CN1317506A - Conjugated biolofin and monovinylarene dual-block rubber with high wet skid resistance and low rolling resistance - Google Patents
Conjugated biolofin and monovinylarene dual-block rubber with high wet skid resistance and low rolling resistance Download PDFInfo
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Abstract
A conjugated biolefin and monovinyl arene dual-block rubber is prepared under the existance of organolithium trigger. It features that the content of vinyl in different block nonovinyl arene and conjugated biolefin chain section is different, the binary distribution index of synthesized polymer is 5-80, and the polymer has excellent physical and mechanical performance, low rolling resistance and high wet skid resistance.
Description
The present invention relates to a kind of conjugated diene and monovinylarene diblock solution polymerized rubber and preparation method thereof, more particularly, relate to a kind of high wet-sliding resistant and the improved rubber of low-rolling-resistance equalization performance and preparation method thereof.
The rubber that was applicable to tread rubber of automobile tires in the past not only will have good tensile strength and wear resisting property, also requires to have high wet-sliding resistant and low-rolling-resistance, could satisfy needs energy-conservation and that travel fully like this.And these two performance demands of low-rolling-resistance and high wet-sliding resistant are conflicting, and the rubber of single variety is difficult to satisfy simultaneously this two kinds of requirements.Method with blend just makes two kinds of performances improve to some extent two kinds of blend rubbers that have low-rolling-resistance and high wet-sliding resistant respectively, is difficult to obtain the ideal product.Current method with anionoid polymerization can synthesize a kind of AB diblock copolymer rubber with different vinylbenzene and contents of ethylene, by adjust A, B two blocks in the copolymer rubber in whole copolymer rubber ratio and two sections in vinylbenzene, contents of ethylene can make the copolymer rubber of gained have low-rolling-resistance and high wet-sliding resistant simultaneously.The anti-slippery of rubber item and rolling resistance can be characterized by 0 ℃ and 50 ℃ of tan δ values in its viscoelastic spectra usually, and the anti-slippery of 0 ℃ of high more rubber of tan δ value is good more, and 50 ℃ of tan δ values are low more, and the rolling resistance of rubber is low more.
EP 0,054,440 disclose a kind of diblock styrene-butadiene rubber(SBR), it has low-rolling-resistance and high wet-sliding resistant, have good wear-resisting, processing and anti-cold flow properties simultaneously, its preparation method is to be that initiator carries out A section or the polymerization of B section with the organic single-lithium in the presence of polar compound, and it is synthetic to carry out next section then, carry out linked reaction with coupling agent again, use the terminator termination reaction then; EP 0,270, and 927 disclose the diblock butylbenzene copolymer of a kind of high wet-sliding resistant and low-rolling-resistance; US 4,433, and 109 disclose a kind of high wet-sliding resistant of tire tread and diblock rubber components of low-rolling-resistance of being used for, and are initiator with the organic single-lithium in its preparation, its structural requirement vinyl Tile Width at least 20%; US 4,463, and 133 to disclose a kind of be the method that initiator prepares Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock with the organic single-lithium, and require to contain in the polymer molecular chain carbon-to-metal bond of at least 20% (in polymer weight).
The purpose of this invention is to provide a kind of conjugated diene and monovinylarene diblock solution polymerized rubber and preparation method thereof, obtain the obvious improved multipolymer of high wet-sliding resistant and low-rolling-resistance equalization performance.
Conjugated diene of the present invention and monovinylarene diblock solution polymerized rubber contain two blocks, a block helps reducing rolling resistance, another block helps improving wet-sliding resistant performance, and this just needs the distribution of diblock microtexture to have certain ununiformity.Simultaneously in the diblock solution polymerized rubber in the monovinylarene content of different blocks and the conjugated diene chain link contents of ethylene also different to the polymkeric substance rolling resistance with the anti-slippery influence degree, the present invention requires A in the synthetic diblock solution polymerized rubber, B block microtexture difference.The present invention is with A, the difference of B block microtexture associates with overall microtexture, the inventor is through discovering in a large number, when the bivariate distribution index (σ) of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of the present invention 0～90 the time, can obtain the obvious improved rubbery copolymer of high wet-sliding resistant and low-rolling-resistance equalization performance, the structure regulator that wherein concrete σ value scope adopts during with the B section according to polymerization A section different and different.The ununiformity that promptly requires different block microtextures to distribute meets bivariate distribution index (σ) scope that the present invention proposes.
