CN112444617B - Odor evaluation method of polyolefin resin and application thereof - Google Patents
Odor evaluation method of polyolefin resin and application thereof Download PDFInfo
- Publication number
- CN112444617B CN112444617B CN201910833897.9A CN201910833897A CN112444617B CN 112444617 B CN112444617 B CN 112444617B CN 201910833897 A CN201910833897 A CN 201910833897A CN 112444617 B CN112444617 B CN 112444617B
- Authority
- CN
- China
- Prior art keywords
- odor
- tvoc
- polyolefin resin
- evaluation
- volatile organic
- 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.)
- Active
Links
- 238000011156 evaluation Methods 0.000 title claims abstract description 105
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000009835 boiling Methods 0.000 claims abstract description 39
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 38
- 238000012216 screening Methods 0.000 claims abstract description 14
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 13
- 238000004458 analytical method Methods 0.000 claims abstract description 10
- -1 polypropylene Polymers 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 30
- 239000012752 auxiliary agent Substances 0.000 claims description 29
- 238000001514 detection method Methods 0.000 claims description 25
- 239000004743 Polypropylene Substances 0.000 claims description 24
- 229920001155 polypropylene Polymers 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 238000004949 mass spectrometry Methods 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 238000003988 headspace gas chromatography Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 238000002347 injection Methods 0.000 abstract description 19
- 239000007924 injection Substances 0.000 abstract description 19
- 201000004569 Blindness Diseases 0.000 abstract description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 52
- DOGIHOCMZJUJNR-UHFFFAOYSA-N 4-methyloctane Chemical compound CCCCC(C)CCC DOGIHOCMZJUJNR-UHFFFAOYSA-N 0.000 description 38
- AUKVIBNBLXQNIZ-UHFFFAOYSA-N 2,4-dimethylheptane Chemical compound CCCC(C)CC(C)C AUKVIBNBLXQNIZ-UHFFFAOYSA-N 0.000 description 25
- 229920000098 polyolefin Polymers 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- ODGLTLJZCVNPBU-UHFFFAOYSA-N 2,3,5-trimethylhexane Chemical compound CC(C)CC(C)C(C)C ODGLTLJZCVNPBU-UHFFFAOYSA-N 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 13
- 238000001819 mass spectrum Methods 0.000 description 13
- WBRFDUJXCLCKPX-UHFFFAOYSA-N 2,3-dimethylheptane Chemical compound CCCCC(C)C(C)C WBRFDUJXCLCKPX-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- LFKIGTZUWPXSIH-UHFFFAOYSA-N but-1-ene;2-methylprop-1-ene Chemical compound CCC=C.CC(C)=C LFKIGTZUWPXSIH-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 210000001331 nose Anatomy 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0001—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00 by organoleptic means
-
- 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
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- 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
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
-
- 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
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/44—Resins; Plastics; Rubber; Leather
- G01N33/442—Resins; Plastics
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Pathology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Library & Information Science (AREA)
- Sampling And Sample Adjustment (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to the field of odor evaluation, in particular to an odor evaluation method of polyolefin resin and application thereof. The method comprises the following steps: (1) Performing odor grading by adopting an artificial odor evaluation method, and performing the step (2) when the evaluated odor grade is greater than the safe odor grade; (2) Measuring TVOC, when TVOC is less than the evaluation threshold value TVOC 0 Ending the evaluation; when TVOC is larger than or equal to the evaluation threshold value TVOC 0 When the step (3) is carried out; (3) And (3) carrying out headspace sample injection gas chromatography mass spectrometry analysis, screening volatile organic compounds with boiling points of 20-200 ℃ from the results, and selecting the first 2-5 volatile organic compounds with the largest peak areas. The method provided by the invention can be used for rapidly identifying the source of main odor of the polyolefin resin, avoiding blindness in the odor reduction operation process, and providing a targeted thought for effectively improving the odor grade.
Description
Technical Field
The invention relates to the field of odor evaluation, in particular to an odor evaluation method of polyolefin resin and application thereof.
Background
Polyolefin resins are important factors affecting the odor of polyolefin materials and articles. The prior polyolefin material and the prior product have the problem of releasing volatile organic compounds to different degrees, which further limits the application of the polyolefin material in the fields of high-grade automobile interior trim parts and the like to a great extent. In recent years, low-odor polyolefin resins have been attracting attention from resin manufacturers at home and abroad. The odor problem of polyolefin resin is reduced in the aspects of catalyst, polymerization process, powder deashing and the like in the production enterprises. The accurate judgment of the source of the smell is also a concern of the manufacturing enterprises.
The types and the concentrations of volatile organic compounds in polyolefin resins are complex and variable. In the production process, the catalyst system, triethylaluminum, an internal and external electron donor, a solvent for diluting the catalyst, a nucleating agent, an antioxidant, low molecular weight hydrocarbon, an oxygen-containing compound and the like can be influenced. In particular fields of application, for example, when polyolefin resins are used for the production of automobile materials, the control of odor becomes very strict. At this time, the selection of the polyolefin resin as a raw material, and the determination of the source of odor in the polyolefin resin become particularly important.
The existing methods for evaluating the smell, such as an artificial smell evaluation method, have great influence on subjective factors and cannot clearly determine the type of smell. However, most of the other detection means are not targeted, and the obtained result is quite huge, so that the person skilled in the art is not aware of how the person should go down at all in the face of a large amount of data.
Thus, the current art is always blind in finding the main source of smell, on the one hand it is not known how to judge the main substance of a particular source of smell from a large amount of data; on the other hand, even if selected, it is not possible to determine whether the selection is correct or not, and on the other hand, it is not known how to further judge or select what method should be done in the face of different situations or different polyolefins. In general, the prior art has not yet been provided with a systematic odor assessment method, so that a referenceable value of the results obtained can be ensured. Therefore, finding a polyolefin odor evaluation method with higher reliability of the obtained results of the system has important guiding significance for the field.
