CN111812141A - Test method for evaluating coupling capacity of white carbon black and silane coupling agent - Google Patents

Test method for evaluating coupling capacity of white carbon black and silane coupling agent Download PDF

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CN111812141A
CN111812141A CN202010662688.5A CN202010662688A CN111812141A CN 111812141 A CN111812141 A CN 111812141A CN 202010662688 A CN202010662688 A CN 202010662688A CN 111812141 A CN111812141 A CN 111812141A
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carbon black
white carbon
silane coupling
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王健
周天明
任衍峰
孙胜焕
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Sailun Jinyu Group Co Ltd
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Abstract

The invention discloses a testing method for evaluating the coupling capacity of white carbon black and a silane coupling agent, and belongs to the technical field of silane coupling agent activity testing. The technical scheme is as follows: respectively carrying out hydroxyl determination on the white carbon black and the white carbon black-silane coupling agent composite sample by adopting a solid nuclear magnetic resonance method to obtain a nuclear magnetic spectrum of the white carbon black and the white carbon black-silane coupling agent composite sample, carrying out peak separation analysis on the nuclear magnetic spectrum, and determining the mass fractions of the dihydroxy and the monohydroxy in the total mass of the white carbon black and the total mass of the composite sample; and finally, the content of the hydroxyl participating in the reaction can be judged by combining the graph difference value processing and the mass fraction difference value with a calculation formula. The method can more intuitively and effectively calculate the ratio of the hydroxyl groups participating in the coupling reaction and the matching capability of the white carbon black and the silane coupling agent, and reasonably determine the accurate dosage of the silane coupling agent.