The present invention proposes to characterize the ununiformity that the diblock microtexture distributes with the method for monovinylarene, vinyl composition distribution variance and the two combination distribution variance, and has proposed the notion of bivariate distribution index (σ), is defined as follows:
In the formula: Δ St-A, B two block monovinylarenes are formed distribution variance: St
1-A section monovinylarene content; St
2-B section monovinylarene content; The overall monovinylarene content of St=; W
1-A section accounts for the weight fraction of gross weight; W
2-B section accounts for the weight fraction of gross weight.
Δ Cv-A, B two block vinyl are formed distribution variance; Cv
1Contents of ethylene in the-A section conjugated diene; Cv
2Contents of ethylene in the-B section conjugated diene; Contents of ethylene in the overall conjugated diene of Cv-; W
1'-A section conjugated diene accounts for the weight fraction of overall conjugated diene; W
2'-B section conjugated diene accounts for the weight fraction of overall conjugated diene.
Δ (St+Cv)-A, B two block monovinylarenes and vinyl combination distribution variance.
Since in the diblock solution polymerized rubber in monovinylarene content and the conjugated diene chain link contents of ethylene that polymkeric substance rolling resistance and anti-slippery are influenced program is different, therefore introduced parameter alpha, 1≤α≤2, promptly monovinylarene content is big than conjugated diene to Effect on Performance.And the inventor finds that the related law between bivariate distribution index and rolling resistance and the anti-slippery is best when α=1.75.The present invention adopts the notion of the bivariate distribution index (σ) of combination distribution variance, is defined as follows:
According to different structure conditioning agent system, the bivariate distribution index can change between 0～90, changes between being preferably in 5～80.Different structure conditioning agent system, the bivariate distribution index range can be different.
The concrete feature of conjugated diene of the present invention and monovinylarene diblock rubber is as follows:
(a) the A section is the random copolymerization section of conjugated diolefin homopolymerization section or conjugated diene and monovinylarene, and wherein monovinylarene content is 0-30% weight, and contents of ethylene is a 10-70% weight in the conjugated diene chain link.
(b) the B section is the random copolymerization section of conjugated diene and monovinylarene, and wherein monovinylarene content is 5-60% weight, and contents of ethylene is a 10-80% weight in the conjugated diene chain link;
(c) the A section accounts for the 10-90% of multipolymer weight;
(d) monovinylarene content is 5-40% weight in the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, and contents of ethylene is a 15-80% weight in the conjugated diene chain link;
(e) according to the difference of the structure regulator that adds in the polymerization, the bivariate distribution index of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock can change between 0～90.
Contents of ethylene can be by the weight ratio of two sections of contents of ethylene and A, B in contents of ethylene in monovinylarene content, the conjugated diene chain link in the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and A section monovinylarene content, the A section conjugated diene chain link in B section monovinylarene content and the conjugated diene chain link among the present invention, calculates by the bivariate distribution index value of the present invention's regulation to get.
Monovinylarene content can not be too high in the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, otherwise influence elasticity, the hardness of rubber, and the rubber rolling resistance obviously increases simultaneously.
The structure regulator system difference that Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of the present invention adopts during according to polymerization and bivariate distribution index (σ) is different, preferably changes between 3～20 between 1～30 as tetrahydrofuran (THF) (THF) system bivariate distribution index (σ); Diethylene Glycol dimethanol (2G) system σ changes between 10～40 between 5～45; N, N, N, ' N '-Tetramethyl Ethylene Diamine (TMEDA) system σ preferably change between 10～30 between 5～35; Composite structure conditioning agent system such as THF/2G or THF/TMEDA system σ are between 30～80; THF/KTB/2G (KTB is a tert.-butoxy potassium) system σ is between 10～40.Different structure conditioning agent and composite structure conditioning agent system σ variation range are different, if diblock polymer bivariate distribution index (σ) departs from above-mentioned scope, it is balanced that polymkeric substance rolling resistance and anti-slippery are difficult to reach.Though listed the σ value scope of common several structure regulator correspondences among the present invention, but under spirit of the present invention and guiding theory, those skilled in the art can draw the σ value scope that other structure regulator system that is suitable for is suitable for by conventional polymerization and analysis means and data computation.Therefore the present invention is not limited only to this.The inventive method is significant to the contribution in the synthetic field of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, the invention provides the novel method of such polymer molecule design, has obtained the polymeric articles of excellent combination property by the microtexture of control copolymer molecule.
