CN111205415A - Method for dispersing white carbon black in nonpolar bottle brush rubber molecule, composition thereof and vulcanized rubber - Google Patents
Method for dispersing white carbon black in nonpolar bottle brush rubber molecule, composition thereof and vulcanized rubber Download PDFInfo
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Abstract
The invention relates to a method for dispersing white carbon black in nonpolar bottle brush rubber molecules, a composition thereof and vulcanized rubber, wherein the nonpolar bottle brush rubber molecules comprise β -myrcene structural units, styrene structural units and butadiene structural units, and the structure can be a linear/star block structure, wherein β -myrcene structural units are distributed in a block mode, and styrene/butadiene is randomly distributed.
Description
Technical Field
The invention relates to a method for preparing a high-dispersion white carbon black/rubber composite material, in particular to a method for selecting nonpolar bottle brush rubber molecule dispersion white carbon black, a composition thereof and vulcanized rubber
Background
The solution polymerized styrene-butadiene rubber occupies a very important position in synthetic rubber and is widely applied to various fields of medical treatment, national defense, traffic, aerospace and the like. Hydrated amorphous Silica (SiO)2·nH2O), commonly known as white carbon black, is an important reinforcing material for the preparation of "green tires", which provides the tires with excellent dynamic mechanical properties, in particular low rolling resistance, compared to carbon black reinforcing systems. However, since silanol is present in a large amount on the surface of silica, these inorganic particles have super-hydrophilicity and high polarity, are difficult to wet and disperse in an organic phase, and aggregates tend to aggregate, so that product performance is affected. For example, in vulcanization, the low degree of dispersion in the polymer due to aggregation of unmodified white carbon black lowers the vulcanization efficiency and the reinforcing property, thereby further affecting the wet skid resistance, rolling resistance, heat generation and other properties of the rubber. In order to improve filler dispersion, the rubber is generally modified by polar functionalization, or the white carbon black is modified with a silane coupling agent or the like.
It is noted that, although the in-chain or terminal functional modification of rubber and the modification of silica with silane coupling agent can improve the dispersibility of silica, for the former rubber functional modification, no matter the functional initiator such as lithium oxyalkylate [ US5621149], tri-n-butyltin lithium [ EP493839A1], 3- (t-butyldimethylsilyloxy) propyllithium [ US5376745] is used to directly initiate polymerization or the terminal functional polymer is obtained by end capping with t-butyldiphenylchlorosilane [ CN102190757A ], disilylamine derivative [ CN200880127028] electrophilic agent, or the terminal functional polymer is obtained by the Japanese friend chemical company [ US6818710] and Korean Korea tire company [ US6133388] as an example of the functionalization in-chain, we can find that the terminal functional modification inevitably introduces the functional initiator preparation, the polymer terminal capping, etc. outside the polymerization process, which complicates the process, and the number of functional groups which can be introduced by the terminal functional modification is limited, the efficiency is low; the polar monomers which can meet the requirement of anion living polymerization and are suitable for the in-chain functionalization modification method are very rare in types, can be obtained only through a complicated synthesis process, and in addition, the content of the introduced functional groups is not high.
The latter method for modifying silane coupling agent, for example, first obtaining a sol solution of the coupling agent by a sol-gel method, and then fully reacting the silica with the coupling agent [ CN102220036A ] by a kinetic means, or an umbrella-shaped siloxane coupling agent [ CN105273442A ] used by shenyang chemical research institute company, and the like, which are not only high in energy consumption and complex, but also may cause pre-crosslinking in the mixing process of active sulfur in the coupling agent, which brings problems to processing, and more importantly, in the reaction process of the silica with the silane coupling agent, volatile organic compounds such as methanol, ethanol and the like are emitted, which is very environmentally-friendly.
In view of the above, the invention provides a method for dispersing silicon dioxide by using styrene butadiene rubber containing a bottle brush block based on the physical adsorption and wetting performance of a bottle brush structure on the surface of silicon dioxide, and the method can obviously improve the dispersibility of filler particles such as white carbon black and the like in a rubber matrix, and further enables vulcanized rubber to have the characteristics of low rolling resistance, high tear strength, high tensile strength and the like.
