WO2018021742A1 - 중합체 변성률 측정 방법 - Google Patents
중합체 변성률 측정 방법 Download PDFInfo
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- WO2018021742A1 WO2018021742A1 PCT/KR2017/007609 KR2017007609W WO2018021742A1 WO 2018021742 A1 WO2018021742 A1 WO 2018021742A1 KR 2017007609 W KR2017007609 W KR 2017007609W WO 2018021742 A1 WO2018021742 A1 WO 2018021742A1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- the present invention relates to a method for measuring polymer modification rate, and more particularly, to a method for measuring polymer modification rate, in which a modification rate measurement process is simplified, measurement accuracy is high, and even a relatively large polymer can be measured.
- a rubber material for tires is required to have a low rolling resistance, excellent wear resistance and tensile characteristics, and a polymer having adjustment stability represented by wet skid resistance.
- the modified site through the interaction with the inorganic filler in the preparation of the rubber composition, has a profound effect on compounding processability and physical properties, which is the modification rate of the conjugated diene-based polymer, that is, conjugated It is determined by how much the polymerization active site of the diene polymer is modified.
- the modification rate is used as an important indicator in determining the physical properties of the rubber composition.
- Japanese Patent Laid-Open No. 5698560 and the like disclose a method of measuring relative denaturation with a polystyrene gel using gel permeation chromatography (GPC) as a measuring method of the denaturation rate.
- GPC gel permeation chromatography
- the standard does not adsorb to the column using a silica column (Silica GPC column) that can adsorb the modified component and a polystyrene column (Normal GPC column, also called PS Column) that does not adsorb the modified component, respectively
- Polystyrene is added to the sample as an internal measurement and measured, and the denaturation rate is calculated according to the following Equation 1 from the difference of the refractive index (RI) obtained through the difference (hatched area of FIG. 1).
- an object of the present invention is to provide a method for measuring the polymer modification rate, the modification rate measurement process is simplified, the measurement accuracy is high, and even a relatively large polymer can be measured. .
- the present invention comprises the steps of dissolving a polymer mixture comprising a modified polymer and an unmodified polymer in a first solvent to prepare a first solution; Injecting the first solution into a column filled with an adsorbent; Adsorbing the modified polymer to the adsorbent and eluting a first solution in which the unmodified copolymer is dissolved; Transferring the eluted first solution to a detector; Injecting a second solvent into the column to elute a second solution in which the adsorbed modified polymer is dissolved; And it provides a polymer modification rate measuring method comprising the step of transferring the eluted second solution to the detector.
- the modification rate of the modified polymer can be measured using only the modified polymer, without the need for comparative measurement with a standard substance, thereby simplifying the modification rate measuring process, high measurement accuracy, and gel permeation chromatography. Has the effect of making it possible to measure the modification rate even in a relatively large polymer that cannot be measured.
- FIG. 1 is a schematic view showing a modification rate measuring method according to the prior art.
- Figure 2 is a reference diagram showing the correlation between the adsorbent and the unmodified polymer or modified polymer according to an embodiment of the present invention.
- 3 is a reference diagram showing that the modified polymer is adsorbed on the adsorbent when the first solution passes through the column to the mobile phase according to an embodiment of the present invention.
- Figure 4 is a reference diagram showing that the modified polymer is desorbed from the adsorbent when the second solution is passed through the column to the mobile phase according to an embodiment of the present invention.
- FIG. 5 is a chromatogram showing the change in detection solution according to the second solvent injection in accordance with an embodiment of the present invention.
- Example 6 is a chromatogram according to Example 1 of the present invention.
- the polymer modification rate measuring method of the present invention uses the property that only the modified polymer is adsorbed to the adsorbent (see FIG. 2).
- the polymer modification rate measuring method of the present invention includes a modified polymer and an unmodified polymer. Dissolving the containing polymer mixture in a first solvent to prepare a first solution; Injecting the first solution into a column filled with an adsorbent; Adsorbing the modified polymer to the adsorbent (see FIG. 3) and eluting the first solution in which the unmodified copolymer is dissolved; Transferring the eluted first solution to a detector; Injecting a second solvent into the column to elute a second solution (see FIG. 4) in which the adsorbed modified polymer is dissolved; And transferring the eluted second solution to the detector.