Disclosure of Invention
The present invention has been made to overcome the above problems occurring in the prior art, and an object of the present invention is to provide a method for evaluating odor of a polyolefin resin and application thereof. The method provided by the invention can effectively and rapidly evaluate the main source of smell, has high credibility, and is very suitable for the field of automobile materials with high smell requirements.
The first aspect of the present invention provides a method for evaluating odor of a polyolefin resin, comprising the steps of:
(1) Grading the odor of the polyolefin resin by adopting an artificial odor evaluation method, ending the evaluation when the evaluated odor grade is less than or equal to the safe odor grade, and making a conclusion of safety; when the evaluated odor level is greater than the safe odor level, performing step (2);
(2) Determining the total volatile organic compound TVOC of the polyolefin resin when TVOC < evaluation threshold TVOC 0 Ending the evaluation, and concluding that the smell mainly comes from the auxiliary agent added in the preparation process of the polyolefin resin; when TVOC is larger than or equal to the evaluation threshold value TVOC 0 When the step (3) is carried out;
(3) And (3) carrying out headspace sample injection gas chromatography-mass spectrometry on the polyolefin resin, screening volatile organic matters with boiling points of 20-200 ℃ from the results of the headspace sample injection gas chromatography-mass spectrometry, sorting the peak areas of the screened volatile organic matters from large to small, selecting the first 2-5 volatile organic matters with the largest peak areas, ending the evaluation, and making a conclusion that the 2-5 volatile organic matters are substances with main odor sources.
The second aspect of the invention provides the use of the method of the invention in the field of automotive materials.
Compared with the prior art, the method of the invention has at least the following advantages: the method can rapidly identify the source of main odor of the polyolefin resin, avoids blindness in the odor operation process, and provides a targeted thought for effectively improving the odor grade.
The method provides an orderly system evaluation method for judging the main odor source in the field, so that a result with higher credibility can be obtained. This has important guidance in the art, for example, can help those skilled in the art quickly determine the main source of odor, can help those skilled in the art select a more appropriate polyolefin as a preparation raw material, can guide those skilled in the art in selecting or replacing a raw material for use in the production process of a polyolefin resin, can guide those skilled in the art how to pretreat the polyolefin resin preparation material first when using the polyolefin resin, and so forth.
Other specific features and advantages of the present invention will be described in the following detailed description.
Drawings
FIG. 1 is a schematic representation of a scent evaluation flow chart according to one embodiment of the present invention;
fig. 2 is a schematic representation of a flow chart for odor assessment according to another embodiment of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a method for evaluating odor of a polyolefin resin, the flow chart of which is intended as shown in fig. 1, comprising the steps of:
(1) Grading the odor of the polyolefin resin by adopting an artificial odor evaluation method, ending the evaluation when the evaluated odor grade is less than or equal to the safe odor grade, and making a conclusion of safety; when the evaluated odor level is greater than the safe odor level, performing step (2);
(2) Determining the total volatile organic compound TVOC of the polyolefin resin when TVOC < evaluation threshold TVOC 0 Ending the evaluation, and concluding that the smell mainly comes from the auxiliary agent added in the preparation process of the polyolefin resin; when TVOC is larger than or equal to the evaluation threshold value TVOC 0 When the step (3) is carried out;
(3) And (3) carrying out headspace sample injection gas chromatography-mass spectrometry on the polyolefin resin, screening volatile organic matters with boiling points of 20-200 ℃ from the results of the headspace sample injection gas chromatography-mass spectrometry, sorting the peak areas of the screened volatile organic matters from large to small, selecting the first 2-5 volatile organic matters with the largest peak areas, ending the evaluation, and making a conclusion that the 2-5 volatile organic matters are substances with main odor sources.
According to the method of the present invention, in the step (1), the safety odor level is set according to the actual situation, and the safety odor level is set lower for a material for an automobile or the like having a relatively high demand, and in some fields having a relatively low demand, the safety odor level is set higher. The artificial odor evaluation method can directly perform preliminary screening, and when the evaluated odor level is smaller than the safe odor level, the subsequent steps are not needed, and the conclusions of safety, standard reaching, raw material serving, pretreatment not needed and the like can be directly obtained.
In the present invention, the method for evaluating artificial odor may be various methods for evaluating artificial odor in the art, and such methods have standards set by themselves or set by a plurality of automobile manufacturers in large scale, but these standards are very similar. Such as the component odor detection standard PV3900 (class 6 method), FORD FLTMBO131-03 (class 6 method) and the like for the interior space of an automobile.
Taking PV3900 as an example, this method requires placing a polyolefin resin in a vessel with a glass container cover with a gasket, allowing the resin to equilibrate at 80 ℃ for 2 hours, removing the resin from the heating box, and cooling the bottle wall to about 60 ℃ before evaluation, and allowing the resin to directly contact the outer wall of the bottle by hand. And scoring by more than five detectors individually in turn.
When the PV3900 standard is used, where the requirements are more stringent, it is preferred that the safety odour rating is in the range 3.5-3.85, more preferably 3.5-3.65.
The artificial smell evaluation result is the comprehensive feeling of different human noses on volatile organic compounds with different thresholds and different concentrations. Sometimes low threshold (e.g. H 2 The presence of a very low S gas content is a significant off-flavor), and sometimes a high concentration. When the odor grade evaluated in the step (1) is greater than the safe odor grade, the odor is proved to be unsatisfactory, and the source of the odor needs to be found. In this case, step (2) is continued.
In step (2), the total volatile organic compounds of the polyolefin resin are determined, the term "total volatile organic compounds" having the general abbreviation form TVOC (Total Volatile Organic Compound) in the art. TVOC in the present invention means the total volatile organic compound. In the present invention, TVOC mainly represents the contribution of alkanes to odor.