Disclosure of Invention
The first purpose of the invention is to provide a technical method which can improve the aggregation of white carbon black particles in a polymer matrix, especially a rubber matrix, and realize the high dispersion of white carbon black in the rubber matrix, and compared with the existing white carbon black dispersion improving method, the method is simple, environment-friendly, efficient and convenient, on one hand, the invention does not need to introduce a polar functional group, so that additional process flows of initiator preparation, end capping, polar monomer synthesis and the like are not needed, and the problems of complex process, low efficiency and high cost of the existing functionalization technology are solved, on the other hand, a silane coupling agent is not needed, so that the problems of complex reaction, high energy consumption, emission of volatile organic compounds and the like when the coupling agent is used are solved, meanwhile, the introduced β -myrcene nonpolar bottle brush chain segment is a bio-based renewable monomer, the source is rich, the price is low, the problem that the nonpolar bottle copolymer prepared by adopting β -myrcene with 10 wt.% to 50 wt.% is increasingly cheap can relieve the problem of fossil resources depletion, and the living anion polymerization characteristic of β -myrcene can be well popularized in large-scale.
The second objective of the invention is to provide the composition and vulcanized rubber using the non-polar bottle brush rubber, and the bottle brush molecules have good infiltration and adhesion with fillers such as white carbon black particles due to the special structure of the bottle brush molecules, so that the dispersibility of the white carbon black in the rubber matrix is obviously improved, and the vulcanized rubber has the characteristics of low rolling resistance, high tear strength, tensile strength and the like.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a non-polar bottle brush rubber molecule containing β -myrcene comprises a β -myrcene structural unit, a styrene structural unit and a butadiene structural unit.
Wherein the β -myrcene structural unit is distributed in a block manner and accounts for 10-50 wt% of the non-polar bottle brush rubber.
Optionally, the β -myrcene structural units account for the non-polar bottle brush rubber at a lower limit independently selected from the group consisting of 10 wt.%, 12 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 40 wt.%, 46 wt.%.
Optionally, the β -myrcene structural units account for an upper limit of the mass percent of the non-polar bottle brush rubber independently selected from the group consisting of 15 wt.%, 18 wt.%, 24 wt.%, 28 wt.%, 34 wt.%, 42 wt.%, 50 wt.%.
Preferably, the β -myrcene structural units account for 10 wt.% to 35 wt.% of the non-polar bottle brush rubber.
Optionally, the styrene structural unit and the butadiene structural unit are randomly distributed to form a random chain segment, and the styrene structural unit accounts for 20 wt.% to 40 wt.% of the nonpolar bottle brush rubber.
Optionally, the lower limit of the mass percent of the styrene structural units to the non-polar bottle brush rubber is independently selected from 20 wt.%, 22 wt.%, 25 wt.%, 30 wt.%, 35 wt.%.
Optionally, the upper mass percent of the styrene building blocks in the non-polar bottle brush rubber is independently selected from 23 wt.%, 26 wt.%, 30 wt.%, 36 wt.%, 38 wt.%, 40 wt.%.
Preferably, the styrene building blocks constitute 20 wt.% to 30 wt.% of the non-polar bottle brush rubber.
Optionally, the butadiene structural units account for 30 wt.% to 70 wt.% of the non-polar bottle brush rubber.
Optionally, the lower limit of the mass percent of the butadiene structural units to the non-polar bottle brush rubber is independently selected from 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 65 wt.%.
Optionally, the upper mass percent of the butadiene structural units to the non-polar bottle brush rubber is independently selected from 30 wt.%, 45 wt.%, 55 wt.%, 60 wt.%, 62 wt.%, 68 wt.%, 70 wt.%.
Preferably, the butadiene structural units account for 45 wt.% to 60 wt.% of the non-polar bottle brush rubber.
Optionally, the number average molecular weight of the nonpolar bottle brush rubber is 14 to 30 ten thousand.
Optionally, the nonpolar bottle brush rubber has a molecular weight distribution of 1.01-1.23.
Preferably, the molecular weight distribution of the nonpolar bottle brush rubber is 1.10-1.20.
In the invention, the control of the content of each structural unit in the nonpolar bottle brush rubber is important, wherein the proper content of the poly β -myrcene structural unit can endow the polymer with side chain density, the high-density side chain can reduce chain entanglement, and the adsorption and infiltration effects on solid silicon dioxide particles are increased, so that the nonpolar bottle brush rubber can obviously improve the dispersibility of filler particles such as white carbon black and the like in a rubber matrix to realize the optimization of rubber performance.
A method for dispersing white carbon black in nonpolar bottle brush rubber molecules is characterized in that a double-roller open mill is adopted, half of white carbon black is added into rubber and mixed uniformly, and then a vulcanization activator and an accelerant are sequentially added and mixed uniformly; and finally, adding half of white carbon black, an anti-aging agent and sulfur, and fully mixing.