- the modified polymer is partially indicated by 'F', which indicates that part of the polymer has been modified to distinguish it from the unmodified polymer, indicating that it has been modified with a specific element. It is not, nor is it limited, the atomic arrangement or composition being modified.
- the modification rate of the present invention may mean, for example, the ratio of the modified polymer to the unmodified polymer when modified with a modifier for a polymer having a polymerizable site in the polymer, which is a modified polymer. And percentage as a percentage of the total unmodified polymer.
- the modifier may be selected according to the polymer and the purpose of modification, for example, and is not particularly limited.
- the polymer capable of measuring the modification rate is not particularly limited as long as it is a polymer that can be modified by the modifier, but may be, for example, a homopolymer polymerized into a single monomer or a copolymer in which two or more monomers are copolymerized. .
- the polymer modification rate measuring method may be used when measuring the modification rate of the conjugated diene-based polymer, and in particular, may be used when measuring the modification rate of the aromatic vinyl compound-conjugated diene polymer.
- the column of the invention can be a column that can be used for chromatography, for example a normal phase column or stationary phase in which the stationary phase is polar and the mobile phase is nonpolar. This may be a reverse phase column in which the nonpolar and mobile phase is polar.
- the adsorbent according to an embodiment of the present invention refers to the stationary phase of the column, and may be a filler filled in the column, which may be appropriately selected according to the denaturation site modified by the denaturing agent.
- the adsorbent may be, for example, one selected from the group consisting of a silica-based adsorbent, a polymer-based adsorbent, an alumina (Al 2 O 3 ) adsorbent, a graphitized carbon adsorbent and a zirconia adsorbent, and in particular, may be a silica-based adsorbent. Adsorption of various modified polymers is easy.
- the silica-based adsorbent is, for example, silica gel adsorbent derived from silica (SiO 2 ); And a silanol (Si-OH) group on the surface of the silica gel has a chain, branched or cyclic alkylsilane having 1 to 30 carbon atoms, an arylsilane having 5 to 30 carbon atoms, a chain, branched or cyclic alkyl city having 1 to 30 carbon atoms.
- silica gel adsorbents examples include silica gel adsorbents; And trimethylsilane, ethyl (dimethyl) silane, propyl (dimethyl) silane, butyl (dimethyl) silane, octyl (dimethyl) silane, decyl (dimethyl) silane, octadecyl (dimethyl) silane, cyanopropyl (dimethyl) silane, amino It may be at least one selected from the group consisting of; adsorbents end capped with at least one derived group selected from the group consisting of propyl (dimethyl) silane and 4-phenylbutyl (dimethyl) silane.
- the adsorbent may have a particle size of 0.001 to 100 ⁇ m, 1 to 100 ⁇ m, 1 to 50 ⁇ m, or 3 to 30 ⁇ m, and easily adsorb the modified polymer within this range.
- the particle size may mean, for example, an average particle diameter according to the shape of the adsorbent.
- the particle size may mean an average particle diameter with respect to a diameter or a long axis. In the case of a polyhedron, it may mean an average particle diameter with respect to the long axis.
- the first solvent and the second solvent may each independently be a polar solvent or a nonpolar solvent, and preferably, when the first solvent is a polar solvent, the second solvent is a nonpolar solvent. And when the first solvent is a nonpolar solvent, the second solvent may be a polar solvent, in which case the effect of eluting the unmodified polymer from the first solution and the modified polymer from the second solution more efficiently have.
- the first solvent and the second solvent may be each independently a polar solvent having a difference in polarity, and preferably, when the first solvent is a polar solvent having high polarity, the second solvent
- the first solvent is a polar solvent having a low polarity
- the second solvent may be a polar solvent having a high polarity
- the polarity is not an absolute value
- the first It may be a relative concept according to the polarity of the polar solvent used in the solvent and the second solvent, respectively, in which case there is an effect of eluting the unmodified polymer from the first solution and the modified polymer from the second solution more efficiently.
- the polar solvent may be used in chromatography, and is not particularly limited as long as it is a polar solvent capable of dissolving the modified polymer and the unmodified polymer.