For polyolefin compounds, the substances responsible for the main source of odor can be classified into hydrocarbons (all of which can be classified as total volatile organic compounds, mainly alkanes) and non-pure hydrocarbons (all of which are essentially auxiliaries added from the polyolefin resin production process (e.g., during pelletization)).
The purpose of the method of step (2) is mainly to screen for non-pure hydrocarbons, since these compounds often give rise to a pronounced taste at very low concentrations (i.e. a low threshold), whereas in this case little if any substance is detected if analyzed by headspace gas chromatography mass spectrometry, or the detected substance is not actually the main source of odour (in which case the person skilled in the art is easily misled by the results). Such a low threshold polar organic must have a phenomenon that the odor is greatly contributed and the ratio of the polar organic is low in TVOC.
In step (2), the evaluation threshold TVOC 0 The selection can be made generally in the range of 5-110 mu g C/g, with lower values when more stringent and higher values when more relaxed.
Evaluation threshold TVOC 0 The selection of the desired source of the odor is more appropriate, and when the selection is too low or too high, it may cause erroneous judgment of the type of the odor source substance. For example, it should be originally mainly derived from the auxiliary agents added in the process of preparing polyolefin resin, but instead, the eyes are put on the detection of volatile organic compounds (mainly alkane compounds), so that an erroneous conclusion is obtained; alternatively, it should be originally derived mainly from volatile organic compounds (mainly alkanes), but is erroneously considered to be derived from an auxiliary agent added during the production of polyolefin resins, without detecting the volatile organic compounds.
Further preferably, the evaluation threshold value TVOC 0 Selected from the range of 5-80 mu g C/g.
In step (2), according to a preferred embodiment of the present invention (the flow chart of this mode is intended to be shown in fig. 2), the evaluation threshold is set to a first evaluation threshold TVOC 1 And a second evaluation threshold TVOC 2 The evaluation is divided into three states:
state-1: TVOC < first evaluation threshold TVOC 1 When the evaluation is finished, the odor is mainly derived from the auxiliary agent added in the preparation process of the polyolefin resinIs a conclusion of (2);
state-2: when the first evaluation threshold value TVOC 1 TVOC is less than or equal to the second evaluation threshold value TVOC 2 When the odor part comes from the auxiliary agent added in the preparation process of the polyolefin resin, and continuing the step (3);
state-3: when TVOC is larger than or equal to the second evaluation threshold value TVOC 2 When it is concluded that the odor does not originate mainly from the auxiliary agent added during the preparation of the polyolefin resin, and step (3) is continued.
More preferably, the first evaluation threshold TVOC 1 5-20 mu g C/g.
More preferably, the second evaluation threshold TVOC 2 50-80 mu g C/g.
According to a specific embodiment of the present invention, in the step (2), the total volatile organic compound TVOC of the polyolefin resin is measured, and when TVOC < 10 mu g C/g, the evaluation is ended, and the conclusion is made that the odor is mainly derived from the auxiliary agent added in the preparation process of the polyolefin resin;
when 10 mu g C/g is less than or equal to TVOC < 80 mu g C/g, concluding that the odor part is derived from the auxiliary agent added in the preparation process of the polyolefin resin, and continuing to carry out the step (3);
when TVOC is not less than 80 mu g C/g, the conclusion is made that the odor is not mainly derived from the auxiliary agent added in the preparation process of the polyolefin resin, and the step (3) is continued.
In step (3), very many organic compounds, even hundreds of results, can be detected by the headspace sample gas chromatography mass spectrometry analysis. In this case, the person skilled in the art is often faced with a large amount of data, and does not know how his hands should be taken.
In order to improve the efficiency and achieve the purpose of rapid evaluation, the volatile organic matters with the boiling point of 25-185 ℃ are screened from the results of the headspace sample gas chromatography-mass spectrometry analysis, preferably, the volatile organic matters with the boiling point of 30-160 ℃ are screened, and further preferably, the volatile organic matters with the boiling point of 35-145 ℃ are screened. The matching degree is higher than 90 percent.
In the invention, the headspace sample injection gas chromatography mass spectrum comprises a gas chromatography provided with a mass spectrum detector and a headspace sample injector, and comprises a chromatography workstation capable of performing a data acquisition function.
Preferably, the analytical column is an HP-5 polar capillary chromatographic column.
Preferably, the headspace sampling conditions are: 4-6g (most preferably 5 g) of the sample was placed in a 20mL headspace bottle and equilibrated at 120℃for 5h. While the standard methods of headspace sampling (such as standard methods PV3341 and VDA 277) and practical operations are generally "put 1.0g sample into 10mL headspace bottle", the inventors of the present invention found that breakthrough change of headspace sampling conditions to "put 4-6g sample into 20mL headspace bottle" enabled more volatile organic compounds present on the surface or even inside of polyolefin particles to volatilize out or migrate and volatilize out.
Preferably, the analysis conditions are: the carrier gas is high-purity helium (purity > 99.999%); the temperature of the sample inlet is 200 ℃; the split ratio is 20:1; the carrier gas speed is 1mL/min; the temperature programming condition is 35 ℃, the balance is carried out for 3min, and then the temperature is increased to 200 ℃ at 10 ℃/min, and the balance is carried out for 5min.
Preferably, mass spectrometry conditions: the temperature of the ion source is 200 ℃, and the full scanning m/z is 20-500.
In the present invention, since some of the above-described operation conditions are parameters in a standard method or a general method in the art, they are described as point values, but this does not affect the scope of the present invention. In fact, the present invention allows a certain degree of operating deviation or error, values within the range of + -10% (preferably 5%) of the present invention fall within the scope of the present invention.