Optionally, the curing activators are zinc oxide and stearic acid.
Optionally, the accelerator is one of DPG, CBS, DM, D.
Optionally, the antioxidant is one of antioxidant RD and antioxidant 4020.
According to another object of the invention, the rubber composition comprises a polymer component and an auxiliary component, wherein the polymer component is any one of the non-polar bottle brush polymers containing β -myrcene.
Optionally, the mixing time is 15min to 30 min.
Optionally, the auxiliary component comprises 10-65 parts of white carbon black, 0.5-2 parts of a vulcanizing agent, 0.2-2 parts of a vulcanization activator, 0.8-1.6 parts of a vulcanization accelerator and 0.5-4 parts of an anti-aging agent based on 100 parts by weight of the polymer component.
According to still another object of the present invention, there is provided a vulcanized rubber obtained by kneading and vulcanizing the above rubber composition. Based on the easy diffusion and adsorption effects of the nonpolar long-chain bottle brush on the surface of the white carbon black filler, the dispersibility of the white carbon black can be obviously improved, so that the prepared vulcanized rubber has the characteristics of low rolling resistance, high tearing strength, high tensile strength on the premise of not sacrificing the elongation at break and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method for dispersing white carbon black by utilizing nonpolar bottle brush rubber molecules is convenient, simple in process, high in efficiency, good in industrial adaptability, environment-friendly, free of volatile organic matters, capable of realizing accurate and controllable copolymer molecular weight, molecular weight distribution, copolymerization composition and microstructure, good in industrial adaptability to the conventional anion polymerization device and suitable for large-scale industrial popularization.
(2) The β -myrcene-containing nonpolar bottle brush rubber molecule provided by the invention has high-density branched chains, the chain entanglement density is reduced, and the adsorption and infiltration effects on solid silicon dioxide particles are added, so that the dispersibility of filler particles such as white carbon black in a rubber matrix can be obviously improved.
(3) The β -myrcene-containing nonpolar bottle brush rubber provided by the invention contains a bio-based renewable monomer, the monomer is rich in source and low in price, the content of the monomer accounts for 10-50 wt% of the bottle brush rubber, and the problem of increasingly exhausted fossil resources can be relieved.
(4) The nonpolar bottle brush rubber composition and vulcanized rubber provided by the invention overcome the defect of poor dispersion of white carbon black particles in the existing solution polymerized styrene-butadiene rubber, have good dispersion of fillers in a polymer matrix, have the characteristics of low rolling resistance, high tearing strength, high tensile strength on the premise of not sacrificing elongation at break and the like, and can be used for novel green energy-saving tread rubber.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows a non-limiting example of an embodiment of the present inventionRPA analysis curve of polar bottle brush polymer; wherein: a. b, c, D, e, f, g represent D1 in comparative example 1#Sample, example 1#、2#、3#、4#、5#、6#RPA analysis curve of the samples.
FIG. 2 is an SEM photograph of a non-polar bottle brush polymer in accordance with an embodiment of the present invention; wherein: a. b, c, d, e represent DS1 in comparative example 1#Sample, S1 in example 1#、S2#、S4#、S6#SEM photograph of the sample.
FIG. 3 is a TEM photograph of a non-polar bottle brush polymer in an embodiment of the present invention; wherein: a. b, c, d, e represent DS1 in comparative example 1#Sample, S1 in example 1#、S2#、S4#、S6#TEM photograph of the sample.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1 method for dispersing white carbon black in nonpolar bottle brush rubber molecule
#White carbon black dispersed after physical blending of 1 β -myrcene and butadiene styrene rubber
Adjusting the roll spacing of a double-roll open mill to 0.5mm, then adding 25g of homopolymerized β -myrcene raw rubber and 75g of random copolymerization styrene-butadiene rubber (the mass ratio of butadiene to styrene is 7: 3) into the roll spacing together for 10 times, then widening the roll spacing (1mm) for mixing, firstly adding 25g of white carbon black for mixing uniformly, sequentially adding 1.0g of stearic acid and 2.5g of zinc oxide, then adding 25g of white carbon black, 1.5g of accelerator DPG, 1.4g of accelerator CBS, 2.0g of antioxidant 4020 and 1.4g of sulfur, mixing for about 15 minutes, repeatedly performing triangular packaging for 5 times, and finally discharging sheets to realize uniform distribution of white carbon blackPowder, the rubber composition obtained is noted as 1#And (6) taking a sample.
