure to fluid sealant product quality loss rate, show that white oil fluid sealant mass loss rate is big, and majority exceedes mark
Accurate technical requirements, but simultaneously it has been found that the technical requirements of mass loss rate are excessively wide in range in standard, lead to part white oil
Glue can be by this mensure, and variable body " qualified " product comes into the market, and causes qualitative problems of construction.
Finally it should be noted that：Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and simultaneously
The non-restriction to embodiment.For those of ordinary skill in the field, can also do on the basis of the above description
Go out change or the variation of other multi-forms.There is no need to be exhaustive to all of embodiment.And thus drawn
Obvious change that Shen goes out or change among still in protection scope of the present invention.
Claims (8)
1. a kind of assay method of silicone sealant is it is characterised in that determination step is as follows,
Swelling or extraction test is carried out to silicone sealant, obtains swelling solution or extract, then swelling solution or extract are entered
Circulation of qi promoting matter coupled HPLC characterizes, and experimental condition and process are as follows：
Testing equipment：Gas chromatography mass spectrometry chromatograph Varian 450-GC and Varian 220-MS；
Testing column：6% fine propyl phenyl/94% polydimethylsiloxane capillary column；
Injector temperature：250℃；
Detector：FID, 260 DEG C of temperature；
Column temperature：80 DEG C of holding 1min of temperature programming, then rise to 230 DEG C of holding 15min with 10 DEG C/min；
Split ratio：Split sampling, split ratio is adjustable；
Sample size：1.0μL；
Test procedure：Take the silicone adhesive sample after 10g solidification, be dissolved in the closed glass jar filling 20ml toluene solution, room temperature
Place 24h, take 10 μ L toluene solutions, 1.0 μ L are to gas chromatography mass spectrometry chromatograph for injection,
If concentrating in special time period and more low alkane proton peak occurring,
Then judge to contain white oil in described silicone sealant.
2. assay method according to claim 1 it is characterised in that solvent used by described swell test be toluene, third
Any one in ketone, oxolane or hexamethylene.
3. assay method according to claim 1 and 2 it is characterised in that comprehensive gas chromatography mass spectrometry colour scale is sought peace thermogravimetric table
Levy two kinds of characterization results white oil-doped silicone sealant is measured.
4. assay method according to claim 3 is it is characterised in that the method that described thermogravimetric characterizes is in nitrogen atmosphere
Under the conditions of be raised to 200～220 DEG C in 20～50 DEG C of temperature elevating range with 20 DEG C/min, and at this temperature keep 5 minutes, so
It is raised to 800～900 DEG C with the heating rate of 20 DEG C/min in the atmosphere of oxygen afterwards.
5. assay method according to claim 1 is it is characterised in that the size of described capillary column is
60mX0.32mmX1.0μm.
6. assay method according to claim 1 is it is characterised in that described split ratio is 20:1.
7. assay method according to claim 1 is it is characterised in that the chromatographic carrier gas flux of described gas chromatography mass spectrometry is：
1.0ml/min, total flow is 24.0ml/min.
8. assay method according to claim 1 is it is characterised in that described special time period is 30-40 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610803782.1A CN106483209A (en) | 2016-09-06 | 2016-09-06 | Method for measuring silicone sealant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610803782.1A CN106483209A (en) | 2016-09-06 | 2016-09-06 | Method for measuring silicone sealant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106483209A true CN106483209A (en) | 2017-03-08 |
Family
ID=58273450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610803782.1A Pending CN106483209A (en) | 2016-09-06 | 2016-09-06 | Method for measuring silicone sealant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106483209A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722305A (en) * | 2017-10-17 | 2018-02-23 | 辽宁省产品质量监督检验院（辽宁省建筑材料监督检验院） | A kind of standard butyl rubber solution |
| CN114441100A (en) * | 2021-12-31 | 2022-05-06 | 航天科工防御技术研究试验中心 | Liquid crystal wave plate sealing performance detection method and device, electronic equipment and storage medium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101650280A (en) * | 2009-09-09 | 2010-02-17 | 广东中烟工业有限责任公司 | Quantitive detection method of volatile organic compounds in additive of cigarette filter stick |