In the present invention, in order to improve the efficiency and achieve the purpose of rapid evaluation, the compounds in the following table 1 are directly screened from the results of the headspace sample gas chromatography-mass spectrometry analysis, that is, substances which may be a main source of odor in each case can be substantially included.
TABLE 1
Then, sorting the peak areas of the selected volatile organic compounds from large to small, and selecting the first 2-5 volatile organic compounds with the largest peak areas. In this case, it can be judged with comparative certainty that the odor is mainly derived from the first 2 to 5 volatile organic compounds. Generally, the first 3 volatile organic compounds are taken, which is more favorable for achieving the purpose of rapid evaluation.
For the conclusion of step (2) above, a further conclusion of step (3) is as follows:
when step (2) is evaluated as state-2, the conclusion of step (3) is that "the smell is also partly derived from the alkane compounds, in particular mainly from the first 2-5 volatile organic compounds";
when step (2) is evaluated as state-3, the conclusion of step (3) is that "the odor is mainly derived from the first 2-5 volatile organics".
In the present invention, the polyolefin is preferably an impact copolymer polypropylene, a random copolymer polypropylene, a homo-polypropylene, a polyethylene, and a copolymer of propylene with ethylene, an alpha olefin.
In the present invention, it is preferred that the polyolefin has a melt flow rate of 0.1 to 250g/10min at 230℃and a load of 2.16 kg.
The method of the invention has good applicability. In general, it is believed that the greater the melt flow rate of a polyolefin, the more likely the odor of that polyolefin will be. Any melt flow rate, various types of polyolefin can be evaluated in the art using the methods of the present invention.
The method provides an orderly system evaluation method for judging the main odor source in the field, so that a result with higher credibility can be obtained. This has important guidance in the art, for example, can help those skilled in the art quickly determine the main source of odor, can help those skilled in the art select a more appropriate polyolefin as a preparation raw material, can guide those skilled in the art in selecting or replacing a raw material for use in the production process of a polyolefin resin, can guide those skilled in the art how to pretreat the polyolefin resin preparation material first when using the polyolefin resin, and so forth.
The second aspect of the invention provides the use of the method of the invention in the field of automotive materials.
According to the use of the present invention, preferably, in step (1), the safety odor level is from 3.5 to 3.8, more preferably from 3.5 to 3.65.
According to the application of the present invention, preferably, in step (2), the evaluation threshold value TVOC 0 Selected from the range of 5-110 mu g C/g; further preferably, the evaluation threshold value TVOC 0 Selected from the range of 5-80 mu g C/g.
When the evaluation threshold is set to a first evaluation threshold TVOC 1 And a second evaluation threshold TVOC 2 When, preferably, the first evaluation threshold TVOC 1 5-20 mu g C/g; preferably, the second evaluation threshold TVOC 2 50-80 mu g C/g.
According to the application of the present invention, preferably, in step (3), volatile organic compounds having a boiling point of 35-145 ℃ are selected from the results of the headspace sample gas chromatography mass spectrometry analysis.
According to the use of the present invention, preferably, in step (3), the first 3 volatile organic compounds having the largest peak areas are selected.
By the application of the method, the main source of the odor in the automobile or the house can be rapidly judged by the person skilled in the art, the person skilled in the art can be helped to select more proper polyolefin as the preparation raw material of the automobile material, the person skilled in the art can be guided to select or replace the raw material used in the production process of the polyolefin resin, the person skilled in the art can be guided to conduct pretreatment when the polyolefin resin is used for preparing the automobile material, and the like.
The present invention will be described in detail by examples. The following examples were evaluated according to the standards for automotive materials,
the standard of the artificial odor evaluation method was set to 3.5 according to PV 3900;
TVOC detection criteria according to PV3341, a first evaluation threshold TVOC 1 Set to 10 mu g C/g, a second evaluation threshold TVOC 2 Set to 80 μ g C/g;
the conditions of the headspace sample injection gas chromatography mass spectrum include: the analysis column is an HP-5 polar capillary chromatographic column; the headspace sample injection conditions are as follows: 5.0g of the sample is placed in a 20ml headspace bottle and equilibrated at 120℃for 5h; the analysis conditions were: the carrier gas is high-purity helium (purity > 99.999%); the temperature of the sample inlet is 200 ℃; the split ratio is 20:1; the carrier gas speed is 1ml/min; the temperature programming condition is 35 ℃, the balance is carried out for 3min, and then the temperature is increased to 200 ℃ at 10 ℃/min, and the balance is carried out for 5min; mass spectrometry conditions: the temperature of the ion source is 200 ℃, and the full scanning m/z is 20-500.
In the detection result of the headspace sample injection gas chromatography mass spectrum, volatile organic compounds with boiling points of 35-145 ℃ and matching degrees of more than 90% are screened.
Example 1
This example was conducted for odor evaluation of K8003 polypropylene of China (Wuhan) petrochemical Co. The melt flow rate of the K8003 polypropylene was 2.5g/10min (230 ℃ C. And 2.16 kg).
(1) The artificial smell evaluation result is 4.2 to 3.5, and the step (2) is carried out;
(2) The TVOC detection result is 104 mu g C/g and is more than 80 mu g C/g, the state-3 is met, the conclusion that the smell is not mainly derived from the auxiliary agent added in the preparation process of the polyolefin resin is made, and the step (3) is carried out;
(3) The detection results of the headspace sample injection gas chromatography mass spectrum after screening are shown in table 2.
TABLE 2
From the results of Table 2, three main volatile organics were screened through the peak area size, n-hexane (boiling point 69 ℃ C.), 2, 4-dimethylheptane (boiling point 133 ℃ C.) and 2-methylpentane (boiling point 63 ℃ C.) in this order.
The evaluation conclusion is that: the alkane organics have a large influence on the smell, and the most main smell sources are n-hexane, 2, 4-dimethylheptane and 2-methylpentane.