#2 β -myrcene-styrene-butadiene ternary random copolymer rubber dispersed white carbon black
100g of β -myrcene-styrene-butadiene ternary random copolymer raw rubber (the mass ratio of butadiene to styrene to myrcene is 52: 23: 25) is thinly passed through a double-roll mill for 10 times with a small roll gap (0.5mm), then the roll gap (1mm) is widened for mixing, 25g of white carbon black is firstly added for mixing uniformly, 1.0g of stearic acid and 2.5g of zinc oxide are sequentially added, then 25g of white carbon black, 1.5g of accelerator DPG, 1.4g of accelerator CBS, 2.0g of anti-aging agent 4020 and 1.4g of sulfur are added for mixing fully for about 15 minutes, triangular wrapping is carried out for 5 times, and finally, the uniform dispersion of the white carbon black can be realized by sheet discharging, the prepared rubber composition is marked as 2#And (6) taking a sample.
#3 β -myrcene-b- (styrene-co-butadiene) block copolymer rubber dispersed white carbon black
100g of β -myrcene-b- (styrene-co-butadiene) block copolymerization raw rubber (the mass ratio of butadiene to styrene to myrcene is 57: 27: 16) is thinly passed through a double-roll open mill for 10 times with a small roll gap (0.5mm), then the roll gap (1mm) is widened for mixing, 25g of white carbon black is firstly added for mixing uniformly, 1.0g of stearic acid and 2.5g of zinc oxide are sequentially added, then 25g of white carbon black, 1.5g of accelerator DPG, 1.4g of accelerator CBS, 2.0g of anti-aging agent 4020 and 1.4g of sulfur are added, after about 15 minutes of full mixing, triangular packaging is carried out for 5 times, and finally, the uniform dispersion of the white carbon black can be realized, the prepared rubber composition is 3#And (6) taking a sample.
#4 β -myrcene-b- (styrene-co-butadiene) block copolymer rubber dispersed white carbon black
100g of β -myrcene-b- (styrene-co-butadiene) block copolymerization raw rubber (the mass ratio of butadiene to styrene to myrcene is 51: 24: 25) is thinly passed through a double-roll mill for 10 times with a small roll gap (0.5mm), then the roll gap (1mm) is widened and mixed, 25g of white carbon black is added and mixed uniformly, 1.0g of stearic acid and 2.5g of zinc oxide are sequentially added, 25g of white carbon black, 1.5g of accelerator DPG, 1.4g of accelerator CBS and 2.0g of antioxidant 402 are added0g and 1.4g of sulfur, fully mixing for about 15 minutes, then packaging by a triangular bag for 5 times, finally discharging the sheet, thus realizing the uniform dispersion of the white carbon black, and marking the prepared rubber composition as 4#And (6) taking a sample.
#5 β -myrcene-b- (styrene-co-butadiene) block copolymer rubber dispersed white carbon black
100g of β -myrcene-b- (styrene-co-butadiene) block copolymerization raw rubber (the mass ratio of butadiene to styrene to myrcene is 46: 20: 34) is thinly passed through a double-roll open mill for 10 times with a small roll gap (0.5mm), then the roll gap (1mm) is widened for mixing, 25g of white carbon black is firstly added for mixing uniformly, 1.0g of stearic acid and 2.5g of zinc oxide are sequentially added, then 25g of white carbon black, 1.5g of accelerator DPG, 1.4g of accelerator CBS, 2.0g of anti-aging agent 4020 and 1.4g of sulfur are added, after about 15 minutes of full mixing, triangular packaging is carried out for 5 times, and finally, the uniform dispersion of the white carbon black can be realized, the prepared rubber composition is marked as 5#And (6) taking a sample.
#6 star poly β -myrcene-b- (styrene-co-butadiene) copolymer rubber dispersed white carbon black
100g of star poly β -myrcene-b- (styrene-co-butadiene) copolymer rubber raw rubber (the mass ratio of butadiene to styrene to myrcene is 56: 27: 16) is thinly passed through a double-roll open mill for 10 times with a small roll gap (0.5mm), then the roll gap (1mm) is widened for mixing, 25g of white carbon black is firstly added for mixing uniformly, 1.0g of stearic acid and 2.5g of zinc oxide are sequentially added, then 25g of white carbon black, 1.5g of accelerant DPG, 1.4g of accelerant CBS, 2.0g of anti-aging agent 4020 and 1.4g of sulfur are added, after fully mixing for about 15 minutes, triangular wrapping is repeatedly carried out for 5 times, and finally, the uniform dispersion of the white carbon black can be realized, the prepared rubber composition is recorded as 6#And (6) taking a sample.