Description

Test method for evaluating coupling capacity of white carbon black and silane coupling agent
Technical Field
The invention relates to the technical field of silane coupling agent activity test, in particular to a test method for evaluating the coupling capacity of white carbon black and a silane coupling agent.
Background
The main component of the white carbon black is silicon dioxide, and the silicon oxygen atoms in the white carbon black are combined in a tetrahedral configuration to form a unique three-dimensional network structure. The white carbon black has excellent performances of dispersibility, chemical stability, high temperature resistance, good electrical insulation, porosity, small mass, no combustion and the like, has excellent reinforcing property, thickening property, thixotropy and the like due to a special surface structure and particle morphology, and becomes one of important inorganic fillers in the fields of rubber and the like. The white carbon black is an important reinforcing filler of rubber products, can improve the physical properties of rubber materials, reduce the hysteresis of the rubber materials, reduce the rolling resistance of tires, and simultaneously does not damage the wet skid resistance of the tires. But the active silicon hydroxyl on the surface of the white carbon black makes the white carbon black hydrophilic and is difficult to wet and disperse in an organic phase; the presence of hydroxyl groups makes the surface energy larger, the aggregates tend to agglomerate and the application properties of the product are affected. Therefore, the determination of the hydroxyl content of the white carbon black has important significance for improving the interaction of the white carbon black and rubber and researching the modification of the white carbon black.
For many years, researchers have tried to determine the hydroxyl content on the surface of the white carbon black by using various methods, mainly including a metal hydride reaction method, a burning method, an organosilane reaction method, an infrared spectroscopy method, a nuclear magnetic resonance method, a chemical derivation method and the like, but the methods have defects in the accuracy and efficiency of determining the hydroxyl content. The solid nuclear magnetic resonance method can determine the total content of hydroxyl on the surface of the white carbon black, but cannot accurately represent the content of active hydroxyl participating in modification.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method can be used for more intuitively and effectively calculating the ratio of hydroxyl groups participating in the coupling reaction and the matching capability of the white carbon black and the silane coupling agent, and reasonably determining the accurate dosage of the silane coupling agent.
The technical scheme of the invention is as follows:
a test method for evaluating the coupling capacity of white carbon black and a silane coupling agent comprises the following steps:
s1 determination of hydroxyl content of white carbon black
Hydroxyl determination is carried out on the white carbon black by using a solid nuclear magnetic resonance method to obtain a nuclear magnetic spectrum of the white carbon black, and peak separation analysis is carried out on the nuclear magnetic spectrum to determine the mass fraction of the dihydroxyl group and the monohydroxy group in the total mass of the white carbon black;
s2 preparation of composite samples
S21: adding 10-15g of white carbon black into 40-80ml of solvent to form white carbon black suspension, and carrying out ultrasonic treatment for 20-40 minutes to obtain stable and uniform suspension;
s22: slowly adding 0.5-2g of silane coupling agent into the suspension obtained in S21 to perform incomplete coupling reaction to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution for 60-180 minutes to obtain a precursor mixed solution;
s23: centrifuging the precursor mixed solution obtained in the step S22, removing supernatant, and adding a solvent to supplement the original volume; repeatedly centrifuging for many times, and performing suction filtration on the centrifuged lower-layer solid to obtain a sample;
s24: drying the sample obtained in the step S23 to remove the solvent, so as to obtain a composite sample;
s3 determination of hydroxyl content of composite sample
Performing white carbon black mass correction on the mass of the composite sample, wherein the mass of the composite sample after modification of the silane coupling agent is n times of the mass of the same group of white carbon black, performing hydroxyl determination on the composite sample obtained in S24 by using a solid nuclear magnetic resonance method to obtain a nuclear magnetic spectrum of the composite sample, performing peak separation analysis on the nuclear magnetic spectrum, and determining the mass fractions of the dihydroxy and the monohydroxy in the total mass of the composite sample and the total mass of the white carbon black; the content of the hydroxyl participating in the reaction can be judged by carrying out graphic difference processing and mass fraction difference,
n＝(m1+m2)/m1
m1m is the mass of white carbon black2Is the mass of a silane coupling agent;
the reaction dihydroxy ratio calculation formula is as follows:
Figure BDA0002579205580000031
the calculated formula of the monohydroxy ratio of the reaction is as follows:
Figure BDA0002579205580000032
preferably, the solvent is DMF, benzamide, succinimide or phthalimide, does not react with silicon oxygen bonds and surface hydroxyl groups, has certain chemical stability, and is a good polar organic solvent.
Preferably, in step S23, the number of centrifugation is 3.
Preferably, in step S24, the sample obtained in S23 is dried in a vacuum drying oven at 40-100 deg.C for 60-360 min to remove the solvent.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, the silane coupling progress can be judged by preparing a composite sample of a white carbon black-silane coupling agent system and testing the surface hydroxyl difference between the composite sample and white carbon black by adopting a solid nuclear magnetic resonance method, and the coupling capability of the silane coupling agent is evaluated. The hydroxyl group ratio participating in the coupling reaction, the fit capability of the white carbon black and the silane coupling agent can be calculated more intuitively and effectively, and the accurate dosage of the silane coupling agent can be determined reasonably.
Drawings
FIG. 1 shows NMR silicon spectra of unmodified silica and silica modified with Si747 and Si 69.
FIG. 2 is the NMR silicon spectra of unmodified silica and KH-550 and A171 modified silica.
FIG. 3 is the NMR silicon spectra of unmodified silica and KH-570 and A151 modified silica.
In the figure, the D1 partial peak represents the content of the bishydroxysiloxy group, the D2 partial peak represents the content of the monohydroxysiloxy group, and the D3 partial peak represents the content of the non-hydroxysiloxy group.
Detailed Description
Example 1
S1: hydroxyl determination is carried out on the white carbon black by using a solid nuclear magnetic resonance method to obtain a nuclear magnetic spectrum of the white carbon black, and peak separation analysis is carried out on the nuclear magnetic spectrum to determine the mass fraction of the dihydroxyl group and the monohydroxy group in the total mass of the white carbon black;
s21: adding 12g (about 0.2mol) of white carbon black into 50ml of DMF (N, N-dimethylformamide) to form a white carbon black suspension, and carrying out ultrasonic treatment for 30 minutes to obtain a stable and uniform suspension;
s22: slowly adding 1g of silane coupling agent into the suspension obtained in S21 to perform incomplete coupling reaction to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution for 120 minutes to obtain a precursor mixed solution;