In order to obtain Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of the present invention, the step that the technical solution used in the present invention comprises successively is as follows:
(1) inert solvent, conjugated diene, the monovinylarene that will react required adds in the reactor, the organic lithium initiator that adds significant quantity then, in the presence of initiator, carry out the polymerization of A section, make A section polymerisation conversion reach 97-100%, wherein the adding weight ratio of conjugated diene and mono vinyl arenes monomer is 100: 0-70: 30;
(2) add conjugated diene, monovinylarene and nonessential structure regulator and carry out the polymerization of B section, wherein the concrete amount that adds of conjugated diene and mono vinyl arenes monomer is calculated by the σ value of weight the present invention when regulation of two sections of the added two kinds of amount of monomer of A section and A of the present invention, B according to the present invention and is definite and control;
(3) not necessarily, treat that B section transformation efficiency reaches 100% back adding coupling agent and carries out linked reaction, after linked reaction finishes;
(4) termination reaction.
The used organic lithium initiator of the present invention can be organic single-lithium, organic pair of lithium and organic many lithiums.Organic single-lithium represents that with RLi wherein R is the C1-C20 alkyl of straight or branched; The C3-C20 cycloalkyl; The aryl of C6-C20.As lithium methide, lithium ethide, propyl lithium, sec.-propyl lithium, tert-butyl lithium, allyl group lithium, n-Butyl Lithium, s-butyl lithium, isobutyl-lithium, n-pentyl lithium, cyclohexyl lithium, 4-heptyl cyclohexyl lithium, 4-cyclohexyl butyllithium, 4-butyl cyclohexyl lithium, phenyl lithium, 4-aminomethyl phenyl lithium, trityl group lithium, 2-naphthyl lithium.Organic multi-lithium initiator (this paper represents with symbol PLi) is to be reacted in varsol by many vinyl-arenes and organic single-lithium to make, the organic pair of lithium and the organic many lithiums that wherein exist the reaction of organic single-lithium and many vinyl-arenes (hereinafter to be referred as MVA) to generate.In reaction process, can add conjugated diene or mono vinyl arenes monomer as additive,, improve initiator solubility property in varsol, obtain homogeneous phase initiator solvent so that on organic single-lithium, two lithium and multi-lithium initiator, form the polymkeric substance galianconism.The used MVA of the present invention preferably 1,3-Vinylstyrene, 1, and the 4-Vinylstyrene also can be its mixture.The consumption of MVA is that every mole of organic single-lithium need add 0.05～1.00mol, preferably adds 0.1～0.8mol.The used organic single-lithium of this organic many lithiums can be in the organic single-lithium in the organic lithium initiator that the present invention carried of above definition any one.Additive in organic multi-lithium initiator preparation process can be with the conjugated diolefine in the undefined synthetic solution polymerized rubber of the present invention in the light or mono vinyl arenes monomer any one.If used this additive, then the mol ratio of additive and organic single-lithium be preferably 2: 1～20: 1, more preferably 5: 1～15: 1.It can be that wherein solvent load is that every 100g solvent need add many vinyl-arene 0～100mmol with any one of the required solvent in the synthetic solution polymerized rubber of undefined synthetic the present invention that organic many lithiums prepare required solvent.Organic multi-lithium initiator prepares required temperature of reaction and is-10～100 ℃, is preferably 30～70 ℃, and the reaction times is 3 minutes to 6 hours, is preferably 30 minutes to 3 hours.