- the polar solvent include water, methanol, ethanol, n-propanol, n-butanol, isopropanol, formic acid, Acetic acid, acetone, nitromethane, propylene carbonate, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran (THF), acetonitrile (MeCN), dimethylformamide (DMF) , Dimethyl sulfoxide (DMSO), methyl ethyl ketone, benzonitrile, pyridine, nitroethane, benzyl alchol, methoxy ethanol and formamide It may be abnormal.
- the non-polar solvent may be used in chromatography, and is not particularly limited as long as it is a polar solvent capable of dissolving the modified polymer and the unmodified polymer.
- a polar solvent capable of dissolving the modified polymer and the unmodified polymer.
- hexane, benzene, toluene, diethyl ether, chloroform, ethyl acetate, dichloromethane It may be one or more selected from the group consisting of cyclohexane, tetrachloromethane, iso-octane, xylene, butyl ether, isopropyl ether and ethylene chloride.
- the first solution may be injected at a flow rate of 0.001 to 30 ml / min, 0.01 to 20 ml / min, 0.1 to 10 ml / min or 0.5 to 1 ml / min.
- the second solvent may be injected at a flow rate of 0.001 to 30 ml / min, 0.01 to 20 ml / min, 0.1 to 10 ml / min or 0.5 to 1 ml / min. Within the range, there is an effect of eluting the second solution in which the modified polymer adsorbed to the adsorbent is dissolved.
- the second solvent may be injected after the total amount of the unmodified polymer is eluted.
- the time point at which the whole of the unmodified polymer is eluted may mean a time point when the signal of the unmodified polymer is no longer detected from the detector.
- the second solvent may be injected into a column into which the first solution is injected after the injection of the first solution is completed, and preferably, the first solvent may be changed according to a gradient elution that continuously changes the composition of the solvent.
- the solution can be continuously injected into the injected column, in this case, the effect can be measured more accurately, without interruption of the signal during detection.
- the first solution and the second solution are separated from when the second solvent is injected. It can be eluted at the same time, and the first and second solutions eluted at the same time can be transferred to the detector at the same time.
- the first solution and the second solution from the time point of the injection of the second solvent, the content of each of the first solvent and the second solvent according to the injection flow rate
- One solution can be gradually increased or decreased from 100% to 0% by volume and the second solution from 0% to 100% by volume.
- the first solution and the second solution may be detected at the same time in the detector from the time of injection of the second solvent, and the detection amount of the pre-injected first solution according to the injection of the second solvent is from 100% by volume to 0% by volume. Decreases, the detection amount of the second solution increases from 0% to 100% by volume as the detection amount of the first solution decreases, and only when the elution of the first solution is completed, only the second solution can be detected (Fig. 5).
- the polymer modification rate measurement method may use a chromatographic measurement instrument, for example, a liquid chromatography measurement instrument, for example, for storing the first solution and the second solvent Mobile phase reservoirs, pumps for consistently and reproducibly supplying mobile phases to columns, injectors to control injection volumes of solutions or solvents injected into columns, for separating denatured polymers and unmodified polymers It may be a chromatographic measuring instrument comprising a column and a detector for sensing the eluted modified or unmodified polymer.
- a chromatographic measurement instrument for example, a liquid chromatography measurement instrument, for example, for storing the first solution and the second solvent Mobile phase reservoirs, pumps for consistently and reproducibly supplying mobile phases to columns, injectors to control injection volumes of solutions or solvents injected into columns, for separating denatured polymers and unmodified polymers
- a chromatographic measuring instrument comprising a column and a detector for sensing the eluted modified or unmodified polymer.
- Two or more mobile phase reservoirs may be provided, for example, and a mobile phase reservoir for storing the first solution and a mobile phase reservoir for storing the second solvent may be provided separately.
- the mobile phase reservoir may include a separate gradient elution device for the application of gradient elution.
- the pump for example, generates a pressure of 0.1 to 10,000 psi or 100 to 5,000 psi, regulates a flow rate of 0.01 to 20 ml or 0.1 to 10 ml, is free of pulses in solution or solvent supply, The rate of change may be maintained at 1% or less, or 0.1 to 0.5%.
- the pump may be a single-head pump or a dual-head pump, preferably a dual-head pump, in which case a gradient elution It is easy to apply elution.
