CN105606430A - Separation and analysis methods of aromatic hydrocarbon additive in polymer with benzene ring structure - Google Patents
Separation and analysis methods of aromatic hydrocarbon additive in polymer with benzene ring structure Download PDFInfo
- Publication number
- CN105606430A CN105606430A CN201510981214.6A CN201510981214A CN105606430A CN 105606430 A CN105606430 A CN 105606430A CN 201510981214 A CN201510981214 A CN 201510981214A CN 105606430 A CN105606430 A CN 105606430A
- Authority
- CN
- China
- Prior art keywords
- polymer
- sulfonation
- additive
- separation method
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- G01N1/34—Purifying; Cleaning
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A separation method of an aromatic hydrocarbon additive in a polymer with a benzene ring structure at least comprises following steps: (1), a step of dissolving: an organic solvent is provided and is used for dissolving the polymer, and a mixed solution is obtained; (2), a step of sulfonation: a sulfonating agent is provided and is used for sulfonating the mixed solution obtained in the step (1), and a solution containing the aromatic hydrocarbon additive is obtained; (3), a step of separation: water is adopted for extraction, filtering is performed, an aqueous phase is collected, and a sulfonated aromatic hydrocarbon additive solution is obtained. A product obtained through separation is tested by adopting one or more of infrared spectrometry, high performance liquid chromatography, a gas chromatographic method, a liquid chromatographic-mass spectrometric method, liquid-ultraviolet spectrometry, an element analysis method, fluorescent spectrometry, a thermal gravity analysis method, a differential thermal analysis method and a nuclear magnetic resonance method.
Description
Technical field
The present invention relates to separation and the detection method of additive in a kind of polymer, particularly a kind of separation and analytical method containing arene additive in the polymer of benzene ring structure.
Background technology
The life that polymer macromolecular material is people provides a lot of facilities, according to different purposes, the high molecular structure difference of polymer, all contains benzene ring structure in most polymer macromolecule, for example, polyphenylene oxide, polystyrene, Merlon, PETG etc. Owing to being heated, the impact of the environment such as light, oxidation easily degraded lose its premium properties, therefore in macromolecular material, must add additive, such as antioxidant, fire retardant, ultraviolet absorber, fluorescent whitening agent, mould inhibitor, antiwear additive etc., in these additives, all contain benzene ring structure. In recent years, about using in polymer, decree and the regulation of additive are also more and more perfect, for example, must observe the standard of FDA and the promulgation of mechanism of European Government for the plastics of packaging for foodstuff, medicine and toy. Therefore the additive in Fast Measurement polymeric articles can provide effective reference frame for the quality control of polymer product on market.
Thereby, be starved of developing of technique a kind of separation and detection method containing arene additive in the polymer of benzene ring structure.
Summary of the invention
In order to solve prior art problem, the invention provides a kind of separation method containing arene additive in the polymer of benzene ring structure, at least comprise following steps:
(1) dissolving step, provides organic solvent, and dissolve polymer obtains mixed solution;
(2) sulfonation procedure, provides sulfonated reagent, and gained mixed solution in sulfonation procedure (1), obtains the solution that contains sulfonated aromatic hydro carbons additive;
(3) separating step, water extraction, filters, and collects water, obtains the solution of sulfonated aromatic hydro carbons additive.
One preferred embodiment in, described in contain benzene ring structure polymer be selected from: the combination of one or more in polystyrene, expanded polystyrene (EPS), high impact polystyrene, Merlon, PETG, polybutylene terephthalate (PBT), polyphenylene oxide, aromatic polyamides, acrylonitrile-butadiene-styrene (ABS), hydrogenated styrene-butadiene block copolymer.
One preferred embodiment in, described arene additive is selected from: the combination of one or more in antioxidant, fire retardant, ultraviolet absorber, fluorescent whitening agent, mould inhibitor, antiwear additive, antioxidizing and antigum agent, tackifier, antirust agent, pour-point depressant, foam reducing composition, anti-knock agent, matal deactivator, anti-freezing agent, antisatic additive.
One preferred embodiment in, described sulfonated reagent contains sulfonate radical.
One preferred embodiment in, described in be selected from least one in chlorosulfonic acid, oleum, the concentrated sulfuric acid.
One preferred embodiment in, described sulfonation temperature is-10 DEG C～50 DEG C.
One preferred embodiment in, described sulfonation temperature is-5 DEG C～25 DEG C.
One preferred embodiment in, the described sulfonation time is 0.5～5h.
Another aspect of the present invention provides a kind of detection method containing arene additive in the polymer of benzene ring structure, through above-mentioned separation method processing, one or more in use infra-red sepectrometry, high performance liquid chromatography, gas chromatography, Liquid Chromatography-Mass Spectrometry, Liquid Chromatography-Mass Spectrometry, liquid UV light spectrometry, elemental microanalysis method, fluorescent spectrometry, thermogravimetry, differential thermal analysis, nuclear magnetic resonance method are tested.
Be easier to understand above-mentioned and further feature, aspect and advantage of the present invention with reference to following detailed description in detail.
Detailed description of the invention
The detailed description of the following preferred implementation method of the present invention of participation in the election and the embodiment comprising can more easily understand content of the present invention. Unless otherwise defined, all technology used herein and scientific terminology have the identical implication of conventionally understanding with one skilled in the art of the present invention. In the time there is contradiction, be as the criterion with the definition in this description.
Term as used herein " by ... preparation " and " comprising " synonym. Term used herein " comprises ", " comprising ", " having ", " containing " or its any other distortion, is intended to cover comprising of non-exclusionism. For example, the composition, step, method, goods or the device that comprise listed key element needn't only limit to those key elements, but can comprise other key element or this kind of key element that composition, step, method, goods or device are intrinsic clearly do not listed.
Conjunction " by ... composition " get rid of any key element of not pointing out, step or component. If for claim, it is closed that this phrase will make claim, makes it not comprise the material except the material of those descriptions, but except relative conventional impurity. In the time that phrase " by ... composition " appears in the clause of claim main body instead of immediately after theme, it is only limited to the key element of describing in this clause; Other key element is not excluded outside described claim as a whole.
When Range Representation that equivalent, concentration or other value or parameter limit with scope, preferable range or a series of upper limit preferred value and lower limit preferred value, this is appreciated that and specifically discloses all scopes that formed by arbitrary pairing of any range limit or preferred value and any scope lower limit or preferred value, no matter and whether this scope discloses separately. For example, in the time disclosing scope " 1 to 5 ", described scope should be interpreted as comprising scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc. In the time that number range is described in this article, unless otherwise indicated, otherwise this scope intention comprises its end value and all integers and mark within the scope of this.
Singulative comprises plural number discussion object, unless clearly indicated in addition in context. " optional " or " any one " refer to that item or the event described thereafter can occur or not occur, and this description comprises the situation of event generation and the situation that event does not occur.
Approximate term in description and claims is used for modifying quantity, represents that the present invention is not limited to this concrete quantity, also comprises approach to this quantity acceptable and can not cause the part of the correction of the change of relevant basic function. Accordingly, modify a numerical value with " approximately ", " approximately " etc., mean and the invention is not restricted to this accurate numerical value. In some example, approximate term may be corresponding to the precision of the instrument of measurement numerical value. In present specification and claims, circumscription can combine and/or exchange, if do not illustrate in addition that these scopes comprise contained all subranges therebetween.
In addition the indefinite article " one " before key element of the present invention or component and " one " quantitative requirement (the being occurrence number) unrestriction to key element or component. Therefore " one " or " one " should be read as and comprise one or at least one, and the key element of singulative or component also comprise plural form, unless the obvious purport of described quantity refers to singulative.
" polymer " means the polymerizable compound prepared by the monomer of the identical or different type of polymerization. Generic term " polymer " comprises term " homopolymers ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means the polymer of preparing by least two kinds of different monomers of polymerization. Generic term " EVA " comprises term " copolymer " (it is the polymer in order to refer to be prepared by two kinds of different monomers generally) and term " terpolymer " (it is the polymer in order to refer to be prepared by three kinds of different monomers generally). It also comprises the polymer of manufacturing by polymerization four or more kinds of monomer. " blend " means two or more polymer by the common polymer forming that mixes of method physics or chemistry.