Conjugated diene monomer in the polymerization process of diblock solution polymerized rubber of the present invention can have 4-12 carbon atom, preferred 4-8 carbon atom, preferably 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2-phenyl-1,3 divinyl, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-pentadiene, 1, the 5-cyclohexadiene.Mono vinyl aromatic compound can have 8～20 carbon atoms, preferred 8-12 carbon atom, as vinylbenzene and derivative thereof, preferably vinylbenzene, alpha-methyl styrene, vinyl toluene, t-butyl styrene, to methoxy styrene, the tertiary butyl-Alpha-Methyl-vinylbenzene, methyl-alpha-methyl styrene, 2,4-dimethyl styrene, ethyl styrene, propylstyrene, isopropyl benzene ethene.
The required solvent of polymerization can be the solvent that is suitable in any solution polymerized rubber, preferably carries out in aliphatic hydrocarbon, naphthenic hydrocarbon and mixed solvent thereof, as Skellysolve A, normal hexane, normal heptane, pentamethylene, hexanaphthene, raffinate oil and composition thereof.The common solvent consumption is that every 100g monomer need add 250～4000g solvent.
The structure regulator that adopts in polymerization process can be conventional use any in the anionoid polymerization solution polymerized rubber system, preferred ether compound or tertiary amine compound are made structure regulator, more preferably tetrahydrofuran (THF), glycol dimethyl ether, diethylene glycol dimethyl ether, N, N, N, ' N '-Tetramethyl Ethylene Diamine, triethylamine etc. are made structure regulator; Also can add simultaneously alkoxyl group potassium compounds and regulate the multipolymer composition, as tert.-butoxy potassium, uncle's pentyloxy potassium (KTA) etc.Synthetic and the synthetic used structure regulator of B section of A section can be identical, also can difference, and the different structure conditioning agent may be used alone, can also be used in combination.
The consumption of structure regulator is the conventional amount used that those skilled in the art can determine in the polymerization process, is preferably: A section consumption is that every mole of organolithium (in lithium atom) adds 0.1 to 50 mole; B section consumption is that every mole of organolithium adds 0 to 80 mole.According to the different structure regulator that adopts, preferred conditioning agent amount ranges is as follows: when selecting THF as conditioning agent for use, A section consumption is that every mole of organolithium need add 1～50 mole of THF, and B section THF consumption is that every mole of organolithium need add 5～80 moles of THF.When selecting glycol dimethyl ether as conditioning agent for use, A section consumption is that every mole of organolithium need add glycol dimethyl ether 0.1-10 mole, and B section glycol dimethyl ether consumption is that every mole of organolithium need add 0.5～40 mole of glycol dimethyl ether.When selecting diethylene glycol dimethyl ether (2G) as conditioning agent for use, A section consumption is that every mole of organolithium need add 0.1～10 mole of 2G, and B section consumption is that every mole of organolithium need add 2G0.2～20 mole.When selecting Tetramethyl Ethylene Diamine (TMEDA) as conditioning agent for use, A section consumption is that every mole of organolithium need add 0.1～10 mole of TMEDA, and B section consumption is that every mole of organolithium need add 0.2～20 mole of TMEDA.Select for use tert.-butoxy potassium (KTB) to regulate multipolymer and form when distributing, the consumption of A and B section respectively need add KTB0.05～1.0 mole for every mole of organolithium, is preferably 0.15～0.45 mole.Select for use uncle's pentyloxy potassium (KTA) to regulate multipolymer and form when distributing, the consumption of A and B section is that every mole of organolithium need add KTA0.05～1.0 mole, is preferably 0.15～0.45 mole.
The consumption of initiator depends on the size of design molecular weight in the polymerization process, and its significant quantity (in lithium atom) is that those skilled in the art can determine.The consumption of general initiator is that per 100 gram monomers need add 0.8～2.05mmol (in lithium atom).Initiator can once add, and also can add several times.