Example 2
This example was conducted for odor evaluation of K7227H polypropylene from China (Wuhan) petrochemical Co. The melt flow rate of the K7227H polypropylene was 29g/10min (230℃and 2.16 kg).
(1) The artificial smell evaluation result is 4.3 to 3.5, and the step (2) is carried out;
(2) The TVOC detection result is 218 mu g C/g which is more than 80 mu g C/g, the state-3 is met, the conclusion that the smell is not mainly derived from the auxiliary agent added in the preparation process of the polyolefin resin is made, and the step (3) is carried out;
(3) The detection results of the headspace sample injection gas chromatography mass spectrum after screening are shown in table 3.
TABLE 3 Table 3
From the results of Table 3, three main volatile organics were screened through the peak area size, 2, 4-dimethylheptane (boiling point 133 ℃ C.), n-hexane (boiling point 69 ℃ C.) and 2-methylpentane (boiling point 63 ℃ C.) in this order.
The evaluation conclusion is that: the alkane organics have a large influence on the smell, and the most main sources of the smell are 2, 4-dimethylheptane, n-hexane and 2-methylpentane.
Comparing the peak areas of 2, 4-dimethylheptane, n-hexane and 2-methylpentane in tables 2-3, it can be seen that the three common volatile organic compounds in K7227H polypropylene are higher than in K8003 polypropylene.
Example 3
This example was used for odor evaluation of 7555KNE2 polypropylene from ExxonMobil (Exxon MobilCorporation). The melt flow rate of this 75555 KNE2 polypropylene was 50g/10min (230℃and 2.16 kg).
(1) The artificial smell evaluation result is 4.3 to 3.5, and the step (2) is carried out;
(2) The TVOC detection result is 90.7 mu g C/g which is more than 80 mu g C/g, the state-3 is met, the conclusion that the smell is not mainly derived from the auxiliary agent added in the preparation process of the polyolefin resin is made, and the step (3) is carried out;
(3) The detection results of the headspace sample injection gas chromatography mass spectrum after screening are shown in table 4.
TABLE 4 Table 4
| Retention time/min | Peak area | Volatile organic compounds |
| 2.001 | 22398245 | 2-methylpentane |
| 2.224 | 1399255 | N-hexane |
| 5.872 | 3256075 | 2,3, 5-trimethylhexane |
| 6.031 | 28138048 | 2, 4-dimethylheptane |
| 6.75 | 1336274 | 2, 3-dimethylheptane |
| 6.911 | 9277022 | 4-methyl octane |
From the results of Table 4, three main volatile organics were screened by peak area size, 2, 4-dimethylheptane (boiling point 133 ℃), 2-methylpentane (boiling point 63 ℃) and 4-methyloctane (boiling point 143 ℃).
The evaluation conclusion is that: the alkanes have a major impact on the odor, the most predominant sources of odor being 2, 4-dimethylheptane, 2-methylpentane and 4-methyloctane.
Example 4
This example was subjected to odor evaluation on BX3900 polypropylene from SK Complex chemical Co. The melt flow rate of the BX3900 polypropylene was 60g/10min (230 ℃ C. And 2.16 kg).
(1) The artificial smell evaluation result is 3.55 to more than 3.5, and the step (2) is carried out;
(2) TVOC detection results are 10 mu g C/g < 57.4 mu g C/g < 80 mu g C/g, the state-2 is met, the conclusion that the odor part is derived from the auxiliary agent added in the preparation process of the polyolefin resin is made, and the step (3) is carried out;
(3) The detection results of the headspace sample injection gas chromatography mass spectrum after screening are shown in table 5.
TABLE 5
| Retention time/min | Peak area | Volatile organic compounds |
| 2.024 | 12340334 | 2-methylpentane |
| 2.243 | 938703 | N-hexane |
| 5.88 | 903283 | 2,3, 5-trimethylhexane |
| 6.036 | 12730830 | 2, 4-dimethylheptane |
| 6.756 | 530593 | 2, 3-dimethylheptane |
| 6.916 | 3796537 | 4-methyl octane |
From the results of Table 5, three main volatile organics were screened by peak area size, 2, 4-dimethylheptane (boiling point 133 ℃), 2-methylpentane (boiling point 63 ℃) and 4-methyloctane (boiling point 143 ℃).
Further, the evaluation conclusion is that: the odor is also partly derived from alkanes, in particular mainly from 2, 4-dimethylheptane, 2-methylpentane and 4-methyloctane.
Example 5
This example was conducted for odor evaluation of M30RHC polypropylene from Zhenhai refining chemical Co., ltd. The melt flow rate of the M30RHC polypropylene was 30g/10min (230 ℃ C. And 2.16 kg).
(1) The artificial smell evaluation result is 3.52 to 3.5, and the step (2) is carried out;
(2) TVOC detection results are 10 mu g C/g < 57.4 mu g C/g < 80 mu g C/g, the state-2 is met, the conclusion that the odor part is derived from the auxiliary agent added in the preparation process of the polyolefin resin is made, and the step (3) is carried out;
(3) The detection results of the headspace sample injection gas chromatography mass spectrum after screening are shown in table 6.
TABLE 6
| Retention time/min | Peak area | Volatile organic compounds |
| 2.007 | 5357969 | 2-methylpentane |
| 5.875 | 1661947 | 2,3, 5-trimethylhexane |
| 6.032 | 16506943 | 2, 4-dimethylHeptane (heptane) |
| 6.753 | 525214 | 2, 3-dimethylheptane |
| 6.913 | 3376229 | 4-methyl octane |
From the results of Table 6, three main volatile organics were screened by peak area size, 2, 4-dimethylheptane (boiling point 133 ℃), 2-methylpentane (boiling point 63 ℃) and 4-methyloctane (boiling point 143 ℃).