#7 β -myrcene-styrene-butadiene ternary random copolymer rubber dispersed white carbon black
100g of β -myrcene-styrene-butadiene ternary random copolymerization raw rubber (the mass ratio of butadiene to styrene to myrcene is 52: 23: 25) is thinly passed through a double-roll mill for 8 times with a small roll spacing (0.5mm), then the roll spacing (1mm) is widened for mixing, 15g of white carbon black is added for mixing uniformly, and then the white carbon black is added in sequenceAdding 0.8g of stearic acid and 2.3g of zinc oxide, then adding 15g of white carbon black, 1.5g of accelerator DPG, 1.4g of accelerator CBS, 2.0g of anti-aging agent 4020 and 1.2g of sulfur, fully mixing for about 15 minutes, repeatedly making triangular bags for 5 times, and finally discharging to realize uniform dispersion of white carbon black, wherein the prepared rubber composition is marked as 7#And (6) taking a sample.
#8 β -myrcene-styrene-butadiene ternary random copolymer rubber dispersed white carbon black
100g of β -myrcene-styrene-butadiene ternary random copolymer raw rubber (the mass ratio of butadiene to styrene to myrcene is 52: 23: 25) is thinly passed through a double-roll mill for 8 times with a small roll gap (0.5mm), then the roll gap (1mm) is widened for mixing, firstly 8g of white carbon black is added for mixing uniformly, 0.8g of stearic acid and 2.0g of zinc oxide are sequentially added, then 8g of white carbon black, 1.4g of accelerator DPG, 1.2g of accelerator CBS, 1.8g of anti-aging agent 4020 and 1.2g of sulfur are added, after fully mixing for about 15 minutes, triangular wrapping is carried out for 4 times, and finally, the uniform dispersion of the white carbon black can be realized by sheet discharging, the prepared rubber composition is marked as 8#And (6) taking a sample.
#9 β -myrcene-b- (styrene-co-butadiene) block copolymer rubber dispersed white carbon black
100g of β -myrcene-b- (styrene-co-butadiene) block copolymerization raw rubber (the mass ratio of butadiene to styrene to myrcene is 51: 24: 25) is thinly passed through a double-roll open mill for 10 times with a small roll gap (0.5mm), then the roll gap (1mm) is widened for mixing, 10g of white carbon black is added for mixing uniformly, 1.0g of stearic acid and 2.5g of zinc oxide are sequentially added, then 10g of white carbon black, 1.5g of accelerator DPG, 1.4g of accelerator CBS, 2.0g of anti-aging agent 4020 and 1.4g of sulfur are added, after about 20 minutes of full mixing, triangular packaging is carried out for 5 times, and finally, the uniform dispersion of the white carbon black can be realized, the prepared rubber composition is 9#And (6) taking a sample.
#10 β -myrcene-b- (styrene-co-butadiene) block copolymer rubber dispersed white carbon black
100g of β -myrcene-b- (styrene-co-butadiene) block copolymer raw gum (mass ratio of butadiene to styrene to myrcene 51: 24: 25) was opened in two rollsPassing the mixture on a mill at a small roll spacing (0.5mm) for 10 times, then widening the roll spacing (1mm) for mixing, firstly adding 5g of white carbon black for mixing uniformly, sequentially adding 1.0g of stearic acid and 2.5g of zinc oxide, then adding 5g of white carbon black, 1.5g of accelerator DPG, 1.4g of accelerator CBS, 2.0g of anti-aging agent 4020 and 1.4g of sulfur, fully mixing for about 25 minutes, then making a triangular bag for 5 times, and finally discharging the sheet to realize uniform dispersion of the white carbon black, wherein the prepared rubber composition is marked as 10#And (6) taking a sample.
#11 star poly β -myrcene-b- (styrene-co-butadiene) copolymer rubber dispersed white carbon black
100g of star poly β -myrcene-b- (styrene-co-butadiene) copolymer rubber raw rubber (the mass ratio of butadiene to styrene to myrcene is 51: 24: 25) is thinly passed through a double-roll open mill for 10 times with a small roll gap (0.5mm), then the roll gap (1mm) is widened for mixing, 20g of white carbon black is firstly added for mixing uniformly, 1.0g of stearic acid and 2.5g of zinc oxide are sequentially added, then 20g of white carbon black, 1.5g of accelerant DPG, 1.4g of accelerant CBS, 2.0g of anti-aging agent 4020 and 1.4g of sulfur are added, after fully mixing for about 15 minutes, triangular wrapping is repeatedly carried out for 5 times, and finally, the uniform dispersion of the white carbon black can be realized, the prepared rubber composition is marked as 11#And (6) taking a sample.