s23: placing the precursor mixed solution obtained in the step S22 in a centrifuge tube, performing centrifugal treatment by using a high-speed centrifuge, removing supernatant, and adding DMF (dimethyl formamide) to supplement the original volume; repeatedly centrifuging for 3 times, performing suction filtration on the centrifuged lower-layer solid by using a Buchner funnel, and collecting the solid to an aluminum foil to obtain a sample;
s24: placing the sample obtained in the step S23 in a vacuum drying oven, and heating at 60 ℃ for 120 minutes to remove the solvent to obtain a composite sample;
s3: performing white carbon black mass correction on the mass of a composite sample, wherein the mass of the composite sample after modification of a silane coupling agent is 13/12 times that of the white carbon black of the same group, performing hydroxyl determination on the composite sample by using a solid nuclear magnetic resonance method to obtain a nuclear magnetic spectrum of the composite sample, performing peak separation analysis on the nuclear magnetic spectrum, and determining the proportion of dihydroxy groups and monohydroxy groups participating in a coupling reaction to total dihydroxy groups and total monohydroxy groups;
the reaction dihydroxy ratio calculation formula is as follows:
Figure BDA0002579205580000041
the calculated formula of the monohydroxy ratio of the reaction is as follows:
Figure BDA0002579205580000042
in this embodiment, silane coupling agents Si747 and Si69 are respectively used to modify white carbon black, and the hydroxyl content of unmodified white carbon black, silane coupling agents Si747 and Si69 modified white carbon black can be calculated according to the formula shown in fig. 1, as shown in table 1:
TABLE 1
Figure BDA0002579205580000043
Figure BDA0002579205580000051
From table 1, it can be judged that, in the reaction of silica and Si747 under the same reaction conditions, more dihydroxy groups and monohydroxy groups are involved in the reaction, and thus it can be judged that the silane coupling agent Si747 has a higher coupling ability.
Example 2
S1: hydroxyl determination is carried out on the white carbon black by using a solid nuclear magnetic resonance method to obtain a nuclear magnetic spectrum of the white carbon black, and peak separation analysis is carried out on the nuclear magnetic spectrum to determine the mass fraction of the dihydroxyl group and the monohydroxy group in the total mass of the white carbon black;
s21: adding 10g of white carbon black into 40ml of benzamide to form white carbon black suspension, and performing ultrasonic treatment for 20 minutes to obtain stable and uniform suspension;
s22: slowly adding 0.5g of silane coupling agent into the suspension obtained in S21 to perform incomplete coupling reaction to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution for 60 minutes to obtain a precursor mixed solution;
s23: placing the precursor mixed solution obtained in the step S22 in a centrifuge tube, performing centrifugal treatment by using a high-speed centrifuge, removing supernatant, and adding benzamide to supplement the original volume; repeatedly centrifuging for 3 times, performing suction filtration on the centrifuged lower-layer solid by using a Buchner funnel, and collecting the solid to an aluminum foil to obtain a sample;
s24: and (4) placing the sample obtained in the S23 in a vacuum drying oven, and heating at 40 ℃ for 60 minutes to remove the solvent to obtain a composite sample.
S3: performing white carbon black mass correction on the mass of a composite sample, wherein the mass of the composite sample after modification of a silane coupling agent is 1.05 times of that of the same group of white carbon black, performing hydroxyl determination on the composite sample by using a solid nuclear magnetic resonance method to obtain a nuclear magnetic spectrum of the composite sample, performing peak separation analysis on the nuclear magnetic spectrum, and determining the proportion of dihydroxy groups and monohydroxy groups participating in a coupling reaction to total dihydroxy groups and total monohydroxy groups;
the reaction dihydroxy ratio calculation formula is as follows:
Figure BDA0002579205580000061
the calculated formula of the monohydroxy ratio of the reaction is as follows:
Figure BDA0002579205580000062
in this embodiment, silane coupling agents KH-550 and a171 are respectively used to modify white carbon black, and the hydroxyl content of unmodified white carbon black, silane coupling agents KH-550 and a171 modified white carbon black can be calculated according to the formula shown in fig. 2, as shown in table 2:
TABLE 2
Figure BDA0002579205580000063
From table 2, it can be determined that the same kind of white carbon black has a little more dihydroxy groups and monohydroxy groups participating in the reaction between white carbon black and KH-550 under the same reaction conditions, and thus, it can be determined that the coupling ability of KH-550 is higher.
Example 3
S1: hydroxyl of the white carbon black is measured by using a solid nuclear magnetic resonance method to obtain a nuclear magnetic spectrum of the white carbon black, and the nuclear magnetic spectrum is subjected to peak analysis to determine the mass fraction of the dihydroxyl and monohydroxy in the total mass of the white carbon black.
S21: adding 15g of white carbon black into 80ml of succinimide to form white carbon black suspension, and performing ultrasonic treatment for 40 minutes to obtain stable and uniform suspension;
s22: slowly adding 2g of silane coupling agent into the suspension obtained in S21 to perform incomplete coupling reaction to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution for 180 minutes to obtain a precursor mixed solution;
s23: placing the precursor mixed solution obtained in the step S22 in a centrifuge tube, centrifuging by using a high-speed centrifuge, removing supernatant, and adding succinimide to supplement the original volume; repeatedly centrifuging for 3 times, performing suction filtration on the centrifuged lower-layer solid by using a Buchner funnel, and collecting the solid to an aluminum foil to obtain a sample;
s24: and (4) placing the sample obtained in the S23 in a vacuum drying oven, and heating at 100 ℃ for 360 minutes to remove the solvent to obtain a composite sample.
S3: performing white carbon black mass correction on the mass of a composite sample, wherein the mass of the composite sample after modification of a silane coupling agent is 17/15 times that of the white carbon black of the same group, performing hydroxyl determination on the composite sample by using a solid nuclear magnetic resonance method to obtain a nuclear magnetic spectrum of the composite sample, performing peak separation analysis on the nuclear magnetic spectrum, and determining the proportion of dihydroxy groups and monohydroxy groups participating in a coupling reaction to total dihydroxy groups and total monohydroxy groups;
the reaction dihydroxy ratio calculation formula is as follows:
Figure BDA0002579205580000071
the calculated formula of the monohydroxy ratio of the reaction is as follows:
Figure BDA0002579205580000072
in this embodiment, silane coupling agents KH-570 and a151 are respectively used to modify white carbon black, and the hydroxyl content of unmodified white carbon black, silane coupling agents KH-570 and a151 modified white carbon black can be calculated according to the formula shown in fig. 3, as shown in table 2:
TABLE 3
Figure BDA0002579205580000073
Figure BDA0002579205580000081
As can be seen from Table 3, it was found that the same kind of white carbon black had a slightly larger number of dihydroxy groups and monohydroxy groups involved in the reaction between white carbon black and KH-570 under the same reaction conditions, and thus it was found that KH-570 had a higher coupling ability.