Further, the evaluation conclusion is that: the odor is also partly derived from alkanes, in particular mainly from 2, 4-dimethylheptane, 2-methylpentane and 4-methyloctane.
Example 6
This example was conducted for odor evaluation of M60RHC polypropylene from Zhenhai refining chemical Co., ltd. The melt flow rate of the M60RHC polypropylene was 60g/10min (230 ℃ C. And 2.16 kg).
(1) The artificial smell evaluation result is 3.62 to more than 3.5, and the step (2) is carried out;
(2) TVOC detection results are 10 mu g C/g < 75.4 mu g C/g < 80 mu g C/g, the state-2 is met, the conclusion that the odor part is derived from the auxiliary agent added in the preparation process of the polyolefin resin is made, and the step (3) is carried out;
(3) The detection results of the headspace sample injection gas chromatography mass spectrum after screening are shown in table 7.
TABLE 7
| Retention time/min | Peak area | Volatile organic compounds |
| 2.002 | 6863153 | 2-methylpentane |
| 5.872 | 1704531 | 2,3, 5-trimethylhexane |
| 6.03 | 22329546 | 2, 4-dimethylheptane |
| 6.752 | 406835 | 2, 3-dimethylheptane |
| 6.911 | 3155482 | 4-methyl octane |
From the results of Table 7, three main volatile organics were screened by peak area size, 2, 4-dimethylheptane (boiling point 133 ℃), 2-methylpentane (boiling point 63 ℃) and 4-methyloctane (boiling point 143 ℃).
Further, the evaluation conclusion is that: the odor is also partly derived from alkanes, in particular mainly from 2, 4-dimethylheptane, 2-methylpentane and 4-methyloctane.
Example 7
This example was conducted for odor evaluation of PE-GD-F polyethylene products from the China petrochemical Co., ltd. The PE-GD-F polyethylene had a melt flow rate of 3.5g/10min (230 ℃ C. And 2.16 kg).
(1) The artificial smell evaluation result is 3.86 to 3.5, and the step (2) is carried out;
(2) TVOC detection result is 1.83 mu g C/g < 10 mu g C/g, which accords with the state-1, and the conclusion is drawn that: the odor is mainly derived from the granulation aid.
In the embodiment, the polyethylene product is also detected by headspace sample injection gas chromatography mass spectrometry, and as a result, volatile organic compounds with boiling points of 35-145 ℃ and matching degrees of more than 90% cannot be screened. Thus, it was demonstrated that the concentration of paraffinic organics was very low and that the odor did not originate mainly from paraffinic organics.
Example 8
This example was conducted for odor evaluation of PPR-MN20-S polypropylene from the company Changling, inc. of petrochemical Co., ltd. The PPR-MN20-S polypropylene had a melt flow rate of 20g/10min (230 ℃ C. And 2.16 kg).
(1) The artificial smell evaluation result is 4.1 to 3.5, and the step (2) is carried out;
(2) The TVOC detection result is 97.4 mu g C/g and is more than 80 mu g C/g, the state-3 is met, the conclusion that the smell is not mainly derived from the auxiliary agent added in the preparation process of the polyolefin resin is made, and the step (3) is carried out;
(3) The detection results of the headspace sample injection gas chromatography mass spectrum after screening are shown in table 8.
TABLE 8
| Retention time/min | Peak area | Volatile organic compounds |
| 1.485 | 40797942 | Isobutene (i-butene) |
| 1.617 | 315077 | 2-methylbutane |
| 1.977 | 8520964 | 2-methylpentane |
| 2.193 | 437198 | Hexane |
| 2.93 | 928193 | 2-methylhexane |
| 3.068 | 501239 | 3-methylhexane |
| 5.832 | 326562 | 2,3, 5-trimethylhexane |
| 5.991 | 2810688 | 2, 4-dimethylheptane |
| 6.875 | 931009 | 4-methyl octane |
From the results of Table 8, three main volatile organics were screened through the peak area size, isobutylene (boiling point-6.9 ℃ C.), 2-methylpentane (boiling point 63 ℃ C.) and 2, 4-dimethylheptane (boiling point 133 ℃ C.) in this order.
The evaluation conclusion is that: the alkanes have a major impact on the odor, the most predominant sources of odor being isobutylene, 2-methylpentane and 2, 4-dimethylheptane.
Example 9
This example is for odor assessment of BI995 polypropylene of Han Huadao Dall (Hanwha total). The melt flow rate of the BI995 polypropylene was 100g/10min (230 ℃ C. And 2.16 kg).
(1) The artificial smell evaluation result is 3.65 to more than 3.5, and the step (2) is carried out;
(2) The TVOC detection result is 106 mu g C/g which is more than 80 mu g C/g, the state-3 is met, the conclusion that the smell is not mainly derived from the auxiliary agent added in the preparation process of the polyolefin resin is made, and the step (3) is carried out;
(3) The detection results of the headspace sample injection gas chromatography mass spectrum after screening are shown in table 9.
TABLE 9
| Retention time/min | Peak area | Volatile organic compounds |
| 1.973 | 934727 | 2-methylpentane |
| 5.839 | 488719 | 2,3, 5-trimethylHexane-based |
| 5.998 | 7057557 | 2, 4-dimethylheptane |
| 6.883 | 1608530 | 4-methyl octane |
From the results of Table 9, three main volatile organics were screened by peak area size, 2, 4-dimethylheptane (boiling point 133 ℃ C.), 4-methyl octane (boiling point 143 ℃ C.) and 2-methyl pentane (boiling point 63 ℃ C.) in this order.
The evaluation conclusion is that: the alkanes have a major impact on the odor, the most predominant sources of odor being 2, 4-dimethylheptane, 4-methyl octane and 2-methylpentane.