#12 star poly β -myrcene-b- (styrene-co-butadiene) copolymer rubber dispersed white carbon black
100g of star poly β -myrcene-b- (styrene-co-butadiene) copolymer rubber raw rubber (the mass ratio of butadiene to styrene to myrcene is 51: 24: 25) is thinly passed through a double-roll open mill for 10 times with a small roll gap (0.5mm), then the roll gap (1mm) is widened for mixing, 10g of white carbon black is firstly added for mixing uniformly, 1.0g of stearic acid and 2.5g of zinc oxide are sequentially added, then 10g of white carbon black, 1.5g of accelerant DPG, 1.4g of accelerant CBS, 2.0g of anti-aging agent 4020 and 1.4g of sulfur are added, after fully mixing for about 15 minutes, triangular wrapping is repeatedly carried out for 5 times, and finally, the uniform dispersion of the white carbon black can be realized, and the prepared rubber composition is marked as 12#And (6) taking a sample.
#13 star poly β -myrcene-b- (styrene-co-butadiene) copolymer rubber dispersed white carbon black
100g of star poly β -myrcene-b- (styrene-co-butadiene) copolymer rubber raw rubber (the mass ratio of butadiene to styrene to myrcene is 51: 24: 25) is thinly passed through a double-roll open mill for 10 times with a small roll gap (0.5mm), then the roll gap (1mm) is widened for mixing, 5g of white carbon black is firstly added for mixing uniformly, 1.0g of stearic acid and 2.5g of zinc oxide are sequentially added, then 5g of white carbon black, 1.5g of accelerant DPG, 1.2g of accelerant CBS, 2.0g of anti-aging agent 4020 and 1.4g of sulfur are added, after fully mixing for about 15 minutes, triangular wrapping is repeatedly carried out for 4 times, and finally sheet discharging is carried out, so that the uniform dispersion of the white carbon black can be realized, and the prepared rubber composition is 13#And (6) taking a sample.
Comparative example 1 dispersed white carbon of styrene-butadiene binary random copolymer rubber
100g of styrene-butadiene raw rubber (the mass ratio of butadiene to styrene is 70: 30) is thinly passed through a double-roll open mill for 10 times with a small roll gap (0.5mm), then the roll gap (1mm) is widened for mixing, 50g of white carbon black is firstly added for mixing uniformly, 1.0g of stearic acid and 2.5g of zinc oxide are sequentially added, 50g of white carbon black, 1.5g of accelerator DPG, 1.4g of accelerator CBS, 2.0g of antioxidant 4020 and 1.4g of sulfur are then added for mixing fully for about 15 minutes, triangular wrapping is repeatedly carried out for 5 times, and finally, the sheet is discharged, so that the prepared rubber composition is marked as D1#And (6) taking a sample.
Example 2 preparation of rubber composition and vulcanized rubber thereof
With 1#、2#、3#、4#、5#、6#、D1#The samples were typical and vulcanized as follows:
mixing the obtained 1#、2#、3#、4#、5#、6#、D1#After the sample wafer is placed for 24 hours, respectively weighing 7g of sample, placing the sample wafer into a vulcanizer to measure a vulcanization curve, and determining the vulcanization time t90(ii) a Vulcanizing on a flat vulcanizing machine according to the vulcanizing time to obtain vulcanized rubber sample sheets with the thickness of 2mm, which are respectively recorded as S1#、S2#、S3#、S4#、S5#、S6#、DS1#And (6) taking a sample.
Experimental example 1 measurement of degree of dispersion of white carbon black in nonpolar bottle brush rubber molecule
As D1 in comparative example 1#、1#～6#The nonpolar bottle brush copolymer sample is typical and the white carbon black dispersion degree test is performed.
Rubber processing analysis test
The rubber mixtures were strain-scanned using model number RPA2000 from Alpha, from which the dispersion of the filler in the rubber network could be analyzed. The tests of the mixes were carried out at 60 ℃ with a frequency of 1Hz and a strain amplitude in the range 0.28% to 400%. The experimental temperature of the vulcanized rubber is 150 ℃, the frequency is 10Hz, and the strain range is 0.28-41.99%.
D1#、1#～6#The results of characterization of the non-polar bottle brush copolymer sample are shown in figure 1.