| CN101887014A (en) * | 2010-06-13 | 2010-11-17 | 郑州中原应用技术研究开发有限公司 | Method for identifying white oil-doped silicone sealant |
| CN103822985A (en) * | 2014-03-12 | 2014-05-28 | 中国建筑科学研究院 | Chemical identifying method of white oil doped silicone sealant |
-
2016
- 2016-09-06 CN CN201610803782.1A patent/CN106483209A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101650280A (en) * | 2009-09-09 | 2010-02-17 | 广东中烟工业有限责任公司 | Quantitive detection method of volatile organic compounds in additive of cigarette filter stick |
| CN101887014A (en) * | 2010-06-13 | 2010-11-17 | 郑州中原应用技术研究开发有限公司 | Method for identifying white oil-doped silicone sealant |
| CN103822985A (en) * | 2014-03-12 | 2014-05-28 | 中国建筑科学研究院 | Chemical identifying method of white oil doped silicone sealant |
Non-Patent Citations (4)
| Title |
|---|
| 中华人民共和国国家质量监督检验检疫总局 中国国家标准化管理委员会: "GB 18582-2008 室内装饰装修材料内墙涂料中有害物质限量", 《中华人民共和国国家标准》 * |
| 刘亮等: "GC-MS法研究白油在肉鸡肾脏中残留的动态变化", 《食品安全质量检测学报》 * |
| 刘盈等: "掺白油硅酮窖封胶耐老化性能研究", 《中国建筑防水》 * |
| 杨元等: "气相色谱-质谱法测定食品中矿物油", 《中国公共卫生》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722305A (en) * | 2017-10-17 | 2018-02-23 | 辽宁省产品质量监督检验院（辽宁省建筑材料监督检验院） | A kind of standard butyl rubber solution |
| CN114441100A (en) * | 2021-12-31 | 2022-05-06 | 航天科工防御技术研究试验中心 | Liquid crystal wave plate sealing performance detection method and device, electronic equipment and storage medium |
| CN114441100B (en) * | 2021-12-31 | 2023-08-22 | 航天科工防御技术研究试验中心 | Liquid crystal wave plate tightness detection method and device, electronic equipment and storage medium |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101762664B (en) | Method for measuring volatility phenol compound in white wine | |
| CN101887014B (en) | Identification method of white oil-doped silicone sealant | |
| CN113960191B (en) | Method for measuring PC, PP, PS, PE microplastic content in soil by pyrolysis gas chromatography | |
| CN104215732A (en) | Method of taking Tenax as simulant to measure migration amount from paper and volatile and semi-volatile organic matter in paperboard by TD-GC/MS | |
| CN101021509A (en) | Method for determining volatile element in shaoxing wine | |
| CN106680409B (en) | The detection method of optical isomer in a kind of tea aroma composition | |
| CN110514756A (en) | A Quantitative Detection Method of Aroma Compounds in Liquor | |
| CN103630647A (en) | Reverse-phase chromatography and mass-spectrometry combined detection method for complete low-molecular-heparin degradation product through precolumn derivatization | |
| CN106483209A (en) | Method for measuring silicone sealant | |
| CN103822985A (en) | Chemical identifying method of white oil doped silicone sealant | |
| CN104034820A (en) | Method for rapidly distinguishing brand of kirschwasser | |
| CN102253137A (en) | Method for the detection of trace volatile sulfides in gypsum board | |
| Liu et al. | Elimination of matrix effects for headspace solid-phase microextraction of important volatile compounds in red wine using a novel coating | |
| CN113237977A (en) | Detection method of volatile flavor substances of white spirit | |
| CN100451648C (en) | Year wine identification method | |
| CN106770875A (en) | The method that grape wine Production area recognition is carried out based on metabolism group research meanses | |
| CN113341018B (en) | Method for measuring migration quantity of 10 volatile and semi-volatile compounds in packaging printing paper to MPPO | |
| CN113267588A (en) | Method for simultaneously detecting 7 acrylic acid and acrylate monomers in plastic product | |
| CN102706975B (en) | Method for identifying crude oil and fuel oil | |
| CN107607634A (en) | The method of chemical root resistance agent in quick discriminating chemistry root-resistant type root-resistant puncturing material | |
| de Carvalho et al. | Manuscripts from Different Brands of Ballpoint Pens–GC/MS Ageing Profile in Brazilian Tropical Weather | |
| CN106770752B (en) | A method for establishing pyrolysis fingerprints of Dalbergia wood and its application | |
| CN110082469A (en) | The measuring method of trace alcohols in transformer insulation oil, letones content | |
| CN109374810A (en) | A kind of hydrocarbon source rock Soluble Organic Matter light hydrocarbon component rapid analysis method | |
| CN104697942A (en) | Comparison of determination methods for formaldehyde content of wood-based plates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170308 |