Example 10
This example is for odor assessment of BI750 polypropylene for Han Huadao Dall (Hanwha Total). The melt flow rate of the BI750 polypropylene was 28g/10min (230 ℃ C. And 2.16 kg).
(1) The artificial smell evaluation result is 3.8 to 3.5, and the step (2) is carried out;
(2) TVOC detection result is 10 mu g C/g < 59.5 mu g C/g < 80 mu g C/g, which accords with state-2, and the conclusion that the odor part is derived from the auxiliary agent added in the preparation process of the polyolefin resin is carried out in step (3);
(3) The detection results of the headspace sample injection gas chromatography mass spectrum after screening are shown in table 10.
Table 10
| Retention time/min | Peak area | Volatile organic compounds |
| 1.984 | 917096 | 2-methylpentane |
| 5.842 | 408804 | 2,3, 5-trimethylhexane |
| 6.002 | 4494439 | 2, 4-dimethylheptane |
| 6.724 | 199917 | 2, 3-dimethylheptane |
| 6.886 | 1469213 | 4-methyl octane |
From the results of Table 10, three main volatile organics were screened by peak area size, 2, 4-dimethylheptane (boiling point 133 ℃ C.), 4-methyl octane (boiling point 143 ℃ C.) and 2-methyl pentane (boiling point 63 ℃ C.) in this order.
The evaluation conclusion is that: the odor is also partly derived from alkanes, in particular mainly from 2, 4-dimethylheptane, 4-methyloctane and 2-methylpentane.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (12)
1. A method for evaluating odor of a polyolefin resin, the method comprising the steps of:
(1) Grading the odor of the polyolefin resin by adopting an artificial odor evaluation method, ending the evaluation when the evaluated odor grade is less than or equal to the safe odor grade, and making a conclusion of safety; when the evaluated odor level is greater than the safe odor level, performing step (2);
(2) Determining the total volatile organic compound TVOC of the polyolefin resin when TVOC < evaluation threshold TVOC 0 Ending the evaluation, and concluding that the smell mainly comes from the auxiliary agent added in the preparation process of the polyolefin resin; when TVOC is larger than or equal to the evaluation threshold value TVOC 0 When the step (3) is carried out; wherein the evaluation threshold TVOC 0 Selecting in the range of 5-110 mu g C/g;
(3) Performing headspace sample gas chromatography-mass spectrometry on the polyolefin resin, screening volatile organic matters with boiling points of 20-200 ℃ from the headspace sample gas chromatography-mass spectrometry analysis result, sorting the peak areas of the screened volatile organic matters from large to small, selecting the first 2-5 volatile organic matters with the largest peak areas, ending the evaluation, and making a conclusion that the 2-5 volatile organic matters are substances with main odor sources;
wherein the polyolefin resin is selected from at least one of impact copolymer polypropylene, random copolymer polypropylene and PE-GD-F polyethylene;
the polyolefin resin has a melt flow rate of 0.1 to 250g/10min at 230 ℃ under a load of 2.16 kg.
2. The method of claim 1, wherein in step (1), the artificial odor assessment method is a component odor detection standard PV3900 for automotive interior spaces, the safety odor rating being 3.5-3.85.
3. The method of claim 2, wherein the safe odor level is 3.5-3.65.
4. A method according to any one of claims 1-3, wherein in step (2), the evaluation threshold is set to a first evaluation threshold TVOC 1 And a second evaluation threshold TVOC 2 The evaluation is divided into three states:
state-1: TVOC < first evaluation threshold TVOC 1 Ending the evaluation, and concluding that the smell mainly comes from the auxiliary agent added in the preparation process of the polyolefin resin;
state-2: when the first evaluation threshold value TVOC 1 TVOC is less than or equal to the second evaluation threshold value TVOC 2 When the odor part comes from the auxiliary agent added in the preparation process of the polyolefin resin, and continuing the step (3);
state-3: when TVOC is larger than or equal to the second evaluation threshold value TVOC 2 When it is concluded that the odor does not originate mainly from the auxiliary agent added during the preparation of the polyolefin resin, and step (3) is continued.
5. The method according to claim 4, wherein the first evaluation threshold TVOC 1 5-20 mu g C/g;
and/or, the second evaluation threshold TVOC 2 50-80 mu g C/g.
6. The method according to claim 4, wherein the total volatile organic compound TVOC of the polyolefin resin is measured, and when TVOC < 10 mu g C/g, the evaluation is ended, and a conclusion is made that the odor is mainly derived from the auxiliary agent added in the polyolefin resin production process;
when 10 mu g C/g is less than or equal to TVOC < 80 mu g C/g, concluding that the odor part is derived from the auxiliary agent added in the preparation process of the polyolefin resin, and continuing to carry out the step (3);
when TVOC is not less than 80 mu g C/g, the conclusion is made that the odor is not mainly derived from the auxiliary agent added in the preparation process of the polyolefin resin, and the step (3) is continued.
7. The method according to claim 5, wherein the total volatile organic compound TVOC of the polyolefin resin is measured, and when TVOC < 10 mu g C/g, the evaluation is ended, and a conclusion is made that the odor is mainly derived from the auxiliary agent added in the polyolefin resin production process;
when 10 mu g C/g is less than or equal to TVOC < 80 mu g C/g, concluding that the odor part is derived from the auxiliary agent added in the preparation process of the polyolefin resin, and continuing to carry out the step (3);
when TVOC is not less than 80 mu g C/g, the conclusion is made that the odor is not mainly derived from the auxiliary agent added in the preparation process of the polyolefin resin, and the step (3) is continued.
8. The method according to claim 1, wherein in step (3), volatile organic compounds having a boiling point of 25-185 ℃ are selected from the results of the headspace gas chromatography mass spectrometry analysis.