For further widening molecular weight distribution, improve the rubber cold flow properties, can add coupling agent and carry out linked reaction.The adding of coupling agent makes the different reactive polymer molecular moiety generation linked reaction of arm number, generates the more coupling polymer molecule of arm number.Along with the increase of coupling agent consumption, molecular weight distribution is further widened, but the coupling agent consumption can not be too high, otherwise easily produces gel.Therefore the mol ratio of coupling agent and organic lithium initiator (in lithium atom) is preferably in 0.05～0.20 scope between 0.05～0.25.Coupling agent can be selected for use: the methyl trichlorosilicane, methyl tribromide silicon, methyl triiodide silicon, the methyl tin trichloride, methyl tribromide tin, methyl triiodide tin, butyl trichlorosilicane, butyl tribromide silicon, butyl triiodide silicon, butyl tin trichloride, butyl tribromide tin, butyl triiodide tin, silicon tetrachloride, Silicon bromide, silicon tetraiodide, tin tetrachloride, tin tetrabromide, tin tetraiodide, germanium tetrachloride, diethylene adipate, dimethyl adipate, Polycizer W 260, isocyanic ester, Vinylstyrene.Preferred coupling agent is a tin tetrachloride.
Polymeric reaction temperature of the present invention is the anionic polymerisation temperature that common organolithium causes.Polymerization temperature preferably changes between 0-150 ℃, and more preferably 20-120 ℃, preferred 20-100 ℃ again, the synthetic and B section synthesized polymer temperature of A section can be identical, also can difference.
The invention will be further described below in conjunction with embodiment, and these embodiment only are illustration purposes, do not limit the present invention.
Embodiment 1
Under the high pure nitrogen protection; press table 1 proportioning with hexanaphthene, 1; 3-divinyl, MVA (1; the 3-Vinylstyrene) joins in the 500ml exsiccant saline bottle and (also can in reactor, synthesize); mix the back and inject n-Butyl Lithium with syringe; behind reaction 30min under 70 ℃, be the multi-chelate organolithium initiator of different MVA/Li, be equipped with following examples and use.Available pair of titration measuring of initiator concentration (in lithium atom) the results are shown in Table 1.
| Numbering | 1 | ?2 | ?3 | ?4 | ?5 | ?6 | ?7 | ?8 | ?g |
| MVA/Li (mol ratio) | 0 | ?0.10 | ?0.15 | ?0.20 | ?0.25 | ?0.30 | ?0.40 | ?0.50 | ?0.60 |
| Initiator concentration (mol/L) | 0.30 | ?0.28 | ?0.28 | ?0.26 | ?0.26 | ?0.27 | ?0.27 | ?0.26 | ?0.25 |
| MVA consumption (mmol) | 0 | ?10 | ?15 | ?20 | ?25 | ?30 | ?40 | ?50 | ?60 |
| Hexanaphthene amount (g) | 220 | ?230 | ?230 | ?250 | ?250 | ?240 | ?240 | ?250 | ?250 |
| 1,3-butadiene consumption (g) | 30 | ?30 | ?30 | ?30 | ?30 | ?30 | ?30 | ?30 | ?30 |
Embodiment 2～7 and Comparative Examples 1～7
The polymkeric substance synthesis step is as follows: diblock polymer synthesizes in 5L stainless steel still and carries out.Before the reaction 2.5kg hexanaphthene and a certain amount of monomer, structure regulator are joined in the reactor, be warming up to temperature requiredly after mixing, treat that the stable back of temperature in the kettle adds the organic single-lithium initiator and begins polymerization.After treating A section conversion of monomer 97～100%, add the B section monomer mixed solution (containing structure regulator on demand) for preparing and carry out the polymerization of B section.After treating its whole conversion, add a certain amount of coupling agent in proportion and carry out linked reaction, treat linked reaction finish after termination reaction, antioxidant 264 is joined in the glue, roll at 110 ℃ cylinder through the product after the poach cohesion and obtain diblock butylbenzene copolymer product after doing.Embodiment and Comparative Examples polymeric reaction condition such as table 2,3, micmstructure of polymer data such as table 4,5.