As can be seen from the results in FIG. 1, comparative example D1 is shown at a small strain#The highest storage modulus, with the introduction of myrcene, 1#～6#Corresponding physical mechanical blending samples (1)#) Random copolymer sample (2)#) Block copolymer sample (3)#、4#、5#) And Star copolymer sample (6)#) The storage modulus begins to be greatly reduced, the payne effect is reduced, the dispersibility of the white carbon black in the rubber matrix becomes good, and the bottle brush structure obtained by introducing myrcene has good infiltration and adsorption effects on fillers such as white carbon black particles and the like, so that the dispersibility of the white carbon black in the polymer can be obviously improved.
Characterization of the microscopic morphology of vulcanized rubber
The dispersion morphology of the white carbon black in the rubber is observed by adopting a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), and the particle size of the white carbon black dispersed in the rubber is characterized by using small-angle X-ray diffraction (SAXS).
And (4) SEM characterization: the cured samples were scanned using a JEOL JSM5310 electron microscope and freeze-fractured in liquid nitrogen and gold-sprayed for 1.5 minutes under nitrogen protection prior to testing. DS1#，S1#，S2#，S4#，S6#SEM characterization of the non-polar bottle brush rubber samples is shown in figure 2. Wherein a, b, c, d and e respectively represent DS1#，S1#，S2#，S4#，S6#。
TEM representation: the frozen sectioned samples were scanned using a Tecnai G220S-Twin Transmission Electron microscope (FEICcompany, USA) operated at an accelerating voltage of 100 kV. DS1#，S1#，S2#，S4#，S6#The TEM characterization of the non-polar bottle brush rubber sample is shown in fig. 3. Wherein a, b, c, d and e respectively represent DS1#，S1#，S2#，S4#，S6#。
SAXS characterisation DS1 was irradiated with Xeuss 2.0 and Cu-K α radiation at different distances using a PW 1830 x-ray generator (Philips, USA)#，S1#，S2#，S4#，S6#Particle size (Rg) of the non-polar bottle brush rubber samples was characterized as shown in table 1.
As can be seen from FIGS. 2 and 3, DS1#Significant agglomeration of the silica particles was observed in the samples due to the strong filler-filler interaction and the weak interfacial interaction between the filler and the rubber matrix caused by the large amount of silanols on the silica surface. When myrcene is introduced to obtain the bottle brush structure rubber, the white carbon black is observed in S6 of star copolymerization#The sample had the best dispersibility, followed by block copolymerization S4#Sample and random copolymerization S2#Sample, S1#Sample comparison to DS1#There is an improvement, but a small amount of aggregation can be observed because there is a strong phase separation between the blended phases due to the apparent difference in chain structure resulting from the physical-mechanical blending. Also as can be seen from the particle size values of the individual samples in Table 1, DS1#The particle size of the white carbon black in the sample is the largest, and the particle size of the bottle brush structure rubber with myrcene is reduced to a certain extent, which is consistent with the microstructure result observed in the front.
TABLE 1 DS1#，S1#，S2#，S4#，S6#Of samplesParticle size number
| Item | DS1# | S1# | S2# | S4# | S6# |
| Particle size (nm) | 22.23 | 21.67 | 20.98 | 20.22 | 17.76 |
Experimental example 2 Properties of vulcanized rubber
Mooney viscosity
The Mooney viscosity of the rubber compound was measured at 100 ℃ using a model GT-7082S2 Mooney viscometer, and this result is one of the important indicators of quality control of synthetic rubber products and is also a comprehensive technical indicator of processability of rubber products.
D1#、1#～6#Characterization results for the non-polar bottle brush copolymer samples are shown in table 2.
As can be seen from the results in Table 2, the introduction of such long-chain nonpolar myrcene segments, whether physically blended, randomly copolymerized, or block copolymerized, lowers the Mooney viscosity, most notablyAfter 6#Has a Mooney viscosity of more than D1#This may be due to its higher molecular weight (85000).
Physical and mechanical properties
The tensile strength, the elongation at break and the like of dumbbell type and right-angle pant type samples are tested by adopting a CMT4104 type micro-control electronic universal tensile testing machine, wherein the tensile strength is tested according to the national standard GB/T528-2009, the tear strength is tested according to GB/T528-2008, and the tensile speed is 550 mm/min.
Dynamic mechanical Properties (DMTA)
A rectangular sample (50 mm. times.6 mm. times.2 mm) was subjected to dynamic mechanical thermal analysis in a tensile mode using a VA 3000 dynamic mechanical thermal analyzer (01dB-Metravib Co, France). The test was carried out at a frequency of 1Hz and a dynamic strain of 0.1% in a temperature sweep range of-80 to 80 ℃.