9. The method of claim 8, wherein in step (3), volatile organics having a boiling point of 35-145 ℃ are selected from the results of the headspace gas chromatography mass spectrometry analysis.
10. The method according to claim 4, wherein when assessed as state-2, the conclusion of step (3) is that the odor is also partly derived from alkanes, in particular mainly from the first 2-5 volatile organics;
when assessed as state-3, step (3) concludes that the odor is predominantly derived from the first 2-5 volatile organics.
11. The method of claim 1, wherein in step (3), the headspace sampling conditions in the headspace sampling gas chromatography mass spectrometry analysis comprise: 4-6g of the sample was placed in a 20mL headspace bottle.
12. Use of the method for evaluating the odor of a polyolefin resin according to any one of claims 1 to 11 in the field of automotive materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910833897.9A CN112444617B (en) | 2019-09-04 | 2019-09-04 | Odor evaluation method of polyolefin resin and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910833897.9A CN112444617B (en) | 2019-09-04 | 2019-09-04 | Odor evaluation method of polyolefin resin and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112444617A CN112444617A (en) | 2021-03-05 |
| CN112444617B true CN112444617B (en) | 2023-05-23 |
Family
ID=74734792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910833897.9A Active CN112444617B (en) | 2019-09-04 | 2019-09-04 | Odor evaluation method of polyolefin resin and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112444617B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002202240A (en) * | 2000-12-28 | 2002-07-19 | Asahi Kasei Corp | Method of estimating permeability of odor component |
| CN104297434A (en) * | 2014-10-29 | 2015-01-21 | 重庆长安汽车股份有限公司 | Odor evaluation method for automotive interior parts |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2640507C1 (en) * | 2016-11-02 | 2018-01-09 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Воронежский государственный университет инженерных технологий" (ФГБОУ ВО "ВГУИТ") | Method of organoleptic evaluation of children's toys based on plastisol from polyvinylchloride |
| CN109212059A (en) * | 2018-08-30 | 2019-01-15 | 上海应用技术大学 | A kind of detection method of automobile leather odour component |
| CN109270193B (en) * | 2018-11-15 | 2020-12-22 | 安徽皖维高新材料股份有限公司 | Method for measuring volatile organic compounds in polyvinyl alcohol by automatic headspace sample injection-gas chromatography-mass spectrometry |
| CN110057952B (en) * | 2019-04-28 | 2024-06-28 | 贵州中烟工业有限责任公司 | Peculiar smell identification method for cigarette label paper |
-
2019
- 2019-09-04 CN CN201910833897.9A patent/CN112444617B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002202240A (en) * | 2000-12-28 | 2002-07-19 | Asahi Kasei Corp | Method of estimating permeability of odor component |
| CN104297434A (en) * | 2014-10-29 | 2015-01-21 | 重庆长安汽车股份有限公司 | Odor evaluation method for automotive interior parts |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112444617A (en) | 2021-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11518863B2 (en) | Aldehyde content reduction process and recycled polyolefin with low aldehyde content | |
| CA3214308C (en) | Mixed-plastics-polypropylene blend | |
| CN112444617B (en) | Odor evaluation method of polyolefin resin and application thereof | |
| CN105784893B (en) | A kind of discrimination method of natural rubber and isoprene rubber | |
| Joaquin et al. | Autocatalytic influence of different levels of arsine on the thermal stability and pyrolysis of polypropylene | |
| Feigenbaum et al. | Safety and quality of food contact materials. Part 1: Evaluation of analytical strategies to introduce migration testing into good manufacturing practice | |
| Barabas et al. | Study of the thermal oxidation of polyole‐fins. V. Volatile products in the thermal oxidation of polyethylene | |
| CN114965973A (en) | Method for identifying recycled plastic based on instrument detection and analysis technology combined with multiple chemometrics methods and/or machine learning algorithm | |
| CN113490708B (en) | Odor-inhibiting compositions for post-consumer resins | |
| Felgel-Farnholz et al. | Comparative study on the degradation of HDPE, LLDPE and LDPE during multiple extrusions | |
| CN109870561B (en) | Method for detecting high-density or low-density polyethylene reclaimed material | |
| Boyron et al. | An advanced technique for linear low‐density polyethylene composition determination: TGA–IST16–GC–MS coupling | |
| Cuthbertson et al. | Characterization of polymer properties and identification of additives in commercially available research plastics | |
| CN105136960A (en) | Method for detecting and distinguishing odor components of donkey hide, horse hide or cattle hide as well as distinguishing standard thereof | |
| Dong et al. | Determination of residual acetaldehyde in polyethylene terephthalate bottles, preforms, and resins by automated headspace gas chromatography | |
| TWI792711B (en) | Removal of odorants from post-consumer polyolefin waste | |
| Pavlova et al. | Gas Chromatography—Mass Spectrometry for Characterization of Liquid Products from Pyrolysis of Municipal Waste and Spent Tyres | |
| Willoughby et al. | Volatile component analysis as a routine characterisation tool: an approach to fingerprinting polyolefin type and process history using ATD-GC/MS | |
| Collins et al. | Analysis of haloanisoles in corks and wines | |
| Petrulionienė et al. | Emission of additives and degradation products from commercial polypropylene, polyethylene and their composite packages | |
| US11780986B2 (en) | Recycled plastics and methods thereof | |
| Ho et al. | Vitamin E based stabilizer components in HDPE polymer | |
| Han et al. | Analysis of off-flavor generated from a polyethylene terephthalate water bottles and caps by using an electronic nose | |
| Choi et al. | Analytical considerations for determination of the microstructures of sulfur‐cured solution styrene− butadiene rubbers | |
| JP2024050507A (en) | Naphtha for producing lower olefin, method of producing lower olefin composition, lower olefin composition, polyolefin polymer, and naphtha discrimination method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |