CN114573941A - TVOC standard sample of ABS matrix and preparation method thereof - Google Patents

TVOC standard sample of ABS matrix and preparation method thereof Download PDF

Info

Publication number
CN114573941A
CN114573941A CN202210234964.7A CN202210234964A CN114573941A CN 114573941 A CN114573941 A CN 114573941A CN 202210234964 A CN202210234964 A CN 202210234964A CN 114573941 A CN114573941 A CN 114573941A
Authority
CN
China
Prior art keywords
abs
tvoc
standard sample
volatile organic
abs resin
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.)
Granted
Application number
CN202210234964.7A
Other languages
Chinese (zh)
Other versions
CN114573941B (en
Inventor
索倩倩
廖成玲
庞承焕
李卫领
吴博
单长国
邵海波
林宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guogao High Polymer Material Industry Innovation Center Co Ltd
Original Assignee
Guogao High Polymer Material Industry Innovation Center Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guogao High Polymer Material Industry Innovation Center Co Ltd filed Critical Guogao High Polymer Material Industry Innovation Center Co Ltd
Priority to CN202210234964.7A priority Critical patent/CN114573941B/en
Publication of CN114573941A publication Critical patent/CN114573941A/en
Application granted granted Critical
Publication of CN114573941B publication Critical patent/CN114573941B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/38—Diluting, dispersing or mixing samples
    • 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
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/007—Arrangements to check the analyser
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
    • C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Analytical Chemistry (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • General Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Food Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a TVOC standard sample of an ABS matrix, and relates to the technical field of chemical standard samples. The TVOC standard sample of the ABS matrix provided by the invention comprises the following components in parts by weight: 80000-120000 parts of ABS resin, 1-5 parts of volatile organic compound, 5-15 parts of adsorbing material and 0-5 parts of auxiliary agent, wherein the adsorbing material is at least one of ZSM-5 molecular sieve and USY type molecular sieve. According to the invention, the TVOC standard sample is prepared by introducing volatile organic compounds, specific adsorption materials and the like into the ABS matrix resin, and the adsorption materials can adsorb the volatile organic compounds through acid sites on the pore channel structure of the TVOC standard sample, so that the TVOC standard sample is difficult to volatilize, thereby being beneficial to improving the uniformity and the storage stability of the TVOC standard sample.

Description

TVOC standard sample of ABS matrix and preparation method thereof
Technical Field
The invention relates to the technical field of chemical standard samples, in particular to a TVOC standard sample of an ABS matrix and a preparation method thereof.
Background
The Total Volatile Organic Compound (TVOC) refers to an organic substance with saturated vapor pressure of more than 133.32Pa at room temperature, and has a boiling point of 50-250 deg.C, and can exist in air in a form of evaporation at room temperature. TVOCs are mainly classified into eight types: alkanes, aromatic hydrocarbons, alkenes, halocarbons, esters, aldehydes, ketones, and others. The TVOC mainly comprises hydrocarbons, halogenated hydrocarbons, oxygen hydrocarbons and nitrogen hydrocarbons, and specifically comprises benzene series, organic chloride, Freon series, organic ketone, amine, alcohol, ether, ester, acid and petroleum hydrocarbon compounds. According to the definition of GB/T18883-2002, the volatile organic compounds with retention time between n-hexane and n-hexadecane are analyzed by sampling with Tenax GC or Tenax TA, a non-polar chromatographic column (polarity index less than 10). The toxicity, irritation, carcinogenicity and special smell of TVOC can affect skin and mucous membrane and cause acute damage to human body.
With the stricter environmental regulations, the emission requirements of the automobile industry on the smell of used materials, TVOC and the like are higher and higher, so that the requirements on the test accuracy are gradually improved with the increase of the test requirements. And the test accuracy not only relates to the equipment state, but also relates to the whole test system, so that the accuracy of the test system is crucial to be evaluated by adopting standard samples. However, the mixed standard on the market at present is mainly a liquid mixed standard of TVOC, and the problems of difficult transportation and the like exist. The solid mixing standard has wide related aspects and is difficult to control due to factors related to raw materials, processing technology, additives and the like, and is a difficulty in obtaining a standard sample with a specified TVOC value. The total volatile organic compound limit value is 50 μ gC/g according to the standard VW50180, Q/BAIC 182022, so the total volatile organic compound content of the TVOC standard sample needs to be referenced against this value, with standard samples containing total volatile organic compounds below and above this value, in order to have a referential to evaluate test samples of different ranges of TVOC values. Due to the low limit value of the total volatile organic compound, in the conventional preparation process of the TVOC standard sample, the addition amount of the total volatile organic compound is extremely low, and the problems of uneven mixing and weighing errors are caused by the excessively low addition amount of the total volatile organic compound, so that the content of the total volatile organic compound in the TVOC standard sample is unstable, and the accuracy of subsequent measurement is affected.
Disclosure of Invention
In order to solve the problems in the prior art, the present invention mainly aims to provide a TVOC standard sample of an ABS matrix and a preparation method thereof.
In order to achieve the above object, in a first aspect, the present invention provides a TVOC standard sample of an ABS matrix, comprising the following components in parts by weight: 80000-120000 parts of ABS resin, 1-5 parts of volatile organic compound, 5-15 parts of adsorbing material and 0-5 parts of auxiliary agent, wherein the adsorbing material is at least one of ZSM-5 molecular sieve and USY type molecular sieve.
The commonly used porous adsorption materials are an activated carbon molecular sieve and a zeolite molecular sieve, and although the activated carbon molecular sieve has a large specific surface area and good adsorption performance, the heat stability of the activated carbon molecular sieve is poor. The zeolite molecular sieve has rich micropores, larger specific surface area and excellent thermal stability, and the adsorption capacity of the zeolite molecular sieve on volatile organic compounds is related to various factors such as a pore channel structure, a silicon-aluminum ratio, balanced cations, surface characteristics and the like. In the technical scheme of the invention, the TVOC standard sample is prepared by introducing volatile organic compounds, specific adsorption materials and the like into ABS matrix resin, and the adsorption materials can adsorb the volatile organic compounds through acid sites on a pore channel structure of the TVOC standard sample, so that the TVOC standard sample is difficult to volatilize, thereby being beneficial to improving the uniformity and the storage stability of the TVOC standard sample.
As a preferred embodiment of the TVOC standard sample of the ABS matrix of the present invention, the volatile organic compound is at least one of benzene, toluene, styrene, ethylbenzene, p-xylene, m-xylene, o-xylene. The volatile organic compounds can be used in combination according to actual needs.
As a preferred embodiment of the TVOC standard sample of the ABS matrix of the present invention, the ZSM-5 molecular sieve has a silica-alumina ratio of 100-300.
The inventor finds that, in the ZSM-5 molecular sieve, the silica-alumina ratio is better than that of a TVOC standard sample correspondingly prepared by the ZSM-5 molecular sieve with the silica-alumina ratio of 100-300-.
As a preferred embodiment of the TVOC standard sample of the ABS matrix of the present invention, the ABS resin is prepared by bulk polymerization, and the addition amounts of styrene, butadiene and acrylonitrile in the ABS resin are styrene: butadiene: acrylonitrile (6-8), (2-3) and (2-3).
The ABS resin prepared by the bulk polymerization method has extremely low residual monomer content (the residual monomer in the bulk polymerization ABS resin is less than that in emulsion polymerization ABS), and the residual monomer can be removed by drying in a high-temperature air blast drying oven, so that the purity of the ABS resin is improved. Therefore, in the technical scheme of the invention, the ABS resin prepared by a bulk polymerization method is used as a base material, and then TVOC volatile substances such as benzene, toluene, styrene and the like are added to obtain a corresponding TVOC value standard sample.
As a preferred embodiment of the TVOC standard sample of the ABS matrix, the auxiliary agent is at least one of an antioxidant and a lubricant. The antioxidant can be selected from 1010 antioxidant, 168 antioxidant, 1076 antioxidant and 627V antioxidant; the lubricant may be selected from stearic acid, stearate, polyolefin wax type lubricants.
In a second aspect, the present invention further provides a preparation method of a TVOC standard sample of an ABS matrix, comprising the following steps:
(1) blending the volatile organic compound and the adsorbing material in a closed system to obtain the adsorbing material containing the volatile organic compound;
(2) preparing ABS mixed master batch: uniformly mixing the first ABS resin and the adsorption material containing the volatile organic compound, and then performing melt extrusion granulation to obtain the ABS mixed master batch;
(3) preparing a TVOC standard sample: uniformly mixing the ABS mixed master batch with a second ABS resin, and performing melt extrusion granulation to obtain the TVOC standard sample;
the TVOC content in the first ABS resin and the TVOC content in the second ABS resin are both lower than the TVOC content in the ABS mixed master batch.
In the technical scheme of the invention, the volatile organic compound is firstly blended with the adsorption substance with a porous structure, so that the volatility of the volatile organic compound is greatly reduced, and the volatile organic compound is more stably existed in resin; and then mixing the first ABS resin with an adsorbing material containing a volatile organic compound to prepare a total volatile organic compound high-concentration master batch (namely an ABS mixed master batch), and mixing the prepared total volatile organic compound high-concentration master batch with a second ABS resin to prepare standard samples with different required TVOC values.
Because the TVOC content in the first ABS resin and the TVOC content in the second ABS resin are both lower than the TVOC content in the ABS mixed master batch, namely, the essence of the technical scheme of the invention is that the adsorbing material containing the volatile organic compound is added into the first ABS resin to prepare the high-concentration ABS mixed master batch, and then the high-concentration ABS mixed master batch and the second ABS resin are mixed and diluted, so that the TVOC standard sample with low total volatile organic compound limit value is obtained. The preparation method can greatly reduce the volatility of the volatile organic compounds, so that the volatile organic compounds exist in the ABS resin in a stable state, in addition, the problem of uneven mixing caused by too small total volatile organic compound addition amount can be avoided, and meanwhile, the weighing error caused by too small total volatile organic compound addition amount can be reduced.
It should be noted that the first ABS resin and the second ABS resin in the technical solution of the present invention are in principle consistent in their sources, and the TVOC content is also the same.
As a preferable embodiment of the preparation method of the TVOC standard sample of the ABS matrix, in the step (2) of preparing the ABS mixed master batch, the first ABS resin, the adsorption material containing the volatile organic compound, and the auxiliary agent are uniformly mixed, and then melt-extruded and granulated to obtain the ABS mixed master batch.
In the technical scheme of the invention, in consideration of factors such as processability of the first ABS resin and the adsorbing material containing the volatile organic compound in the melt extrusion process after mixing, an auxiliary agent can be added on the basis of the first ABS resin and the adsorbing material containing the volatile organic compound to obtain the stable ABS mixed master batch. It is to be noted that the choice of auxiliaries is essential to be able to introduce no new VOC substances and to improve the processability.
As a preferable embodiment of the preparation method of the TVOC standard sample of the ABS matrix, in the step (3) of preparing the TVOC standard sample, the TVOC standard sample is obtained by uniformly mixing the ABS mixed masterbatch with the second ABS resin and the auxiliary agent, and then performing melt extrusion granulation.
In the technical scheme of the invention, the addition agent can be added to obtain the stable TVOC standard sample by considering the factors such as processability of the melt extrusion process after the ABS mixed master batch and the second ABS resin are mixed.
As a preferred embodiment of the method for preparing the TVOC standard sample of the ABS matrix of the present invention, the method for preparing the first ABS resin and the second ABS resin comprises the steps of: drying the ABS resin until the TVOC content is 10-20 mu gC/g.
In the technical scheme of the invention, a small amount of volatile organic compounds inevitably exist in the ABS resin, so that the influence of residual monomers on the accuracy is avoided, the purity of the ABS resin is improved, the ABS resin can be dried, the volatile organic compounds in the ABS resin cannot be completely removed by drying, and the TVOC content in the dried ABS resin can be reduced to 10-20 mu gC/g by detection.
As a preferred embodiment of the preparation method of the TVOC standard sample of the ABS matrix, the TVOC content of the ABS mixed masterbatch in the step (2) is 1000-2500 μ g C/g; the melt extrusion temperature in the step (2) and the step (3) is 180-200 ℃.
In the technical scheme of the invention, the TVOC content of the ABS mixed master batch in the step (2) has a direct influence on the amount of ABS resin required to be added in the subsequent dilution process, the TVOC content of the ABS mixed master batch is controlled within the range, the dilution rate can be controlled within a proper range, and the operation is convenient.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, volatile organic compounds, an adsorption material and the like are introduced into ABS matrix resin to prepare the TVOC standard sample, and the adsorption material can adsorb the volatile organic compounds to make the volatile organic compounds not easy to volatilize, so that the storage stability of the TVOC standard sample is improved;
(2) according to the technical scheme, the adsorption material containing the volatile organic compounds is added into the first ABS resin to prepare the high-concentration ABS mixed master batch, and then the high-concentration ABS mixed master batch is mixed with the second ABS resin to be diluted, so that the TVOC standard sample with the low total volatile organic compound limit value is obtained. By adopting the preparation method, the preparation requirements of standard samples with different TVOC values can be met, the problem of uneven mixing caused by too small addition amount of the total volatile organic compound can be avoided, and meanwhile, the weighing error caused by too small addition amount of the total volatile organic compound can be reduced;
(3) the technical scheme of the invention provides an evaluation mode for daily evaluation of the TVOC detection equipment state and the testing skill level of the checker for the third-party detection institution and the enterprise laboratory engaged in the detection project, so that the equipment state, the staff testing level and the like can be accurately confirmed, and the problem of difficulty in transportation and storage of the liquid standard sample does not exist.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The raw materials used in the embodiment of the invention are as follows:
ABS resin: adopting a bulk polymerization method, and taking a styrene monomer, a butadiene monomer and an acrylonitrile monomer as the styrene monomer according to the addition amount: butadiene monomer: acrylonitrile monomer (6: 2: 2) with the trade name of ABS275, which is purchased from Shanghai Gaoqiao petrochemical company Limited;
adsorbing material: ZSM-5 molecular sieve with the silicon-aluminum ratio of 50, Ziborun Xin chemical technology Co., Ltd;
ZSM-5 molecular sieve with the silicon-aluminum ratio of 100, Ziborun Xin chemical technology Co., Ltd;
ZSM-5 molecular sieve with the silicon-aluminum ratio of 200, Ziborun Xin chemical technology Co., Ltd;
ZSM-5 molecular sieve with the silicon-aluminum ratio of 300, Ziborun Xin chemical technology Co., Ltd;
ZSM-5 molecular sieve with the silicon-aluminum ratio of 400, Ziborun Xin chemical technology Co., Ltd;
USY type molecular sieve, ZiBorun Xin chemical science and technology Co;
13X zeolite molecular sieves, Ziborun Xin chemical technology Co., Ltd;
zeolite Beta molecular sieves, zibo run xin chemical technology ltd;
volatile organic compound (c): are all commercial products;
antioxidant: it is commercially available.
In the following examples and comparative examples, unless otherwise specified, volatile organic compounds and antioxidants were commercially available and used in parallel experiments in the same manner.
The examples of the invention and comparative examples relate to the following performance test standards or methods:
1. and (3) uniformity testing: according to CNAS-GL003 'guide for evaluating homogeneity and stability of capacity-verified samples', single-factor analysis of variance was used to test the homogeneity between samples, as follows: randomly extracting 15 prepared packets of samples, taking two samples from each packet of samples, measuring in parallel twice under a repeated condition, and calculating a variance test value of the statistic F;
2. and (3) stability testing: the stability of the samples was tested by the consistency between the two mean values in the t-test method according to CNAS-GL003 "guidelines for the evaluation of homogeneity and stability of samples for capacity verification". The specific method comprises the following steps: the uniformity test data was used as one of the average values, 10 samples were randomly selected from 15 packs of samples subjected to uniformity test, and after standing for 6 months, the test was performed in the same manner as in the uniformity test conditions, each sample was subjected to duplicate measurement under duplicate conditions, and the average value of the measurement was calculated. The value of t is calculated by averaging the measured data over two tests and calculating the standard deviation, with n degrees of freedom if t < significance level α (typically α ═ 0.05)1+n2-2 critical value t α (n)1+n2-2), then there is no significant difference between the two averages.
Example 1
In this example, a TVOC standard sample with a TVOC content of 30 μ g C/g was prepared, which included the following components: 1000g of ABS resin, 0.02g of volatile organic compounds (the mass ratio of toluene, ethylbenzene, o-xylene, m-xylene and p-xylene is 1:1:1:1), and 0.1g of adsorbing materials (ZSM-5 molecular sieves with the silicon-aluminum ratio of 200);
the preparation method comprises the following steps:
(1) mixing 2g of volatile organic compound with 10g of ZSM-5 molecular sieve with the silicon-aluminum ratio of 200 in a closed system to obtain 12g of adsorbing material containing the volatile organic compound;
(2) drying the ABS resin in a blast drying oven at 80 ℃ to obtain the ABS resin with TVOC content of 10 mu gC/g;
(3) preparing ABS mixed master batch with TVOC content of 2000 mu gC/g: putting 1000g of ABS resin (namely first ABS resin) and 12g of adsorbing material containing volatile organic compounds in a high-speed mixer, uniformly mixing, and performing melt extrusion granulation at the temperature of 180-200 ℃ by using a double-screw extruder to obtain ABS mixed master batch;
(4) preparing a TVOC standard sample: 10.1g of ABS mixed master batch and 990g of second ABS resin are placed in a high-speed mixer to be uniformly mixed, and then melt extrusion granulation is carried out at the temperature of 180-200 ℃ by a double-screw extruder to obtain the TVOC standard sample with the TVOC content of 30 mu gC/g.
The standard sample prepared in example 1 was tested according to the standard PV3341 "emission measurement of organic compounds from non-metallic materials for automotive interiors".
TABLE 1 homogeneity test data for TVOC standard sample of example 1
Figure BDA0003539697860000071
Figure BDA0003539697860000081
TABLE 2 stability test data for TVOC standard sample of example 1
Detecting items TVOCμgC/g
1 29.84
2 29.91
3 29.67
4 29.81
5 29.77
6 29.75
7 29.69
8 29.57
9 29.85
10 29.87
17 29.78
12 29.67
13 29.83
14 29.79
15 29.89
16 29.76
17 29.79
18 29.94
19 29.94
20 29.78
Mean value of 29.81
Standard deviation of 0.0994
TABLE 3 evaluation of the results of stability test of TVOC standard sample of example 1
Stability test Total mean 29.81
Total mean value of homogeneity test 29.83
t value 0.46
t0.05(30+20-2) 1.677
Tables 1-3 show the results of the uniformity and stability tests, respectively, for example 1; it can be seen from Table 1 that F < F0.05(14,15), showing that there is no significant difference between core samples in the samples, and the samples are uniform. It can be seen from tables 2 and 3 that t < t0.05(30+20-2), indicating that there is no significant difference between the two averages and that the sample stability is good.
Example 2
This example is substantially the same as the preparation of the TVOC standard sample of example 1, except that: this example uses a ZSM-5 molecular sieve having a silica to alumina ratio of 100.
Example 3
This example is substantially the same as the preparation of the TVOC standard sample of example 1, except that: this example uses a ZSM-5 molecular sieve having a silica to alumina ratio of 300.
Example 4
This example is substantially the same as the preparation of the TVOC standard sample of example 1, except that: this example uses a ZSM-5 molecular sieve having a silica to alumina ratio of 50.
Example 5
This example is substantially the same as the method for preparing the TVOC standard sample in example 1, except that: this example uses a ZSM-5 molecular sieve having a silica to alumina ratio of 400.
Example 6
This example is substantially the same as the method for preparing the TVOC standard sample in example 1, except that: this example uses a USY type molecular sieve.
Example 7
In this example, a TVOC standard sample with a TVOC content of 70 μ gC/g was prepared, which comprises the following components: 998.8g of ABS resin, 0.05g of volatile organic compound (the mass ratio of toluene to ethylbenzene is 1:1), 0.25g of adsorbing material (ZSM-5 molecular sieve with the silicon-aluminum ratio of 300) and 0.025g of auxiliary agent (antioxidant);
the preparation method comprises the following steps:
(1) mixing 2g of volatile organic compound (1.0 g of toluene and 1.0g of ethylbenzene) and 10g of ZSM-5 molecular sieve with the silica-alumina ratio of 300 in a closed system to obtain 12g of adsorbing material containing the volatile organic compound;
(2) drying the ABS resin in a blast drying oven at 80 ℃ to obtain the ABS resin with the TVOC content of 20 mu gC/g;
(3) preparing ABS mixed master batch with TVOC content of 2000 mu gC/g: putting 1000g of ABS resin (namely first ABS resin), 12g of adsorbing material containing volatile organic compounds and 1g of antioxidant into a high-speed mixer, uniformly mixing, and performing melt extrusion granulation at the temperature of 180-200 ℃ through a double-screw extruder to obtain ABS mixed master batches;
(4) preparing a TVOC standard sample: placing 25.1g of ABS mixed master batch and 974g of second ABS resin in a high-speed mixer for uniform mixing, and performing melt extrusion granulation at 180-200 ℃ by using a double-screw extruder to obtain a TVOC standard sample with the TVOC content of 70 mu gC/g;
the prepared standard sample is tested according to the standard PV3341 emission determination of organic compounds of non-metallic materials of automotive interiors. The test results are shown in tables 4-6 below.
TABLE 4 homogeneity test data for TVOC standard sample of example 7
Figure BDA0003539697860000101
TABLE 5 stability test data for TVOC standard sample of example 7
Figure BDA0003539697860000102
Figure BDA0003539697860000111
TABLE 6 evaluation of the results of stability test of TVOC standard sample of example 7
Stability test Total mean 69.71
Total mean value of homogeneity test 69.63
Value of T 0.875
t0.0s(30+20-2) 1.677
From Table 4, it can be seen that F < F0.05(14,15), showing that the core samples in the samples have no significant difference, and the samples are uniform; from tables 5 and 6, it can be seen that t < t0.05(30+20-2), indicating that there is no significant difference between the two averages and that the sample stability is good.
Example 8
In this example, a TVOC standard sample with a TVOC content of 110 μ gC/g was prepared, which comprises the following components: 999.2g of ABS resin, 0.09g of volatile organic compound (the mass ratio of o-xylene, m-xylene, p-xylene and styrene is 1:1:1), 0.47g of adsorbing material (USY type molecular sieve) and 0.047g of auxiliary agent (antioxidant);
the preparation method comprises the following steps:
(1) blending 2g of volatile organic compounds (0.5 g of o-xylene, 0.5g of m-xylene, 0.5g of p-xylene and 0.5g of styrene) with 10g of USY type molecular sieve to obtain 12g of adsorbing material containing the volatile organic compounds;
(2) drying the ABS resin in a blast drying oven at 80 ℃ to obtain the ABS resin with the TVOC content of 15 mu gC/g;
(3) preparing ABS mixed master batch with TVOC content of 2000 mu gC/g: putting 1000g of ABS resin (namely first ABS resin), 12g of adsorbing material containing volatile organic compounds and 1g of antioxidant into a high-speed mixer, uniformly mixing, and performing melt extrusion granulation at the temperature of 180-200 ℃ through a double-screw extruder to obtain ABS mixed master batches;
(4) preparing a TVOC standard sample: placing 47.8g of ABS mixed master batch and 952g of second ABS resin in a high-speed mixer for uniform mixing, and then performing melt extrusion granulation at the temperature of 180-200 ℃ by a double-screw extruder to obtain a TVOC standard sample with the TVOC content of 110 mu gC/g;
the prepared standard sample is tested according to the standard PV3341 emission determination of organic compounds of non-metallic materials of automotive interiors. The test results are shown in tables 7 to 9 below.
TABLE 7 homogeneity test data for TVOC standard sample of example 8
Figure BDA0003539697860000121
Figure BDA0003539697860000131
TABLE 8 stability test data for TVOC standard sample of example 8
Detecting items TVOCμgC/g
1 110.02
2 109.98
3 109.87
4 109.85
5 110.07
6 110.00
7 109.97
8 109.94
9 109.82
10 109.91
17 110.02
12 109.86
13 109.86
14 109.93
15 110.07
16 109.8
17 109.94
18 109.92
19 109.85
20 109.81
Mean value of 109.92
Standard deviation of 0.08401
TABLE 9 evaluation of the results of stability test of TVOC standard sample of example 8
Stability test Total mean 109.92
Total mean value of homogeneity test 109.93
t value 0.388
t0.05(30+20-2) 1.677
It can be seen from Table 7 that F < F0.05(14,15), showing that the core samples in the samples have no significant difference, and the samples are uniform; from tables 8 and 9, it can be seen that t < t0.05(30+20-2), indicating that there is no significant difference between the two averages and that the sample stability is good.
Comparative example 1
Comparative example 1 is prepared substantially the same as the TVOC standard sample of example 1 except that: the comparative example used a 13X zeolite molecular sieve.
Comparative example 2
Comparative example 2 is prepared substantially the same as the TVOC standard sample of example 1, except that: the comparative example used zeolite Beta molecular sieve.
The results of the performance tests of examples 2 to 8 and comparative examples 1 to 2 are shown in table 10 below. (for comparison purposes only the F value, the Total average stability test, the Total average homogeneity test and the t value are recorded)
TABLE 10 results of the Performance test of examples 1 to 8 and comparative examples 1 to 2
Figure BDA0003539697860000141
Since the uniformity and stability of examples 2-8 and comparative examples 1-2 were consistent in terms of the selection method and the number of tests, the uniformity and stability of the samples of examples 2-8 and comparative examples 1-2 were determined according to the same criteria as in example 1, wherein F < F is determined according to the uniformity test data of the samples0.05(14,15) ═ 2.42 and data from the sample stability test t < t0.05(30+20-2) ═ 1.677 is the basis for judging whether the uniformity and stability of the sample meet the requirements.
As can be seen from Table 10, F > F in comparative examples 1 and 20.05(14,15)Indicating that there is a significant difference between the samples of comparative example 1; furthermore, t > t for comparative examples 1 and 20.05(30+20-2)The significant difference exists between the two average values, and the stability of the sample is poor; the reason for this is that the pore size of the zeolite 13X and zeolite Beta in the comparative example is large, and the adsorbed organic molecules have better stability only when the pore size of the adsorbent material matches the analytical kinetic diameter of the volatile organic compound.