The mechanical and dynamic mechanical property test results are shown in table 2. As can be seen from the results in Table 2, comparative example DS1#Tan delta value of 0.38 at 0 ℃ and 0.10 at 60 ℃, with the introduction of myrcene, S1#～S6#Tan delta values at 60 ℃ are all lower than DS1#Further proves that the myrcene-introduced bottle brush structure rubber has good infiltration and adhesion effects on fillers such as white carbon black particles and the like, and can obviously improve the dispersibility of white carbon black in a polymer, so that the obtained vulcanized rubber has low rolling resistance and higher tear strength and tensile strength.
TABLE 2 DS1#、S1#～S6#Mooney viscosity, physico-mechanical properties, dynamic mechanical properties data of Block copolymer samples
| Item | DS1# | S1# | S2# | S3# | S4# | S5# | S6# |
| Mooney viscosity [ ML ]1+4100] | 111.52 | 86.62 | 98.69 | 109.46 | 101.03 | 94.62 | 117.42 |
| Tensile strength/MPa | 9.71 | 9.15 | 11.92 | 16.05 | 16.99 | 17.26 | 13.36 |
| 300% stress at definite elongation/MPa | 3.47 | 4.13 | 4.03 | 6.14 | 5.22 | 6.45 | 5.47 |
| Elongation at break/%) | 651.43 | 594.39 | 635.29 | 600.57 | 636.47 | 648.68 | 572.09 |
| Permanent deformation/%) | 16.00 | 14.00 | 20.00 | 120.00 | 20.00 | 16.00 | 10.00 |
| Tear Strength/kN/m | 32.57 | 36.90 | 33.37 | 36.62 | 33.58 | 39.34 | 38.11 |
| Shore A hardness | 70.3 | 73.9 | 72.3 | 73.8 | 75.3 | 73.6 | 74.2 |
| Crosslink Density/10-4mol/cm3 | 3.14 | 3.42 | 3.21 | 3.57 | 5.16 | 6.23 | 3.73 |
| Tanδ/0℃ | 0.38 | 0.31 | 0.28 | 0.22 | 0.31 | 0.26 | 0.31 |
| Tanδ/60℃ | 0.10 | 0.09 | 0.07 | 0.07 | 0.07 | 0.06 | 0.05 |
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. A nonpolar bottle brush rubber molecule is characterized by consisting of β -myrcene structural units, styrene structural units and butadiene structural units, and the structure of the nonpolar bottle brush rubber molecule is a linear/star block structure;
the β -myrcene structural unit is distributed in a block manner;
the β -myrcene structural units account for 10-50 wt.% of the bottle brush polymer;
the styrene structural unit and the butadiene structural unit are randomly distributed to form a random chain segment;
the styrene building blocks comprise 20 wt.% to 40 wt.% of the bottle brush polymer;
the butadiene structural units account for 30 wt.% to 70 wt.% of the bottle brush polymer.
2. The non-polar bottle brush rubber molecule according to claim 1, wherein the number average molecular weight of the non-polar bottle brush rubber molecule is 14 to 30 ten thousand, and the molecular weight distribution is 1.10 to 1.20.
3. A method for dispersing white carbon black in nonpolar bottle brush rubber molecules is characterized in that a rubber composition is mixed and dispersed in a two-roll open mill, and comprises the following steps:
firstly, adding half of white carbon black into rubber, uniformly mixing, and then sequentially adding a vulcanization activator and a vulcanization accelerator, and uniformly mixing; and finally, adding half of white carbon black, an anti-aging agent and sulfur, and fully mixing.
4. A rubber composition characterized by comprising a polymer component and an auxiliary component; the polymer component is selected from the bottle brush rubber molecule of any of claims 1 to 2; the auxiliary agent component comprises white carbon black, a vulcanization activator, a vulcanization accelerator, an anti-aging agent and sulfur;
the mixing time is 15 min-30 min;
the auxiliary agent component comprises, by 100 parts by weight of the polymer component, 10-65 parts of white carbon black, 0.5-2 parts of a vulcanizing agent, 0.2-2 parts of a vulcanizing activator, 0.8-1.6 parts of a vulcanization accelerator and 0.5-4 parts of an anti-aging agent.
5. A vulcanized rubber, which is produced by kneading the rubber composition according to claim 4 in a twin roll mill and vulcanizing the kneaded rubber composition on a vulcanizing press.
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| TW201942169A (en) * | 2018-03-29 | 2019-11-01 | 日商可樂麗股份有限公司 | Block copolymer, method for producing same, rubber composition using said block copolymer, and tire |
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