Claims (4)

1. A test method for evaluating the coupling capacity of white carbon black and a silane coupling agent is characterized by comprising the following steps:
s1 determination of hydroxyl content of white carbon black
Hydroxyl determination is carried out on the white carbon black by using a solid nuclear magnetic resonance method to obtain a nuclear magnetic spectrum of the white carbon black, and peak separation analysis is carried out on the nuclear magnetic spectrum to determine the mass fraction of the dihydroxyl group and the monohydroxy group in the total mass of the white carbon black;
s2 preparation of composite samples
S21: adding 10-15g of white carbon black into 40-80ml of solvent to form white carbon black suspension, and carrying out ultrasonic treatment for 20-40 minutes to obtain stable and uniform suspension;
s22: slowly adding 0.5-2g of silane coupling agent into the suspension obtained in S21 to perform incomplete coupling reaction to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution for 60-180 minutes to obtain a precursor mixed solution;
s23: centrifuging the precursor mixed solution obtained in the step S22, removing supernatant, and adding a solvent to supplement the original volume; repeatedly centrifuging for many times, and performing suction filtration on the centrifuged lower-layer solid to obtain a sample;
s24: drying the sample obtained in the step S23 to remove the solvent, so as to obtain a composite sample;
s3 determination of hydroxyl content of composite sample
Performing white carbon black mass correction on the mass of the composite sample, wherein the mass of the composite sample after modification of the silane coupling agent is n times of the mass of the same group of white carbon black, performing hydroxyl determination on the composite sample obtained in S24 by using a solid nuclear magnetic resonance method to obtain a nuclear magnetic spectrum of the composite sample, performing peak separation analysis on the nuclear magnetic spectrum, and determining the mass fractions of the dihydroxy and the monohydroxy in the total mass of the composite sample and the total mass of the white carbon black; the content of the hydroxyl participating in the reaction can be judged by carrying out graphic difference processing and mass fraction difference,
n＝(m1+m2)/m1
m1m is the mass of white carbon black2Is the mass of a silane coupling agent;
the reaction dihydroxy ratio calculation formula is as follows:
Figure FDA0002579205570000021
the calculated formula of the monohydroxy ratio of the reaction is as follows:
Figure FDA0002579205570000022
2. the test method for evaluating the coupling ability of silica white with silane coupling agent according to claim 1, wherein the solvent is DMF, benzamide, succinimide or phthalimide.
3. The method for testing the ability of white carbon black to couple with a silane coupling agent according to claim 1, wherein the centrifugation frequency is 3 times in step S23.
4. The method for testing the ability of silica white to couple with silane coupling agent according to claim 1, wherein in step S24, the sample obtained in step S23 is dried in a vacuum oven at 40-100 ℃ for 60-360 minutes to remove the solvent.
CN202010662688.5A 2020-07-10 2020-07-10 Test method for evaluating coupling capacity of white carbon black and silane coupling agent Pending CN111812141A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006337342A (en) * 2005-06-06 2006-12-14 Yokohama Rubber Co Ltd:The Method of measuring reaction amount of silica, and rubber composition with reaction amount defined using the method
CN101514263A (en) * 2009-04-01 2009-08-26 苏州大学 Modified white carbon black and preparation method thereof
CN102220036A (en) * 2011-06-02 2011-10-19 北京化工大学 Method for preparing white carbon black modified by silane coupling agent
WO2013118801A1 (en) * 2012-02-08 2013-08-15 住友ゴム工業株式会社 Method for quantifying strength of interface bonding between silica and modified polymer, rubber composition adjusted by said method, and pneumatic tire using same
JP2013231694A (en) * 2012-05-01 2013-11-14 Sumitomo Rubber Ind Ltd Method for obtaining reaction active group amount of silica, rubber composition whose reaction amount of silica is specified by using the same, and pneumatic tire using rubber composition
CN104048911A (en) * 2014-06-30 2014-09-17 哈尔滨工业大学 Method for analyzing aging degree of silicone rubber according to relative content of silicon hydroxyl
CN106566290A (en) * 2016-11-11 2017-04-19 青岛科技大学 White carbon black with dyeing groups on surface and preparation method of white carbon black
CN107478781A (en) * 2017-09-14 2017-12-15 中策橡胶集团有限公司 A kind of detection method of white carbon and silane coupler Silanization reaction degree
CN109709276A (en) * 2019-01-04 2019-05-03 中策橡胶集团有限公司 The detection method of white carbon black and silane coupling agent Silanization reaction degree in a kind of silica compound