In order to solve prior art problem, the invention provides a kind of separation method containing arene additive in the polymer of benzene ring structure, at least comprise following steps:
(1) dissolving step, provides organic solvent, and dissolve polymer obtains mixed solution;
(2) sulfonation procedure, provides sulfonated reagent, and gained mixed solution in sulfonation procedure (1), obtains the solution that contains sulfonated aromatic hydro carbons additive;
(3) separating step, water extraction, filters, and collects water, obtains the solution of sulfonated aromatic hydro carbons additive.
Both can refer to and only having contained the single polymer that contains benzene ring structure containing the polymer of benzene ring structure described in the present invention can be again blend or the alloy of two kinds or two or more polymer.
The polymer that contains benzene ring structure that can enumerate in the present invention can also be rubber polymer for Plastic polymer.
What described Plastic polymer can be enumerated has, polystyrene, expanded polystyrene (EPS), high impact polystyrene, Merlon, PETG, polybutylene terephthalate (PBT), polyphenylene oxide, aromatic polyamides, acrylonitrile-butadiene-styrene (ABS), hydrogenated styrene-butadiene block copolymer etc.
What described rubber polymer can be enumerated has, butadiene-styrene rubber.
Arene additive described in the present invention refers to the additive that contains benzene ring structure, such as antioxidant, fire retardant, ultraviolet absorber, fluorescent whitening agent, mould inhibitor, antiwear additive, antioxidizing and antigum agent, tackifier, antirust agent, pour-point depressant, foam reducing composition, anti-knock agent, matal deactivator, anti-freezing agent, antisatic additive etc.
The antioxidant that can enumerate has, and phenolic antioxidant is as antioxidant 1010, antioxidant 1076, antioxidant 330, irgasfos 168, antioxidant 215, antioxidant BHT, antioxidant T502, antioxidant B215, antioxidant 1330 etc.
The fire retardant that can enumerate has, and fire retardant is as: triphenyl phosphite, tricresyl phosphate, resorcinol two (hexichol phosphate), hydroquinones two (hexichol phosphate) etc.
The ultraviolet absorber that can enumerate has, and ultraviolet absorber for example, as salicylate class (, phenyl salicytate), benzophenone class (benzophenone), benzotriazole (UV-326), triazines (UV-1164, UV-1577, triazine-5) etc.
The ultraviolet absorber that can enumerate has, and fluorescent whitening agent is as fluorescent whitening agent OM (3-phenyl-5,6-benzo α-pyrones) etc.
The mould inhibitor that can enumerate has, and mould inhibitor is as the two benzene first phthalein amine of 2-benzisothiazole-3-ketone, 2-(4-thiazolyl) benzimidazole (TBZ), Dao Weixier-75,1,3,5-tri-(2-ethoxy)-s-triazine, two sulfo--2,2'-, N, N-dimethyl-N'-phenol-N'-(fluorine dichloromethane sulfenyl)-phenyl sulphur phthalein amine (A4), monobromo-acetic acid benzyl ester, salicylanilide, the bromo-N-of 2-methyl-4-(chloro second phthalidyl)-aniline (Cosan528) etc. 1. Wherein, 2-(4-thiazolyl) benzimidazole, salicylanilide and 1,2-benzisothiazole-3-ketone are current conventional biocide mildewcides.
The antiwear additive that can enumerate has, T306 tricresyl phosphate etc.
The matal deactivator that can enumerate has, CDA-1, CDA-6, CDA-10, Chel-180 etc.
Pulverization process：
One preferred embodiment in, described polymer in step (1) through pulverization process.
So-called pulverizing, just refers to the process that material size reduces. Conventionally adopt various types of crushing mechanisms, material is applied to different mechanical forces complete, as tensile force, extruding force, impulsive force and shearing force etc. The pulverizing of high molecular polymer can be to crush, smash, grind or shred.
Crushing is that the be squeezed effect of power of material is pulverized, the mode crushing can be to use the metallic plate of two relative motions mutually to push, also can be to use two relatively rolling of rotation rods, can be also to do eccentric rotary in conically shaped outside with inner cone to push.
Smashing is that material is subject to outer impact force action and is pulverized, and the mode smashing can be the strike of external hard objects, can be also between material self and with the generation high speed impact of fixing hard steel plate, can be also the mutual shock between material.
Grind is that material is subject to rolling effect and is pulverized between difformity abrasive body.
To shred be material in the shearing of the sharp weapon such as blade, puncture, tear etc. under effect and pulverized.
Pulverizing can be also freezing pulverizing. For example can list using liquid nitrogen as abrasive media, use freezing crusher to carry out freezing pulverizing to polymer.
Organic solvent：
In the present invention, the not special restriction of described organic solvent, if energy dissolve polymer, and technical scheme of the present invention is not affected and all can.
Described organic solvent be selected from chlorinated hydrocarbon, alkane, ethers, ketone, ester class, in one or more combination.
What described chlorinated hydrocarbon organic solvent can be given an example has: chloroform, chloroform, dichloropropane etc.
What described alkanes organic solvent can be given an example has: cyclohexane, n-hexane, normal heptane, normal octane etc.
What described ether organic solvent can be given an example has: oxolane, dioxane etc.
What described organic solvent of ketone can be given an example has: diisopropyl ketone, hexone etc.
What described ester class organic solvent can be given an example has: isobutyl acetate, ethyl acetate etc.
One preferred embodiment in, described organic solvent is oxolane, chloroform.
Those skilled in the art select water-insoluble solvent conventionally, as chloroform, cyclohexanone carry out dissolve polymer, because water-insoluble solvent and water can form two-phase, use water-insoluble solvent to be convenient to separate in the time of follow-up water extraction sulfonated products, and water-soluble solvent can and the water formation single-phase that dissolves each other, cannot separate. But some systems in the present invention, also can adopt water-soluble solvent, for example tetrahydrofuran solvent, adopts oxolane dissolved polystyrene, in the operation of follow-up water extraction sulfonation antioxidant, still can form obvious two-phase with water, realizes both separation. The inventor infers that wherein possible reason is when be dissolved with polystyrene in oxolane, can reduce the degree of dissolving each other of itself and water, thus formation two-phase.
Sulfonating reaction：
Sulfonating reaction is to point to organic molecule to introduce sulfonic group (SO3H), sulphonate-base is (as-SO3Or sulphonyl halogen (SO Na)2X) chemical reaction, the reaction of wherein introducing sulphonyl halogen can be defined as again halogen sulfonating reaction. The substituting group of introducing according to sulfonating reaction, the product of sulfonating reaction can be sulfonic acid (RSO3H), sulfonate (RSO3M, M is ammonium or metal ion) or sulfonic acid halide (RSO2X). According to sulphur atom in sulfonic group and the atom difference being connected in organic molecule, the product obtaining can be the sulfoacid compound (RSO being connected with carbon atom3H); Sulfuric ester (the ROSO being connected with oxygen atom3H); Amine compound (the RNHSO being connected with nitrogen-atoms3H)。
The kind of sulfonating agent is more, and reaction mechanism is also different. Has plenty of electrophilic reaction, as sulfuric acid, sulfur trioxide, oleum etc.; Has plenty of necleophilic reaction, as sodium sulfite, sodium hydrogensulfite etc.; Has plenty of radical reaction, as sulfur dioxide and chlorine, sulfur dioxide and oxygen etc. Sulfonation on phenyl ring is electrophilic reaction. First be electrophilic reagent attack phenyl ring, Formed cation, then loses a proton, generates benzene sulfonic acid or substituted benzenesulfonic acid.
Conventional sulfonating agent has sulfur trioxide, the concentrated sulfuric acid, oleum, chlorosulfonic acid.
Sulfur trioxide is a kind of colourless easy-sublimation solid, has three kinds of thing phases. Use sulfur trioxide fast as sulfonating agent reaction speed, volume of equipment is little, and does not need extra heating. Because the activity of sulfur trioxide is large, respond is strong, and can not generate water, the consumption of sulfur trioxide can approach theoretical amount, after sulfonation, do not need concentrating waste acid, need not in and spent acid and produce unnecessary neutral salt, have advantages of that other sulfonating agent is incomparable. But its shortcoming is that sulfonating reaction heat release is violent, easily cause substrate to decompose or generate the accessory substances such as sulfone class, and the viscosity of reactant is high, brings difficulty to heat transfer.
The concentrated sulfuric acid is a kind of strong mineral acid with high corrosion, and the concentrated sulfuric acid has strong oxidizing property, dehydration property, severe corrosive, difficult volatility, acidity, water imbibition. The concentrated sulfuric acid is during as sulfonating agent, and the side reaction of generation is less, but the reaction rate of sulfonating reaction is slower. Every generation 1mol sulfonated products can generate 1mol water simultaneously, can make the concentration of the concentrated sulfuric acid decline, and simultaneously for sulfonating reaction is carried out smoothly, need to add excessive sulfuric acid dehydration, and the 3-4 that the amount of the concentrated sulfuric acid generally adding is reactant doubly.
Oleum is the product that sulfur trioxide is dissolved in the concentrated sulfuric acid, conventionally has two kinds of specifications, is 20%-25% and 60%-65% containing free sulfur trioxide. The freezing point of these two kinds of oleums is low, is liquid under normal temperature, easy to use and transport. Oleum is during as sulfonating agent, and reaction speed is fast, and reaction temperature is lower, has the advantages such as technique is simple, equipment investment is low, easy to operate simultaneously. Shortcoming is too violent to organic effect, often with oxidation, generates the byproducts such as sulfone. In addition, after sulfonation, can produce water.
Chlorosulfonic acid is a kind of colourless or flaxen liquid, has pungent smell, in air, is fuming, and is that a hydroxyl of sulfuric acid is replaced the rear compound forming by chlorine. When chlorosulfonic acid uses as sulfonating agent, respond is strong, reaction condition gentleness, and the product obtaining is purer. Accessory substance is hydrogen chloride, can under negative pressure, discharge, and is conducive to react completely and carries out. Shortcoming is that price is higher, and molecular weight is large, introduces a sulfonic sulfonating agent consumption and sees many. In addition the hydrogen chloride producing in reaction, has severe corrosive.
The sulfonating agent of sulfonating reaction can be also inorganic salts sulfonating agent, for example can list: sodium sulfite, sodium hydrogensulfite, sodium pyrosulfite. This class sulfonating agent can for the sulfonation of alkene or with the organic compound reaction that contains active halogen atom.
Sulfonating agent can also be mist, chlorosulfuric acid, the sulfamic acid of mist, sulfur dioxide and the oxygen of sulfur dioxide and chlorine.
The mist that uses sulfur dioxide and chlorine during as sulfonating agent, reacts for radical reaction, can cause with ultraviolet light. The mist that uses sulfur dioxide and oxygen during as sulfonating agent, reacts for radical reaction, can use illumination, radiation or ozone initiation. Chlorosulfuric acid during as sulfonating agent, carries out conventionally under illumination, and the mist of reaction mechanism and sulfur dioxide and chlorine is similar as sulfonating agent. Sulfamic acid is stable nonhygroscopic solid, is similar to sulfur trioxide tertiary amine complex compound in sulfonating reaction, and difference is that sulfamic acid is applicable to high-temperature anhydrous medium.
One preferred embodiment in, described sulfonating agent contains sulfonate radical.
One preferred embodiment in, described sulfonating agent is selected from least one in chlorosulfonic acid, oleum, the concentrated sulfuric acid.
The complexity that substituting group on aromatic rings carries out sulfonating reaction has very large impact. Because the sulfonating reaction on aromatic rings is electrophilic substitution reaction, when substituting group electron donation on aromatic rings is stronger, be more conducive to the carrying out of sulfonating reaction; When substituting group electron-withdrawing power on aromatic rings is stronger, be more unfavorable for the generation of sulfonating reaction. In one embodiment of the present of invention, on the phenyl ring of phenol antioxidant, cloud density is higher than the cloud density on styrene, and the activity of sulfonating reaction is stronger.
Sulfonation degree has important impact for structure and the performance of the polymer containing sulfonic acid group. The method of measuring sulfonation degree includes but not limited to: elemental microanalysis method, conductometry, gas chromatography, colorimetric method, thin layer chromatography.
Elemental microanalysis method is to utilize elemental analyser directly to measure the percentage composition of element sulphur in polymer, and the mass fraction of element sulphur has directly reflected the content of sulfonic acid group in polymer. Elemental microanalysis method is simple and convenient, but elementary analysis need to be by means of elemental analyser, and cost is higher, especially in the time needing the sulfonation degree of copolymer of the multiple different sulfonating agent dosages of system measurement, and somewhat expensive.
Conductometry is to use standard solution of sodium hydroxide titration, by adding the hydrogen ion reaction in hydroxyl and solution, generates nonconducting hydrone. Along with adding of standard solution of sodium hydroxide, the electrical conductivity of solution declines gradually, and while arriving titration end-point, electrical conductivity drops to minimum. Continue to add NaOH, can make again the ion populations in solution increase, electrical conductivity increases. The stereometer that is the standard solution of sodium hydroxide that consumes while reaching minimum of electrical conductivity by titration end-point calculates sulfonic content, and computing formula is:
M is the concentration of standard solution of sodium hydroxide, and unit is mol/L; V is for arriving the volume of the standard solution of sodium hydroxide that consumes when titration end-point, and unit is mL; M is the quality of sample, and unit is g.
In the present invention, the dissolubility of polymer and arene additive is very approaching, and conventional separation method separates as added good solvent and poor solvent cannot realize both. Need to consume a large amount of time and use column chromatography to separate, reduce operating efficiency, also will consume a large amount of solvents, cost is higher, also can affect the rate of recovery of sample simultaneously, makes quantitative result inaccurate. In addition, contain benzene ring structure polymer and arene additive sulfonating reaction all can occur, both separation are existed to technology resistance by the method for sulfonation. The discovery that the inventor is unexpected, is used chlorosulfonic acid as sulfonating agent, only can obtain sulfonated aromatic hydro carbons additive, and only can obtain minute quantity or can not obtain sulfonated polymer. Infer that its possible reason is: on the one hand, the cloud density in arene additive on phenyl ring is larger than the cloud density on the phenyl ring in polymer, and reactivity is higher. On the other hand, arene additive is generally small molecule structure, and it is sterically hindered also less that it has, and is more conducive to the carrying out of sulfonating reaction.
The addition of sulfonated reagent is 5%～15% of total polymer mass, and sulfonating agent addition is too little, can cause arene additive sulphonation rate inadequate, has reduced the dissolubility with respect to water, can affect the separation of arene additive. Sulfonating agent addition is too high, can cause polymer sulfonation excessive, and in the time that sulfonation degree is too high, even the meeting in polymer occurs to be cross-linked, and is unfavorable for analyzing and testing of the present invention.
In described process for sulfonation, sulfonation temperature is at-10 DEG C to 50 DEG C, preferably at-5 DEG C to 25 DEG C, carries out sulfonating reaction. The temperature of sulfonation processing is-5 DEG C～25 DEG C, can enumerate as :-5 DEG C, 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C. If temperature is too high, can cause the side reaction such as oversulfonate or oxidation.
In described process for sulfonation, the sulfonation time is 0.5 hour to 5 hours, is preferably 1 hour to 3 hours. Can enumerate as 1h, 1.5h, 2h, 2.5h, 3h.
If the sulfonation time is too short, sulfonating reaction is carried out insufficient; If the sulfonation time is oversize, can make polymer also there will be excessive sulfonation, it is water-soluble that partial polymer reaches, and affects the separation of arene additive.
Affect sulfonation degree because have molar ratio of material, sulfonating reaction temperature, sulfonating reaction time. The condition that increases sulfonation degree can be: add more sulfonating agent, higher sulfonating reaction temperature, longer sulfonating reaction time. In order to obtain desired sulfonation degree, can be by the relation between amount, reaction temperature and reaction time three factors of balance sulfonating agent. For example: in the time that the sulfonation dosage adding is certain, lower reaction temperature, longer reaction time and shorter reaction time, higher reaction temperature all can obtain identical sulfonation degree. Be example taking chlorosulfonic acid as sulfonating agent, in the present invention, taking the content of sample in polyphenylene oxide engineering plastics, (unit is as g), and the content of irgasfos 168 is 1% of polyphenylene oxide gross mass by weight; The content of chlorosulfonic acid is (unit is mL) by volume, and sulfonating reaction temperature remains on 10 DEG C, and when the content ratio of sample and sulfonating agent is 100:5, the sulfonating reaction time, while being 0.5h, the sulfonation degree of polyphenylene oxide was 0, and the sulfonation degree of irgasfos 168 is 95%; The sulfonating reaction time, while being 1h, the sulfonation degree of polyphenylene oxide was 0.4%, and the sulfonation degree of irgasfos 168 is 99%; The sulfonating reaction time, while being 2h, the sulfonation degree of polyphenylene oxide was 0.5%, and the sulfonation degree of irgasfos 168 is 100%; The sulfonating reaction time, while being 3h, the sulfonation degree of polyphenylene oxide was 0.9%, and the sulfonation degree of irgasfos 168 is 100%; The sulfonating reaction time, while being 4h, the sulfonation degree of polyphenylene oxide was 1.3%, and the sulfonation degree of irgasfos 168 is 100%; The sulfonating reaction time, while being 5h, the sulfonation degree of polyphenylene oxide was 1.5%, and the sulfonation degree of irgasfos 168 is 100%.
The inventor is unexpected finds that the sulfonating reaction time is increased to after certain value, then extends the reaction time when sample and sulfonating agent content are than (unit is g/mL) and sulfonation temperature when constant, and sulfonation degree is substantially constant.
In order to ensure the accuracy of separation and detection of antioxidant, the sulfonation degree of antioxidant should at least reach more than 98%, most preferably is 100%, and should, by controlling sulfonating conditions, preferably be controlled at below 10% for the sulfonation degree of the polymer of polyphenylene oxide or its blend.
The inventor finds under study for action, in the time that sulfonation is processed to the time that passes into inert gas in containing sulfonation system and can significantly shorten sulfonation processing. Described inert gas is selected from the one in nitrogen, argon gas.
The inventor is unexpected discovery also, in process for sulfonation, in polymeric system, passes into a small amount of inert gas, can significantly shorten the time of sulfonation processing. The described mode that passes into inert gas can continue to pass into, also can be for pass into the inert gas of 5min every 10min.
Analyzing and testing ：
Another aspect of the present invention provides a kind of detection method containing arene additive in the polymer of benzene ring structure, through above-mentioned separation method processing, one or more in use infra-red sepectrometry, high performance liquid chromatography, gas chromatography, Liquid Chromatography-Mass Spectrometry, Liquid Chromatography-Mass Spectrometry, liquid UV light spectrometry, elemental microanalysis method, fluorescent spectrometry, thermogravimetry, differential thermal analysis, nuclear magnetic resonance method are tested.
Infra-red sepectrometry ：
Infra-red sepectrometry is called for short FT-IR, and those that the test condition of FT-IR is well known to those skilled in the art, for example can list: use VERTEX70 Fourier transformation infrared spectrometer and 769YP-15A type tablet press machine. The resolution ratio of infrared spectrometer is made as 4cm-1, scanning times is 32 times, sweep limits is 4000-400cm-1. Get about 1.5mg sample, add KBr in the ratio of 1:100, be ground into powder, grind evenly.
High performance liquid chromatography ：
High performance liquid chromatography (HighPerformanceLiquidChromatography, HPLC) claims again " high pressure liquid chromatography ", " high-speed liquid chromatography ", " high separation liquid chromatogram ", " column chromatography in modern age " etc. High performance liquid chromatography is a chromatographic important branch, taking liquid as mobile phase, adopt high pressure transfusion system, pump into by thering is the single solvent of opposed polarity or the mobile phase such as mixed solvent, buffer solution of different proportion the chromatographic column that fixing phase is housed, in post each composition separated after, enter detector and detect, thereby realize the analysis to sample.
It is high that high performance liquid chromatography has separative efficiency, and selectively good, detection sensitivity is high, operation automation, applied range; Have advantages of compared with gas chromatography: the not volatility of test sample and thermal stability limit, applied range; Mobile phase kind is many, can reach high separative efficiency by the optimization of mobile phase; Generally at room temperature analyze, do not need high column temperature.
In one embodiment, the test condition of described HPLC is: chromatographic column: C18, column temperature: 30 DEG C; Flow velocity: 1.0mlmin-1; Sample size: 10 μ L; Detect wavelength: 310nm; Mobile phase: A: oxolane; B: acetonitrile, wherein, acetonitrile: oxolane volume ratio 60:40.
Gas chromatography ：
Gas chromatography (gaschromatography is called for short GC), GC is using inert gas as mobile phase, utilize the gas phase of each component in chromatographic column in sample different with fixing alternate distribution coefficient, when the sample after vaporization is brought into while moving in chromatographic column by carrier gas, component with regard to therein two alternately carry out repeated multiple times distribution, due to the adsorption capacity difference (i.e. preservation effect difference) of fixing relatively various components, therefore the speed of service of each component in chromatographic column is just different, after certain column length, just separated from one another, order is left chromatographic column and is entered detector, the ion current signal producing is after amplifying, on logger, depict the chromatographic peak of each component.
Liquid Chromatography-Mass Spectrometry ：
Liquid chromatography mass combined instrument (liquidChromatographMassSpectrometer), is called for short LC-MS, is the high end instrument in Analysis of Organic Substances market. Liquid chromatogram (LC) can effectively be separated the organic components in organic matter testing sample, and mass spectrum (MS) can be to the organic matter separating analysis one by one, obtain organic matter molecular mass, the information of structure (in some cases) and concentration (quantitative analysis).
In one embodiment, the test condition of described LC-MS is: the chromatographic system of LC-MS is Agilent1200 liquid chromatograph, and chromatographic column is selected AgilentEclipsePlusC18, and chromatogram column length is 100mm, internal diameter 2.1mm, and packing material size is 3.5. Mobile phase is 10mmol/L ammonium acetate solution (A) and acetonitrile (B). Adopt gradient elution, elution program is 0-8min, 35%-85%B; 8-10min, 85%B; Dwell time is 9min; Be 8min rear running time; Flow velocity is 0.25mL/min; Sampling volume is 20 μ L; Column temperature is set as 40 DEG C. The mass spectrometer system of LC-MS is the triple level Four bar of Agilent6410 mass spectrum. Ion gun is electric spray ion source; Adopt negative ion mode; Atomization gas is used nitrogen, and pressure is 38psi; Dry gas is used nitrogen, and flow velocity is set as 9L/min; Dry gas Temperature Setting is 350 DEG C; Capillary voltage is 4000V; Scanning of the mass spectrum mode is many reactive ion monitorings.
Nuclear magnetic resonance method ：
Nuclear magnetic resonance spectroscopy (NuclearMagneticResonanceSpectroscopy, NMR) NMR is the absorption of research atomic nucleus to radio-frequency radiation, it is one of the most strong instrument various organic and composition, structures inorganic matter being carried out qualitative analysis, sometimes also can carry out quantitative analysis.
1Those that HNMR test condition is well known to those skilled in the art, for example can list: use German Bruker to produce DMX500 type nuclear magnetic resonance chemical analyser, operating frequency is 500MHz. Operable deuterated reagent is such as deuterochloroform, deuterated DMSO, deuterated THF etc.
The inventive method operating procedure is simple, can accurately separate and quantitatively containing the content of arene additive in the polymer of benzene ring structure, get rid of the puzzlement that in analytic process, other materials bring. Hereinafter, by embodiment, the present invention is explained in more detail, but should be understood that these embodiment are only illustrative and nonrestrictive. If there is no other explanation, raw materials used is all commercially available.
Embodiment 1：
(1) get 1gPS, wherein, in PS, contain mass fraction and be 0.5% ultraviolet absorber triazine-5, through freezing pulverizing, this polymer is dissolved in the organic solvent of 60mL oxolane, at 30 DEG C, stir 4 hours, until polymer dissolves completely, obtain mixed solution;
(2) in the reaction unit with backflow, stirring and temperature-controlling system, add in advance above-mentioned polymer solution, controlling temperature is-10 DEG C of left and right, under vigorous stirring, in system, slowly drip 0.10g chlorosulfonic acid, after dropwising, in system, continue to pass into nitrogen, the sulfonation time is: 5h, obtains containing sulfonation triazine-5 solution.
(3) sulfonated polymer solution is heated to room temperature, adds the aqueous solvent of 50mL, in separatory funnel, acutely rock 10min, after leaving standstill, isolate water. Use HPLC to detect, the chromatographic system of HPLC is Agilent1200 liquid chromatograph: chromatographic column: C18, column temperature: 30 DEG C; Flow velocity: 1.0mlmin-1; Sample size: 10 μ L; Detect wavelength: 310nm; Mobile phase: A: oxolane; B: acetonitrile, wherein, acetonitrile: oxolane volume ratio 60:40.
Calibration curve preparation: precision takes the triazine-5 standard items 50mg that is dried to constant weight, puts in 50mL volumetric flask, adds mobile phase and is mixed with the standard liquid that mass concentration is 1000mgL-1. Precision measures standard liquid 5mL, 10mL, 15mL, 20mL, 25mL, is placed in respectively 50mL volumetric flask, is diluted to scale with mobile phase, shakes up, for subsequent use.
Sample introduction 100mgL respectively-1、200mg·L-1、300mg·L-1、400mg·L-1、500mg·L-1Triazine-5 standard liquid, record peak area. With peak area, the concentration of triazine-5 is carried out to linear regression, obtain calibration curve equation: y=75.11x-21.17, R=0.9997.
Experiment records: sulfonation triazine-5 retention time is 5.945min. Adopting external standard method to measure sulfonation triazine-5 content in sample is 0.49%.
Embodiment 2：
(1) get 1g expanded polystyrene (EPS), wherein, in expanded polystyrene (EPS), contain mass fraction and be 1% mould inhibitor 2-(4-thiazolyl) benzimidazole, after pulverizing with freezing crusher, this polystyrene is dissolved in 60mLDMSO, at 30 DEG C, stir 4 hours, until polymer dissolves completely, obtain mixed solution;
(2) in the reaction unit with backflow, stirring and temperature-controlling system, add in advance above-mentioned polymer solution, controlling temperature is-5 DEG C of left and right, under vigorous stirring, in system, slowly drip 0.10g chlorosulfonic acid, after dropwising, in system, continue to pass into nitrogen, the sulfonation time is: 4.5h, obtains containing sulfonation 2-(4-thiazolyl) benzimidazole solution.
(3) sulfonated polymer solution is heated to room temperature, adds the aqueous solvent of 50mL, in separatory funnel, acutely rock 10min, after leaving standstill, isolate water.
Use LC-MS to detect, the chromatographic system of LC-MS is Agilent1200 liquid chromatograph, and chromatographic column is selected AgilentEclipsePlusC18, and chromatogram column length is 100mm, internal diameter 2.1mm, and packing material size is 3.5. Mobile phase is 10mmol/L ammonium acetate solution (A) and acetonitrile (B). Adopt gradient elution, elution program is 0-8min, 45%-95%B; 8-10min, 75%B; Dwell time is 9min; Be 8min rear running time; Flow velocity is 0.25mL/min; Sampling volume is 20 μ L; Column temperature is set as 40 DEG C. The mass spectrometer system of LC-MS is the triple level Four bar of Agilent6410 mass spectrum. Ion gun is electric spray ion source; Adopt negative ion mode; Atomization gas is used nitrogen, and pressure is 38psi; Dry gas is used nitrogen, and flow velocity is set as 9L/min; Dry gas Temperature Setting is 350 DEG C; Capillary voltage is 4000V; Scanning of the mass spectrum mode is many reactive ion monitorings. Sulfonation 2-(4-thiazolyl) benzimidazole, retention time is 7.421min. Measure in sample by internal standard method using dibutyl phthalate as internal standard compound, 2-(4-thiazolyl) benzimidazole content is 0.99%.
Embodiment 3：
(1) get 1g expanded polystyrene (EPS), wherein, in expanded polystyrene (EPS), contain mass fraction and be 0.01% fluorescent whitening agent PEB, after pulverizing with freezing crusher, this polystyrene is dissolved in 60mLDMSO, at 30 DEG C, stirs 4 hours, until polymer dissolves completely, obtain mixed solution;
(2) in the reaction unit with backflow, stirring and temperature-controlling system, add in advance above-mentioned polymer solution, controlling temperature is 0 DEG C of left and right, under vigorous stirring, in system, slowly drip 0.10g chlorosulfonic acid, after dropwising, in system, continue to pass into nitrogen, the sulfonation time is: 4h, obtains containing sulfonation PEB solution.
(3) sulfonated polymer solution is heated to room temperature, adds the aqueous solvent of 50mL, in separatory funnel, acutely rock 10min, after leaving standstill, isolate water.
Use LC-MS to detect, the chromatographic system of LC-MS is Agilent1200 liquid chromatograph, and chromatographic column is selected AgilentEclipsePlusC18, and chromatogram column length is 100mm, internal diameter 2.1mm, and packing material size is 3.5. Mobile phase is 10mmol/L ammonium acetate solution (A) and acetonitrile (B). Adopt gradient elution, elution program is 0-8min, 25%-95%B; 8-10min, 80%B; Dwell time is 9min; Be 8min rear running time; Flow velocity is 0.25mL/min; Sampling volume is 20 μ L; Column temperature is set as 40 DEG C. The mass spectrometer system of LC-MS is the triple level Four bar of Agilent6410 mass spectrum. Ion gun is electric spray ion source; Adopt negative ion mode; Atomization gas is used nitrogen, and pressure is 38psi; Dry gas is used nitrogen, and flow velocity is set as 9L/min; Dry gas Temperature Setting is 350 DEG C; Capillary voltage is 4000V; Scanning of the mass spectrum mode is many reactive ion monitorings. Sulfonation PEB retention time is 6.234min. Measuring PEB content in sample taking dibutyl phthalate as internal standard compound by internal standard method is 0.01%.
Embodiment 4：
(1) get 1g polyphenylene oxide engineering plastics, wherein, in polyphenylene oxide engineering plastics, contain mass fraction and be 0.1% light stabilizer TinuvinP, this polymer is dissolved in 60mL chloroform solvent, at 30 DEG C, stir 6 hours, until polymer dissolves completely, obtain mixed solution;
(2) in the reaction unit with backflow, stirring and temperature-controlling system, add in advance above-mentioned polymer solution, controlling temperature is 5 DEG C of left and right, adopts UV-irradiation half an hour, under vigorous stirring, in system, slowly drip the 0.10g concentrated sulfuric acid, after dropwising, in system every 10min, in system, pass into nitrogen 5min, the sulfonation time is: 3.5h, obtains containing sulfonation TinuvinP solution.
(3) sulfonated polymer solution is heated to room temperature, adds the aqueous solvent of 50mL, in separatory funnel, acutely rock 10min, after leaving standstill, isolate water.