- the injector may be, for example, a rheodyne injector or an automatic injector, and the leodyne injector may have, for example, a volume of a loop of 1 to 500 ⁇ l, 5 to 200 ⁇ l, or 10 to It may be 100 ⁇ l, and there is an effect of high injection accuracy within this range.
- the detector may be selected from among a UV / Vis detector, a fluorescence detector, a refractive index detector, or an evaporative light scattering detector, and preferably a vaporized light scattering detector.
- the response factor is constant, accurate composition analysis is possible without preparing a calibration curve by a standard material, and detection according to gradient elution enables excellent resolution and separation sensitivity.
- the denaturation rate of the present invention may be calculated from, for example, a chromatogram detected through the chromatographic measuring instrument, and may be calculated according to Equation 2 below.
- the peak area of the unmodified polymer may be the peak area of the chromatogram for the first solution transferred to the detector, and the peak area of the modified polymer is the peak area of the chromatogram for the second solution transferred to the detector Can be.
- styrene 710 g of 1,3-butadiene, 5,000 g of normal hexane, 0.86 g of 2,2-bis (2-oxolanyl) propane as a polar additive were added to a 20L autoclave reactor, and the temperature inside the reactor was increased to 40 ° C. It heated up. When the internal temperature of the reactor reached 40 ° C., 4 mmol of n-butyllithium was added to the reactor to perform an adiabatic heating reaction.
- N, N-bis (triethoxysilylpropyl) aminopropyl-1-imidazole N, N-bis
- (triethoxysilylypropyl) aminopropyl-1-imidazole) was added 4.3 mmol (purity 98%) and reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a hexane solution containing 0.3 wt% of butylated hydroxy toluene (BHT) was added as an antioxidant.
- BHT butylated hydroxy toluene
- the obtained polymer was put in hot water heated with steam, stirred to remove the solvent, and then roll dried to remove the residual solvent and water, thereby preparing a styrene-butadiene copolymer modified at the ends.
- the modified styrene-butadiene copolymer was dissolved in cyclohexane and stored in a mobile phase reservoir, tetrahydrofuran (THF) in another mobile phase reservoir Stored.
- THF tetrahydrofuran
- the mobile phase reservoirs were respectively connected to dual-head pumps, and a solution of the mobile phase reservoirs in which the modified styrene-butadiene copolymer was dissolved was first injected into the column filled with silica adsorbent through the pump and an injector with a 20 ⁇ l loop volume. .
- the pressure of the pump was 450 psi and the injection flow rate was 0.5 ml / min.
- the detector confirmed that the unmodified styrene-butadiene copolymer in the modified styrene-butadiene copolymer is no longer detected, and at 5 minutes from the start of injection, the tetrahydrofuran was injected into the column through a pump.
- the pressure of the pump was 380 psi and the injection flow rate was 0.5 ml / min.
- N, N-bis (triethoxysilylpropyl) aminopropyl-1-imidazole N, N-bis (triethoxysilylypropyl) aminopropyl-1-imidazole
- the modification rate was measured in the same manner as in the above example, and the modification rate (%) was calculated according to Equation 2 from the detected chromatogram result (see FIG. 7). . At this time, the denaturation rate was 31.6%.
- the modified styrene-butadiene copolymers of Example 1 and Comparative Example 1 which show a difference in the modification rate, have a pattern viscosity (MV), styrene monomer and vinyl content in the copolymer, and a weight average, respectively.
- MV pattern viscosity
- Mw number average molecular weight
- PDI molecular weight distribution
- the MV-2000 manufactured by ALPHA Technologies Co., Ltd. was preheated for 1 minute using two rubber specimens weighing more than 15 g and then measured at 100 ° C. for 4 minutes.
- the peak molecular weight (Mp), weight average molecular weight (Mw) and number average molecular weight (Mn) of each copolymer were measured by gel permeation chromatograph (GPC) analysis under 40 ° C.
- GPC gel permeation chromatograph
- the column (column) was used in combination with two bags of PLgel Olexis of Polymer Laboratories Co., Ltd. and one PLgel mixed-C column, all of the newly replaced column was a mixed bed column.
- PS polystyrene
- the molecular weight distribution (PDI) was calculated by calculating the ratio of the weight average molecular weight and the number average molecular weight measured by the above method, and rounded off to the second decimal place.
- the rubber compositions comprising the modified styrene-butadiene copolymers of Example 1 and Comparative Example 1, which show a difference in the modification rate, and the molded articles prepared therefrom,
- rubber specimens for measuring physical properties were prepared, and tensile and viscoelastic properties were measured and shown in Table 3 below.
- Example 1 Each modified styrene-butadiene copolymer of Example 1 and Comparative Example 1 was blended under the mixing conditions shown in Table 2 below as a raw material rubber.
- the content of each raw material in Table 2 is calculated based on 100 parts by weight of rubber.
- the rubber specimen is kneaded through the first stage kneading and the second stage kneading.
- the raw rubber styrene-butadiene copolymer
- filler styrene-butadiene copolymer
- organosilane coupling agent styrene-butadiene copolymer
- oil process oil
- galvanizing agent stearic acid
- antioxidant antioxidant
- aging a half-barrier mixer equipped with a temperature controller.
- Inhibitors, waxes and promoters were kneaded.
- the temperature of the kneader was controlled to 150 ° C.
- the primary blend was obtained at a discharge temperature of 145 ° C. to 155 ° C.
- the primary compound, sulfur, and a vulcanization accelerator were added to the kneader, and it mixed at the temperature of 100 degrees C or less, and obtained the secondary compound. Thereafter, rubber specimens were prepared through a curing process at 100 ° C. for 20 minutes.
- Tensile properties of the prepared rubber specimens were measured according to the tensile test method of ASTM 412 and the tensile strength at the time of cutting the specimen and the tensile stress at 300% elongation (300% modulus).
- the viscoelastic properties of the rubber specimens prepared above were measured using a dynamic mechanical analyzer manufactured by TA, and the viscoelastic coefficients (tan ⁇ ) were measured at a frequency of 10 Hz and at respective measurement temperatures ( ⁇ 60 ° C. to 60 ° C.) in a torsion mode.
- the Payney effect is expressed as the difference between the minimum and maximum values at 0.28% to 40% of the strain. The smaller the Faye effect, the better the dispersibility of fillers such as silica.
- higher tan ⁇ at low temperature of 0 ° C. means better wet road resistance
- lower tan ⁇ at high temperature of 60 ° C. means less hysteresis loss and better rolling resistance, that is, low fuel consumption.
- Example 1 in which the denaturation rate measured according to the present invention is high by denaturation through a high purity denaturant, the denaturation rate measured according to the present invention is modified by a low purity denaturant.
- 300% modulus (tensile stress) and tensile strength are excellent, the value of Tan ⁇ at 60 °C is low, the value of Tan ⁇ at 0 °C is high, tensile and viscoelastic properties All were excellent.
- the G 'value at 60 ° C is significantly lower than that of Comparative Example 1, it was confirmed that the dispersion degree of the filler, that is, silica is very high.
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Abstract
Description
구분 | 실시예 1 | 비교예 1 | |
n-부틸리튬(mmol/h) | 4 | 4 | |
극성첨가제 (g/h) | 0.86 | 0.86 | |
변성제 (mmol/h) | 4.3 | 4.3 | |
무늬 점도 (MV) | 74 | 62 | |
NMR (%) | 스티렌 단량체 | 27 | 27 |
비닐(Vinyl) | 42 | 43 | |
GPC (x104) | Mp | 22 | 20 |
Mn | 35 | 28 | |
Mw | 50 | 36 | |
PDI | 1.4 | 1.3 |
구분 | 원료 | 함량(중량부) |
제1단 혼련 | 고무 | 100 |
실리카 | 70 | |
커플링제 | 11.2 | |
오일(공정유) | 37.5 | |
아연화제 | 3 | |
스테아르산 | 2 | |
산화 방지제 | 2 | |
노화 방지제 | 2 | |
왁스 | 1 | |
고무촉진제 | 1.75 | |
제2단 혼련 | 황 | 1.5 |
가황촉진제 | 2 | |
총 중량 | 233.95 |
구분 | 실시예 1 | 비교예 1 |
300% 모듈러스(kgf/cm2) | 130 | 119 |
인장강도 (kgf/cm2) | 203 | 187 |
점탄성 계수(Tanδ at 0℃) | 0.988 | 0.911 |
점탄성 계수(Tanδat 60℃) | 0.109 | 0.121 |
페이니 효과 (60 ℃, G') | 0.29 | 0.35 |
Claims (11)
- 변성 중합체 및 미변성 중합체를 포함하는 중합체 혼합물을 제1 용매에 용해시켜 제1 용액을 준비하는 단계;상기 제1 용액을, 흡착제가 충진된 컬럼(column)에 주입시키는 단계;상기 변성 중합체를 상기 흡착제에 흡착시키고, 상기 미변성 공중합체가 용해된 제1 용액을 용출시키는 단계;상기 용출된 제1 용액을 검출기로 이송시키는 단계;제2 용매를 상기 컬럼에 주입시켜 상기 흡착된 변성 중합체가 용해된 제2 용액을 용출시키는 단계; 및상기 용출된 제2 용액을 상기 검출기로 이송시키는 단계를 포함하는 중합체 변성률 측정 방법.
- 제1항에 있어서,상기 중합체는 공액디엔계 중합체인 중합체 변성률 측정 방법.
- 제1항에 있어서,상기 흡착제는 실리카계 흡착제인 중합체 변성률 측정 방법.
- 제1항에 있어서,상기 제1 용매는 극성 용매 또는 비극성 용매이고,상기 제2 용매는 극성 용매 또는 비극성 용매이며,상기 제1 용매가 극성 용매일 때, 상기 제2 용매는 비극성 용매이고,상기 제1 용매가 비극성 용매일 때, 상기 제2 용매는 극성 용매인 중합체 변성률 측정 방법.
- 제4항에 있어서,상기 극성 용매는 물, 메탄올, 에탄올, n-프로판올, n-부탄올, 이소프로판올, 포름산, 아세트산, 아세톤, 니트로메탄, 프로필렌 카보네이트, 1,2-디옥산, 1,3-디옥산, 1,4-디옥산, 테트라하이드로퓨란(THF), 아세토니트릴(MeCN), 디메틸포름아미드(DMF), 디메틸설폭시드(DMSO), 메틸 에틸 케톤, 벤조니트릴, 피리딘(pyridine), 니트로에탄(nitroethane), 벤질 알콜(benzyl alchol), 메톡시 에탄올(methoxy ethanol) 및 포름아미드로 이루어진 군으로부터 선택된 1종 이상인 중합체 변성률 측정 방법.
- 제4항에 있어서,상기 비극성 용매는 헥산, 벤젠, 톨루엔, 디에틸 에터, 클로로포름, 에틸아세테이트, 디클로로메탄, 시클로헥산, 테트라클로로메탄, 이소-옥탄(iso-octane), 자일렌(xylene), 부틸 에터(butyl ether), 이소프로필 에터(isopropyl ether) 및 에틸렌 클로라이드로 이루어진 군으로부터 선택된 1종 이상인 중합체 변성률 측정 방법.
- 제1항에 있어서,상기 제1 용액는 0.001 내지 30 ml/min의 유속으로 주입되는 것인 중합체 변성률 측정 방법.
- 제1항에 있어서,상기 제2 용매는 0.001 내지 30 ml/min의 유속으로 주입되는 것인 중합체 변성률 측정 방법.
- 제1항에 있어서,상기 제2 용매는 미변성 중합체 전량이 용출된 후 주입되는 것인 중합체 변성률 측정 방법.
- 제9항에 있어서,상기 제2 용매는 경사 용리법(gradient elution)에 따라 제1 용액이 주입된 컬럼에 연속적으로 주입되는 것인 중합체 변성률 측정 방법.
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JP2018504193A JP6847916B2 (ja) | 2016-07-26 | 2017-07-14 | 重合体変性率の測定方法 |
CN201780002520.8A CN107923891A (zh) | 2016-07-26 | 2017-07-14 | 聚合物改性率的测量方法 |
EP17808737.5A EP3315962B1 (en) | 2016-07-26 | 2017-07-14 | Method for measuring polymer modification ratio |
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