In addition, in example 4, the silica-alumina ratio of the ZSM-5 molecular sieve is too small, so that the acting force between the ZSM-5 and the volatile organic compound molecules is weak, the uniformity and stability of the prepared sample are affected, and the F value and the t value of the prepared standard sample are slightly high; in example 5, because the silica-alumina ratio of the ZSM-5 molecular sieve is too large, the pore size of the ZSM-5 molecular sieve is slightly reduced with the increase of the silica-alumina ratio, so that the adsorption effect of the ZSM-5 molecular sieve on volatile organic compounds is affected, and the F value and the t value of the prepared standard sample are slightly higher.
Although there was some difference in uniformity and stability between examples 1-8, all examples had F values less than F0.05(14,15)All t values are less than t0.05(30+20-2)The TVOC standard sample meets the basic requirements of the standard sample, and is suitable for evaluation test of personnel test methods and detection equipment as the TVOC standard sample.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The TVOC standard sample of the ABS matrix is characterized by comprising the following components in parts by weight: 80000-120000 parts of ABS resin, 1-5 parts of volatile organic compound, 5-15 parts of adsorbing material and 0-5 parts of auxiliary agent, wherein the adsorbing material is at least one of ZSM-5 molecular sieve and USY type molecular sieve.
2. The TVOC standard sample of ABS matrix of claim 1, wherein said volatile organic compound is at least one of benzene, toluene, styrene, ethylbenzene, para-xylene, meta-xylene, ortho-xylene.
3. The TVOC standard sample of ABS matrix of claim 1 wherein said ZSM-5 molecular sieve has a silica to alumina ratio of 100-300.
4. The TVOC standard sample of ABS matrix of claim 1, wherein said ABS resin is prepared by bulk polymerization, and the addition amount of styrene, butadiene and acrylonitrile in said ABS resin is styrene: butadiene: acrylonitrile is (6-8), (2-3) and (2-3).
5. The TVOC standard sample of ABS matrix of claim 1, wherein said adjuvant is at least one of an antioxidant, a lubricant.
6. A preparation method of a TVOC standard sample of an ABS substrate is characterized by comprising the following steps:
(1) blending the volatile organic compound and the adsorbing material in a closed system to obtain the adsorbing material containing the volatile organic compound;
(2) preparing ABS mixed master batch: uniformly mixing the first ABS resin and the adsorption material containing the volatile organic compound, and then performing melt extrusion granulation to obtain the ABS mixed master batch;
(3) preparing a TVOC standard sample: uniformly mixing the ABS mixed master batch with a second ABS resin, and performing melt extrusion granulation to obtain the TVOC standard sample;
the TVOC content in the first ABS resin and the TVOC content in the second ABS resin are both lower than the TVOC content in the ABS mixed master batch.
7. The method for preparing the TVOC standard sample of the ABS matrix according to claim 6, wherein in the step (2) of preparing the ABS blended masterbatch, the first ABS resin, the adsorbing material containing the volatile organic compound and the auxiliary agent are uniformly mixed, and then are subjected to melt extrusion granulation to obtain the ABS blended masterbatch.
8. The method for preparing a TVOC standard sample of an ABS matrix according to claim 6, wherein in the step (3) of preparing a TVOC standard sample, the TVOC standard sample is obtained by uniformly mixing the ABS blend mother particle with the second ABS resin and the auxiliary agent, and then performing melt extrusion granulation.
9. The method of preparing a TVOC standard sample of an ABS substrate of claim 6, wherein the method of preparing the first ABS resin and the second ABS resin comprises the steps of: drying the ABS resin until the TVOC content is 10-20 mu gC/g.
10. The method for preparing the TVOC standard sample of the ABS matrix as claimed in claim 8, wherein the TVOC content of the ABS blended masterbatch in the step (2) is 1000-; the melt extrusion temperature in the step (2) and the step (3) is 180-200 ℃.
CN202210234964.7A 2022-03-10 2022-03-10 TVOC standard sample of ABS (Acrylonitrile butadiene styrene) matrix and preparation method thereof Active CN114573941B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210234964.7A CN114573941B (en) 2022-03-10 2022-03-10 TVOC standard sample of ABS (Acrylonitrile butadiene styrene) matrix and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210234964.7A CN114573941B (en) 2022-03-10 2022-03-10 TVOC standard sample of ABS (Acrylonitrile butadiene styrene) matrix and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114573941A true CN114573941A (en) 2022-06-03
CN114573941B CN114573941B (en) 2023-08-18

Family

ID=81780160

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210234964.7A Active CN114573941B (en) 2022-03-10 2022-03-10 TVOC standard sample of ABS (Acrylonitrile butadiene styrene) matrix and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114573941B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1730543A (en) * 2005-07-29 2006-02-08 上海普利特复合材料有限公司 Little odor acrylonitrile-butadiene-styrene ternary copolymerized resin compound
CN101928429A (en) * 2010-08-27 2010-12-29 金发科技股份有限公司 Low TVOC polypropylene composite for motor vehicles and preparation method thereof
CN106633505A (en) * 2016-11-26 2017-05-10 金发科技股份有限公司 Preparation method of standard sample composed of more than ten elements (As, Se, P and the like) and multiple phthalates in polyvinyl chloride (PVC)
CN109342134A (en) * 2018-09-25 2019-02-15 金发科技股份有限公司 The preparation method of PP plastics Reference Materials of PAHs
CN112795093A (en) * 2020-12-31 2021-05-14 国高材高分子材料产业创新中心有限公司 Resin-based aldehyde ketone standard substance and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1730543A (en) * 2005-07-29 2006-02-08 上海普利特复合材料有限公司 Little odor acrylonitrile-butadiene-styrene ternary copolymerized resin compound
CN101928429A (en) * 2010-08-27 2010-12-29 金发科技股份有限公司 Low TVOC polypropylene composite for motor vehicles and preparation method thereof
CN106633505A (en) * 2016-11-26 2017-05-10 金发科技股份有限公司 Preparation method of standard sample composed of more than ten elements (As, Se, P and the like) and multiple phthalates in polyvinyl chloride (PVC)
CN109342134A (en) * 2018-09-25 2019-02-15 金发科技股份有限公司 The preparation method of PP plastics Reference Materials of PAHs
CN112795093A (en) * 2020-12-31 2021-05-14 国高材高分子材料产业创新中心有限公司 Resin-based aldehyde ketone standard substance and preparation method thereof

Also Published As

Publication number Publication date
CN114573941B (en) 2023-08-18

Similar Documents

Publication Publication Date Title
Jerabek Characterization of swollen polymer gels using size exclusion chromatography
Macko et al. Characterization of ethylene‐propylene copolymers with high‐temperature gradient adsorption liquid chromatography and CRYSTAF
Hopkins et al. A dual channel gas chromatograph for atmospheric analysis of volatile organic compounds including oxygenated and monoterpene compounds
Jandera et al. Comparison of various stationary phases for normal-phase high-performance liquid chromatography of ethoxylated alkylphenols
MacCrehan et al. Reproducible vapor–time profiles using solid-phase microextraction with an externally sampled internal standard
CN114573941B (en) TVOC standard sample of ABS (Acrylonitrile butadiene styrene) matrix and preparation method thereof
COCHEO et al. Rubber manufacture: Sampling and identification of volatile pollutants
Schuberth A full evaporation headspace technique with capillary GC and ITD: a means for quantitating volatile organic compounds in biological samples
US3545930A (en) Colorimetric oxygen detection
CN112795093A (en) Resin-based aldehyde ketone standard substance and preparation method thereof
Coulson Hydrocarbon compound-type analysis of automobile exhaust gases by mass spectrometry
Widdoes et al. Vapor-liquid equilibrium constants for carbon monoxide
Wampler et al. Effect of heating rate on oxidative degradation of polymeric materials
Corish Analysis of cis-and trans-1: 4 contents of polyisoprenes by near infra-red spectroscopy
CN113341018B (en) Method for measuring migration quantity of 10 volatile and semi-volatile compounds in packaging printing paper to MPPO
Shen In-situ sampling system for thermal volatilization analysis of nonvolatile materials by gas chromatography-mass spectrometry
CN111077255A (en) Method for detecting migration volume of 4, 4&#39;-biphenol and 4,4&#39; -dichlorodiphenyl sulfone in PPSU (polypropylene sulfone) milk bottle
CN110646547A (en) Method for simultaneously measuring di (2-ethyl) hexyl ortho-, meta-and terephthalate in food simulant
Allen et al. International comparison of key volatile organic components in indoor air
Fujii Trace determination of vinyl chloride in water by direct aqueous injection gas chromatography-mass spectrometry
Venema Dynamic headspace capillary gas chromatography: A versatile analytical technique
Petruzzelli et al. STDS study for the identification of released compounds from commercial ion-exchange resins
Hu Chromatopyrography analysis of rubbers and other high polymers
RU2088634C1 (en) Method of determining optimal composition of coal charge for coking process
Rohrschneider Dependence of GC-retention data on phase constants a and b in the James-Martin relationship for homologous n-alkanes

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