The chromatographic system of LC-MS is Agilent1200 liquid chromatograph, and chromatographic column is selected AgilentEclipsePlusC18, and chromatogram column length is 100mm, internal diameter 2.1mm, and packing material size is 3.5. Mobile phase is 10mmol/L ammonium acetate solution (A) and acetonitrile (B). Adopt gradient elution, elution program is 0-8min, 35%-85%B; 8-10min, 85%B; Dwell time is 9min; Be 8min rear running time; Flow velocity is 0.25mL/min; Sampling volume is 20 μ L; Column temperature is set as 40 DEG C. The mass spectrometer system of LC-MS is the triple level Four bar of Agilent6410 mass spectrum. Ion gun is electric spray ion source; Adopt negative ion mode; Atomization gas is used nitrogen, and pressure is 38psi; Dry gas is used nitrogen, and flow velocity is set as 9L/min; Dry gas Temperature Setting is 350 DEG C; Capillary voltage is 4000V; Scanning of the mass spectrum mode is many reactive ion monitorings. The retention time of sulfonation TinuvinP is 7.141min. Be 0.1% taking dibutyl phthalate as internal standard compound with the content that internal standard method is measured sulfonation TinuvinP in sample.
Embodiment 5:
(1) get 1g butadiene-styrene rubber, wherein; in butadiene-styrene rubber, containing mass fraction is 1%N; N '-diphenyl-para-phenylene diamine, after pulverizing with freezing crusher, this polymer is dissolved in the NaOH solution of 1mol/L; then put into autoclave; at 120 DEG C, react 4h, after cold filtration, is washed till neutrality with distilled water.
(2) in the reaction unit with backflow, stirring and temperature-controlling system, sample is dissolved in to 100ml acetone soln, controlling temperature is 10 DEG C of left and right, under stirring condition, slowly add 0.10g chlorosulfonic acid, after dropwising, in system, continue to pass into nitrogen, the sulfonation time is: 3h, obtains containing sulfonation N, N '-diphenyl-para-phenylene diamine solution.
(3) sulfonated polymer solution is heated to room temperature, adds the aqueous solvent of 50mL, in separatory funnel, acutely rock 10min, after leaving standstill, isolate water.
Use HPLC to detect, to wherein contained sulfonation N, N '-diphenyl-para-phenylene diamine's concentration is carried out qualitative and quantitative analysis mensuration. HPLC determination step carries out in the usual way, and wherein, Details as Follows for each parameter: chromatographic column: and AgilentHC-CN post (250mm × 4.6mm, 5 μ are m); Mobile phase: methanol-water (volume ratio is 55:45) mixed solution; Flow velocity: 1.0mL/min; Sample size: 20 μ L; Column temperature: 35 DEG C; Ultraviolet detects wavelength: 290nm.
Experiment records: sulfonation N, N '-diphenyl-para-phenylene diamine's retention time is 5.925min. Adopt external standard method to measure sulfonation N in sample, N '-diphenyl-para-phenylene diamine's content is 0.99%.
Embodiment 6:
(1) get 1gPET fiber, wherein, in fiber, contain mass fraction and be 0.05% antiwear additive diphenyl silanediol, this fiber is dissolved in the mixed solvent of 40mL carrene and oxolane, at 30 DEG C, stir 4 hours, until polymer fiber dissolves completely, obtain the polymer solution that contains diphenyl silanediol;
(2) in the reaction unit with backflow, stirring and temperature-controlling system, add in advance above-mentioned polymer solution, controlling temperature is 15 DEG C of left and right, under vigorous stirring, in system, slowly drip 0.15g chlorosulfonic acid, the sulfonation time is: 2.5h, obtains sulfonation diphenyl silanediol solution.
(3) sulfonated polymer solution is heated to room temperature, adds the aqueous solvent of 50ml, there is water and organic solvent phase after leaving standstill in vigorous stirring 30min, isolates water.
(4) by the aqueous solution obtained above after vacuum drying, adopt HPLC-MS test, its test condition is: the chromatographic system of HPLC-MS is Agilent1200 liquid chromatograph, and chromatographic column is selected AgilentEclipseXDBC18, chromatogram column length is 250mm, internal diameter 4.6mm. Mobile phase is acetonitrile (A) and 0.1% aqueous formic acid (B). Adopt gradient elution, elution program is 0-4min, 40%-50%B; 4-6min, 25% ~ 40%B; 6-15min, 25% ~ 10%B; 15-25min, 10%B; 25-28min, 10% ~ 0%B. The mass spectrometer system of HPLC-MS is the triple level Four bar of Agilent6410 mass spectrum. Ion gun is electric spray ion source; Cation scanning, atomization gas is used nitrogen, ion source temperature: 325 DEG C, pressure is 45psi, dry gas (N2) flow velocity: 5.0L/min; Sheath temperature degree: 350 DEG C, sheath gas velocity: 11.0L/min; Capillary voltage: 3500V; Spray nozzle voltage: 50V; Mass scanning scope: m/z=100 ~ 1500.
Experiment records: the retention time of sulfonation diphenyl silanediol is 6.915min. The content that adopts external standard method to measure sulfonation diphenyl silanediol in sample is 0.05%.
Embodiment 7:
(1) get 1gSEB, wherein, in SEBS, contain mass fraction and be 0.5% antioxidant 1010, this polymer is dissolved in the mixed solvent (dioxane and oxolane volume ratio 1:1) of 40mL dioxane and oxolane, at 30 DEG C, stir 6 hours, until polymer dissolves completely, obtain mixed solution;
(2) in the reaction unit with backflow, stirring and temperature-controlling system, add in advance above-mentioned polymer solution, controlling temperature is 20 DEG C of left and right, under vigorous stirring, to slowly dripping 0.12g chlorosulfonic acid in system, after dropwising, to the mist (sulfur dioxide and nitrogen volume ratio 1:8) that passes into sulfur dioxide and nitrogen in system, the sulfonation time is: 2h, obtains containing sulfonation antioxidant 1010 solution.
(3) sulfonated polymer solution is heated to room temperature, adds the aqueous solvent of 50mL, in separatory funnel, acutely rock 10min, after leaving standstill, isolate water. Use HPLC to detect, the chromatographic system of HPLC is Agilent1200 liquid chromatograph: chromatographic column: C18, column temperature: 30 DEG C; Flow velocity: 1.0mlmin-1; Sample size: 10 μ L; Detect wavelength: 310nm; Mobile phase: A: oxolane; B: acetonitrile, wherein, acetonitrile: oxolane volume ratio 60:40.
Experiment records: sulfonation antioxidant 1010 retention time is 5.894min. Adopting external standard method to measure antioxidant 1010 content in sample is 0.49%.
Embodiment 8:
(1) get 1gPC and ABS plastic alloy (wherein, the mass ratio of PC and ABS is 2:3), in plastic alloy, contain mass fraction and be 3% RDP, these plastics are dissolved in the mixed solvent of 50mL, chloroform and carbon tetrachloride, at 60 DEG C, stir 5 hours, until polymer plastic dissolves completely, obtain polymer solution;
(2) in the reaction unit with backflow, stirring and temperature-controlling system, add in advance above-mentioned polymer solution, controlling temperature is 30 DEG C of left and right, under vigorous stirring, in system, slowly drips 0.2g chlorosulfonic acid, the sulfonation time is: 1.5h. Obtain sulfonation RDP solution.
(3) sulfonated polymer solution is heated to room temperature, adds the aqueous solvent of 50ml, there is water and organic solvent phase after leaving standstill in vigorous stirring 20min, isolates water.
(4) by the aqueous solution obtained above after vacuum drying, adopt GC-MS test, its test condition is:
The aqueous solution obtained above is adopted to HPLC, and its test condition is: detect wavelength: 245nm; Mobile phase: methanol/water=85/15 (V/V); Flow velocity: 0.80mL/min; Column temperature: 30 DEG C; Sample size: 20 μ l; Molten sample solvent: methyl alcohol.
Experiment records: sulfonation RDP retention time is 6.094min. Adopting external standard method to measure sulfonation RDP content in sample is 2.96%.
Embodiment 9:
(1) get 1gPVC CABLE MATERIALS, wherein, in PVC CABLE MATERIALS, containing mass fraction is 0.5% passivator CDA-1, after pulverizing, sample is dissolved in to 50mL oxolane with freezing crusher, and keeping reaction temperature is 20 DEG C, until polymer dissolves completely, obtains mixed solution;
(2) in the reaction unit with backflow, stirring and temperature-controlling system, add in advance above-mentioned polymer solution, controlling temperature is 35 DEG C of left and right, under vigorous stirring, in system, slowly drip 0.10g chlorosulfonic acid, after dropwising, in system, continue to pass into nitrogen, the sulfonation time is: 1h, obtains containing sulfonation CDA-1 solution.
(3) sulfonated polymer solution is heated to room temperature, adds the aqueous solvent of 50mL, in separatory funnel, acutely rock 10min, after leaving standstill, isolate water.
Use LC-MS to detect, the chromatographic system of LC-MS is Agilent1200 liquid chromatograph, and chromatographic column is selected AgilentEclipsePlusC18, and chromatogram column length is 100mm, internal diameter 2.1mm, and packing material size is 3.5. Mobile phase is 10mmol/L ammonium acetate solution (A) and acetonitrile (B). Adopt gradient elution, elution program is 0-8min55%B; 8-10min, 85%B; Dwell time is 9min; Be 8min rear running time; Flow velocity is 0.25mL/min; Sampling volume is 20 μ L; Column temperature is set as 40 DEG C. The mass spectrometer system of LC-MS is the triple level Four bar of Agilent6410 mass spectrum. Ion gun is electric spray ion source; Adopt negative ion mode; Atomization gas is used nitrogen, and pressure is 38psi; Dry gas is used nitrogen, and flow velocity is set as 9L/min; Dry gas Temperature Setting is 350 DEG C; Capillary voltage is 4000V; Scanning of the mass spectrum mode is many reactive ion monitorings. Sulfonation CDA-1 retention time is 6.8min, and M1 peak is 283. Measuring CDA-1 content in sample taking dibutyl phthalate as internal standard compound by internal standard method is 0.5%.
Embodiment 10:
(1) get 1gABS plastic products, wherein, contain mass fraction and be the ABS plastic goods of 0.3% phenyl salicytate, it is carried out to liquid nitrogen frozen pulverizing, then it is dissolved in 100mL acetone, obtain lysate.
(2) in the reaction unit with backflow, stirring and temperature-controlling system, add in advance above-mentioned polymer solution, controlling temperature is 50 DEG C of left and right, under vigorous stirring, in system, slowly drip 0.10g chlorosulfonic acid, after dropwising, in system, continue to pass into argon gas, the sulfonation time is: 0.5h, obtains containing sulfonation CDA-1 solution.
(3) sulfonated polymer solution is heated to room temperature, adds the aqueous solvent of 50mL, in separatory funnel, acutely rock 10min, after leaving standstill, isolate water.
Use HPLC to detect above-mentioned water, the chromatographic system of HPLC is WatersLC510 type high performance liquid chromatograph, chromatographic column: μ-BondapakC18 post (250 × 3.9mm), flow velocity: 1.0mL/min; Sample size: 10 μ L; Detect wavelength: 310nm; Mobile phase, methyl alcohol: oxolane: water=200:200:160.
Calibration curve preparation: take the standard phenyl salicytate sample of variable concentrations, with mobile phase solvent constant volume, then carry out linear regression analysis, obtain calibration curve equation: y=1.652 × 107X-689.6, R=0.9996, concentration limit 0.55 μ g/mL, wherein y is sample concentration (μ g/mL), x is sample peak area (μ VS).
Adopting above-mentioned external standard method to measure phenyl salicytate content in sample is 0.29%.
Comparative example 1:
Specific experiment process is with embodiment 1, and difference is, without pulverization process. Measuring sulfonation triazine-5 content in sample is 0.48%.
Comparative example 2:
Specific experiment process is with embodiment 1, and difference is, sulfonation temperature is 100 DEG C. Measuring sulfonation triazine-5 content in sample is 0.29%.
Comparative example 3:
Specific experiment process is with embodiment 1, and difference is, the sulfonation time is 20h. Measuring sulfonation triazine-5 content in sample is 0.35%.
Comparative example 4:
Specific experiment process is with embodiment 1, and difference is, does not pass into inert gas. Measuring sulfonation triazine-5 content in sample is 0.45%.
Comparative example 5:
Specific experiment process is with embodiment 4, and difference is, without UV-irradiation, measuring sulfonation TinuvinP content in sample is 0.096%.
Claims (10)
1. containing a separation method for arene additive in the polymer of benzene ring structure, at least comprise following steps:
(1) dissolving step, provides organic solvent, and dissolve polymer obtains mixed solution;
(2) sulfonation procedure, provides sulfonated reagent, and gained mixed solution in sulfonation procedure (1), obtains the solution that contains sulfonated aromatic hydro carbons additive;
(3) separating step, water extraction, filters, and collects water, obtains the solution of sulfonated aromatic hydro carbons additive.
2. separation method as claimed in claim 1, it is characterized in that, described polymer is selected from: the combination of one or more in polystyrene, expanded polystyrene (EPS), high impact polystyrene, Merlon, PETG, polybutylene terephthalate (PBT), polyphenylene oxide, acrylonitrile-butadiene-styrene (ABS), hydrogenated styrene-butadiene block copolymer.
3. separation method as claimed in claim 1, it is characterized in that, described arene additive is selected from: the combination of one or more in antioxidant, fire retardant, ultraviolet absorber, fluorescent whitening agent, mould inhibitor, antiwear additive, antioxidizing and antigum agent, tackifier, antirust agent, pour-point depressant, foam reducing composition, anti-knock agent, matal deactivator, anti-freezing agent, antisatic additive.
4. separation method as claimed in claim 1, is characterized in that, described dissolving step also comprises pulverization process polymer.
5. separation method as claimed in claim 1, is characterized in that, described sulfonating agent contains sulfonate radical.
6. separation method as claimed in claim 1, is characterized in that, described in be selected from least one in chlorosulfonic acid, oleum, the concentrated sulfuric acid.
7. separation method as claimed in claim 1, is characterized in that, described sulfonation temperature is-10 DEG C～50 DEG C.
8. separation method as claimed in claim 1, is characterized in that, the described sulfonation time is 0.5～5h.
9. separation method as claimed in claim 1, is characterized in that, in described sulfonation procedure, in mixed solution, passes into inert gas.
10. the detection method containing arene additive in the polymer of benzene ring structure, it is characterized in that, through the separation method as described in any one claim in claim 1-9, one or more in employing infra-red sepectrometry, high performance liquid chromatography, gas chromatography, Liquid Chromatography-Mass Spectrometry, Liquid Chromatography-Mass Spectrometry, liquid UV light spectrometry, elemental microanalysis method, fluorescent spectrometry, thermogravimetry, differential thermal analysis, nuclear magnetic resonance method are tested.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510981214.6A CN105606430A (en) | 2015-12-24 | 2015-12-24 | Separation and analysis methods of aromatic hydrocarbon additive in polymer with benzene ring structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510981214.6A CN105606430A (en) | 2015-12-24 | 2015-12-24 | Separation and analysis methods of aromatic hydrocarbon additive in polymer with benzene ring structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105606430A true CN105606430A (en) | 2016-05-25 |
Family
ID=55986539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510981214.6A Pending CN105606430A (en) | 2015-12-24 | 2015-12-24 | Separation and analysis methods of aromatic hydrocarbon additive in polymer with benzene ring structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105606430A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108088924A (en) * | 2017-12-13 | 2018-05-29 | 三明出入境检验检疫局综合技术服务中心 | The rapid detection method of fluorescent whitening agent PF in a kind of plastics package white wine |
| CN108120787A (en) * | 2017-12-21 | 2018-06-05 | 上海微谱化工技术服务有限公司 | The qualitative-and-quantitative method of antioxidant in polyolefin |
| CN108956804A (en) * | 2018-05-29 | 2018-12-07 | 三明出入境检验检疫局综合技术服务中心 | The quantitative detecting method of fluorescent whitening agent WS in a kind of edible mushroom |
| US10364395B2 (en) | 2017-04-13 | 2019-07-30 | Kuwait Institute For Scientific Research | Pyrolysis reactor system for the conversion and analysis of organic solid waste |
| CN114088797A (en) * | 2021-11-09 | 2022-02-25 | 中国石油大学(北京) | Sulfonation method and analysis method of aromatic hydrocarbon compounds in petroleum oil products |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490348A (en) * | 1996-07-08 | 2004-04-21 | ������������ʽ���� | Method for preparing polyelectrolyte |
| CN101549217A (en) * | 2009-04-17 | 2009-10-07 | 天津博纳艾杰尔科技有限公司 | Medicament extracting device and method from body fluid example |
| CN102633964A (en) * | 2012-04-28 | 2012-08-15 | 南京信息工程大学 | Sulfonated SBS (styrene-butadiene-styrene) ionomer and application thereof |
| CN103901067A (en) * | 2014-04-10 | 2014-07-02 | 扬州大学 | Detection method for polycyclic aromatic hydrocarbons in rubber product |
-
2015
- 2015-12-24 CN CN201510981214.6A patent/CN105606430A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490348A (en) * | 1996-07-08 | 2004-04-21 | ������������ʽ���� | Method for preparing polyelectrolyte |
| CN101549217A (en) * | 2009-04-17 | 2009-10-07 | 天津博纳艾杰尔科技有限公司 | Medicament extracting device and method from body fluid example |
| CN102633964A (en) * | 2012-04-28 | 2012-08-15 | 南京信息工程大学 | Sulfonated SBS (styrene-butadiene-styrene) ionomer and application thereof |
| CN103901067A (en) * | 2014-04-10 | 2014-07-02 | 扬州大学 | Detection method for polycyclic aromatic hydrocarbons in rubber product |
Non-Patent Citations (4)
| Title |
|---|
| RONG GUAN ET AL: "Polyethersulfone sulfonated by chlorosulfonic acid and its membrane characteristics", 《EUROPEAN POLYMER JOURNAL》 * |
| YASUSHI TAMADA: "Sulfation of silk fibroin by chlorosulfonic acid and the anticoagulant activity", 《BIOMATERIALS》 * |
| 张光华等: "系列磺酸钠型Gemini表面活性剂的合成及表征", 《化工学报》 * |
| 张巧玲、栗秀萍: "《化学工艺学》", 31 July 2015, 国防工业出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10364395B2 (en) | 2017-04-13 | 2019-07-30 | Kuwait Institute For Scientific Research | Pyrolysis reactor system for the conversion and analysis of organic solid waste |
| CN108088924A (en) * | 2017-12-13 | 2018-05-29 | 三明出入境检验检疫局综合技术服务中心 | The rapid detection method of fluorescent whitening agent PF in a kind of plastics package white wine |
| CN108120787A (en) * | 2017-12-21 | 2018-06-05 | 上海微谱化工技术服务有限公司 | The qualitative-and-quantitative method of antioxidant in polyolefin |
| CN108120787B (en) * | 2017-12-21 | 2021-03-30 | 上海微谱化工技术服务有限公司 | Qualitative and quantitative method for antioxidant in polyolefin |
| CN108956804A (en) * | 2018-05-29 | 2018-12-07 | 三明出入境检验检疫局综合技术服务中心 | The quantitative detecting method of fluorescent whitening agent WS in a kind of edible mushroom |
| CN108956804B (en) * | 2018-05-29 | 2021-07-30 | 三明出入境检验检疫局综合技术服务中心 | Quantitative detection method for fluorescent whitening agent WS in edible fungi |
| CN114088797A (en) * | 2021-11-09 | 2022-02-25 | 中国石油大学(北京) | Sulfonation method and analysis method of aromatic hydrocarbon compounds in petroleum oil products |
| CN114088797B (en) * | 2021-11-09 | 2024-06-11 | 中国石油大学(北京) | Sulfonation method and analysis method of aromatic hydrocarbon compounds in petroleum products |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105606430A (en) | Separation and analysis methods of aromatic hydrocarbon additive in polymer with benzene ring structure | |
| Alfassi et al. | Electrospray ionization mass spectrometry of ionic liquids and determination of their solubility in water | |
| Ferrer et al. | Analysis of 100 pharmaceuticals and their degradates in water samples by liquid chromatography/quadrupole time-of-flight mass spectrometry | |
| Wang et al. | Thermodynamic mechanism of selective cocrystallization explored by MD simulation and phase diagram analysis. | |
| CN105486847B (en) | The separation of phenol antioxidant and detection method in high impact polystyrene | |
| Zhao et al. | Ionic liquid/ionic liquid dispersive liquid–liquid microextraction, a new sample enrichment procedure for the determination of hexabromocyclododecane diastereomers in environmental water samples | |
| CN105486846B (en) | The separation of amine antioxidants and detection method in a kind of butadiene-styrene rubber | |
| CN105585537A (en) | Methods for separating and detecting triazine ultraviolet absorbent in SEBS (styrene-ethylene-butylene-styrene) | |
| SunáKoo et al. | Limitations of the transition state variation model. Part 2. Dual reaction channels for solvolyses of 2, 4, 6-trimethylbenzenesulphonyl chloride | |
| Yokoyama et al. | Alkali-cation affinities of polyoxyethylene dodecylethers and helical conformations of their cationized molecules studied by electrospray mass spectrometry | |
| Celiz et al. | Study on thermal decomposition of polymers by simultaneous measurement of TG–DTA and miniature ion trap mass spectrometry equipped with skimmer-type interface | |
| CN105606415B (en) | Separation and detection method of fluorescent whitening agent in expanded polystyrene | |
| CN105486558B (en) | The separation of benzotriazole light stabilizer and detection method in polyphenyl ether engineering plastic | |
| Hadavi et al. | Ion mobility spectrometry-tandem mass spectrometry strategies for the on-line monitoring of a continuous microflow reaction | |
| Chen et al. | Separation and characterization of the impurities in 3, 3-diamino-4, 4-azoxyfurazan by ultrahigh-performance liquid chromatography combined with Q‑orbitrap mass spectrometry | |
| Strehmel et al. | Synthesis of 4-sulfonatooxy-2, 2, 6, 6-tetramethylpiperidine-1-yloxyl derivatives for investigation of ionic liquids | |
| CN109912512A (en) | A kind of new Telmisartan impurity compound and its preparation method and application | |
| CN105628483B (en) | The separation and detection method of mould inhibitor in expanded polystyrene (EPS) | |
| CN105561629A (en) | Separation and analysis detection methods of diphenyl silanediol in PET (polyethylene glycol terephthalate) fiber | |
| Buncel et al. | HYDROLYSIS OF A SERIES OF PRIMARY ALKYL CHLOROSULFATES: ENTROPY OF ACTIVATION AS A CRITERION OF FRAGMENTATION IN SOLVOLYTIC REACTIONS | |
| Strehmel et al. | Synthesis of 4-trimethylammonio-2, 2, 6, 6-tetramethylpiperidine-1-yloxyl with various anions for investigation of ionic liquids | |
| CN109761953A (en) | A kind of fluorine-containing crown ether compound and its application | |
| CN112824888B (en) | Analytical reagent and method for aminobenzenesulfonic acid positional isomer based on beta cyclodextrin | |
| CN105486772B (en) | The separation of phenyl salicylate and detection method in ABS plastic | |
| CN105601547A (en) | Separation and detection methods of heavy metal ion passivator in PVC (polyvinyl chloride) cable material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160525 |
|
| RJ01 | Rejection of invention patent application after publication |