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006337342A (en) * 2005-06-06 2006-12-14 Yokohama Rubber Co Ltd:The Method of measuring reaction amount of silica, and rubber composition with reaction amount defined using the method
CN101514263A (en) * 2009-04-01 2009-08-26 苏州大学 Modified white carbon black and preparation method thereof
CN102220036A (en) * 2011-06-02 2011-10-19 北京化工大学 Method for preparing white carbon black modified by silane coupling agent
WO2013118801A1 (en) * 2012-02-08 2013-08-15 住友ゴム工業株式会社 Method for quantifying strength of interface bonding between silica and modified polymer, rubber composition adjusted by said method, and pneumatic tire using same
JP2013231694A (en) * 2012-05-01 2013-11-14 Sumitomo Rubber Ind Ltd Method for obtaining reaction active group amount of silica, rubber composition whose reaction amount of silica is specified by using the same, and pneumatic tire using rubber composition
CN104048911A (en) * 2014-06-30 2014-09-17 哈尔滨工业大学 Method for analyzing aging degree of silicone rubber according to relative content of silicon hydroxyl
CN106566290A (en) * 2016-11-11 2017-04-19 青岛科技大学 White carbon black with dyeing groups on surface and preparation method of white carbon black
CN107478781A (en) * 2017-09-14 2017-12-15 中策橡胶集团有限公司 A kind of detection method of white carbon and silane coupler Silanization reaction degree
CN109709276A (en) * 2019-01-04 2019-05-03 中策橡胶集团有限公司 The detection method of white carbon black and silane coupling agent Silanization reaction degree in a kind of silica compound

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