Table 2 embodiment polymeric reaction condition
Embodiment numbers 23456 7A section Bd/St (g) 189,/81 2,1/9 10,0/0 15,0/0 15,0/0 55/5
Structure regulator (g) THF TMEDA 2G THF THF THF/KTB
(1.2) (1.3/0.05) initiator n-BuLi consumption (g) 12.2 12.5 12.3 12.5 12.8 12.5B section Bd/St (g) 18,/12 256,/14 130,/70 84,/66 84,/66 192/48 of (9.3) (4.2) (1.3) (1.2)
Structure regulator (g) 2G 2G TMEDA 2G
(1.0)???(10.7)?(14.4)???(7.8)
A/B (weight ratio) 9/1 1/9 1/2 1/1 1/1 1/4 polymeric reaction temperatures (℃) A 50 50 50 50 50 50
B 50 50 50 50 50 50 coupling agent SnCl
4(g) 6.5 7.0 7.0 7.8 8.0 7.2
*The n-BuLi-n-Butyl Lithium.
Table 3 Comparative Examples polymeric reaction condition
Comparative Examples is numbered 123456 7A section Bd/St (g) 10,0/0 13,7/0 10,0/0 50,/10 50,/10 15,0/0 225/75
Structure regulator (g) THF TMEDA 2G THF THF THF/KTB THF
(8.7) (1.2/0.055) (7.4) initiator n-BuLi consumption (g) 12.5 12.8 12.6 12.0 12.6 12.5 12.5B section Bd/St (g) 161,/39 125,/38 130,/70 1,36/,106 1,36/,106 84/66 of (0.9) (4.2) (1.2) (1.3)
Structure regulator (g) THF TMEDA 2G 2G TMEDA 2G
(75)????(2.5)???(1.5)??(10.0)??(14.7)???(10.4)
A/B (weight ratio) 1/2 1/1.2 1/2 1/4 1/4 1/1 polymeric reaction temperatures (℃) A 50 50 50 50 50 50 50
B 50 50 50 50 50 50 coupling agent SnCl
4(g) 7.2 7.5 7.5 7.0 7.5 7.6 8.0
*N-BuLi-n-Butyl Lithium, Comparative Examples 7 are a block randomly solution polymerized butadiene-styrene rubber with low
Table 4 embodiment micmstructure of polymer data sheet
Embodiment numbers 23456 7A section Cv (wt%) 24.54 60.12 23.56 25.7 25.05 26.8
St (wt%) 30.0 30.0 000 8B section Cv (wt%) 26.38 79.47 57.09 68.29 65.48 43.4
St(wt％)????40.0??5.0???29.1??44.0???46.28?20.0A-B????Cv(wt％)????24.7??78.01?41.84?40.99??39.18?40.0
St (wt%) 31.0 7.5 19.39 22.0 23.14 17.6 bivariate distribution indexes (σ) 5.8 6.76 39.8 60.1 64 15 table 5 Comparative Examples micmstructure of polymer data sheet
Comparative Examples is numbered 123456 7A section Cv (wt%) 23.9 20.02 23.56 34.14 31.9 30.07
St (wt%) 000 16.0 18.82 0B section Cv (wt%) 57.89 52.53 64.37 54.67 48.1 59.82
St(wt％)????52.22?23.88?30.7???44.0??40.65?45.78A-B????Cv(wt％)????35.23?35.6??46.33??49.07?43.97?40.53?34.0
St (wt%) 26.11 13.0 19.33 38.4 36.28 22.89 25.0 bivariate distribution indexes (σ) 64.8 37.1 45.03 27.9 21.8 55.11 polymkeric substance rubber unvulcanizates prescription is as follows, its physical and mechanical properties and dynamic properties such as table 5,6.
Mixing formula: Wt%
Rubber 100 of the present invention
Zinc oxide 5
Stearic acid 2
Antioxidant D 1.0
Aromatic hydrocarbon oil 5
Carbon black HAF 45
Accelerant CZ 1.0
Sulphur 1.7 table 6 embodiment polymer physics mechanical property and dynamic propertiess
Embodiment numbers 234567 tensile strength, (Mpa) 24.9 19.8 20.7 20.1 21.5 20.5300% stretching strength, (Mpa) 10.8 9.5 10.4 9.6 10.1 10.7 specific elongation rates, (%) 568 494 504 544 532 495 permanent deformations, (%) 13 9 11 15 14 10 Shao Er hardness, 66 64 65 62 65 62 tearing strengths, (kN/m) 58.4 54.5 56.0 52 55.6 51.5tan δ 0 ℃ 0.3269 0.4484 0.330 0.269 0.357 0.314
50℃??????0.0740????0.0737?0.0921??0.080??0.1021????0.1007
Table 7 Comparative Examples polymer physics mechanical property and dynamic properties
Comparative Examples is numbered 1234567 tensile strength (Mpa), 20.2 19.9 19.0 20.8 22.0 19.2 21.6300% stretching strength (Mpa), 9.5 9.1 9.0 10.1 11.9 9.2 12.0 specific elongation rate (%) 490 480 485 508 508 544 500 permanent deformations (%) 10 9 11 17 20 17 9.8 Shao Er hardness, 61 64 66 64 72 72 66 tearing strengths (kN/m), 55.0 53.5 49.5 51.0 51.0 54.5 54.7tan δ 0 ℃ 0.158 0.143 0.268 0.4443 0.4094 0.2082 0.2736
50 ℃ 0.131 0.0452 0.106 0.1426 0.1705 0.1392 0.114 embodiment 8～13 and Comparative Examples 8～13
The polymkeric substance synthesis step is as follows: diblock polymer synthesizes in 5L stainless steel still and carries out.Before the reaction 2.5kg hexanaphthene and a certain amount of monomer, structure regulator are joined in the reactor, be warming up to temperature requiredly after mixing, treat that the stable back of temperature in the kettle adds among the embodiment 1 organic multi-lithium initiator of No. 3 and begins polymerization.After treating A section conversion of monomer 97～100%, add the B section monomer mixed solution (containing structure regulator on demand) for preparing and carry out the polymerization of B section.After treating its whole conversion, add a certain amount of coupling agent in proportion and carry out linked reaction, treat linked reaction finish after termination reaction, antioxidant 264 is joined in the glue, roll at 110 ℃ of cylinders through the product after the poach cohesion and obtain diblock butylbenzene copolymer product after doing.Embodiment and Comparative Examples polymeric reaction condition such as table 8,9, micmstructure of polymer data such as table 10,11.
Table 8 embodiment and Comparative Examples polymeric reaction condition
Embodiment numbers 89 10 11 12 13 A section Bd/St (g) 189,/81 63,/27 63,/27 63,/27 15,0/0 150/0
Additive (g) THF THF TMEDA 2G THF THF
(3) (40) (7.8) (8.5) (2.5) (2.6) initiator PLi consumptions (g) 50 65 60 67 60 66B section Bd/St (g) 2,1/9 200,/10 200,/10 200,/10 84,/66 84/66
Additive (g) 2G TMEDA
(0.78)????(1.5)
A/B (weight ratio) 9/1 3/7 3/7 3/7 1/1 1/1 polymeric reaction temperatures (℃) A 50 30 35 35 50 50
B 50 30 35 35 50 50 coupling agent SnCl
4(g) 6.5 9.8 7.8 7.5 7.8 8.2
(annotate: the PLi initiator is No. 3 initiators among the embodiment 1)
Table 9 Comparative Examples polymeric reaction condition
Comparative Examples is numbered 89 10 11 12 13A section Bd/St (g) 10,0/0 13,7/0 10,0/0 50,/10 50,/10 150/0
Structure regulator (g) THF TMEDA 2G THF THF THF/KTB
(3.0) (0.9/0.036) initiator PLi consumption (g) 52 62 65 61 136/106 62B section Bd/St (g) 161,/39 161,/39 130,/70 1,36/,106 67 84/66 of (0.5) (3.0) (0.9) (0.9)
Structure regulator (g) THF TMEDA 2G 2G TMEDA 2G
(26)???(1.4)????(1.1)??(8.2)???(9.7)???(8.2)
A/B (weight ratio) 1/2 1/1.2 1/2 1/4 1/4 1/1 polymeric reaction temperatures (℃) A 50 50 50 50 50 50
B 50 50 50 50 50 50 coupling agent SnCl
4(g) 6.5 7.8 7.5 7.1 8.0 7.9 (annotate: the PLi initiator is No. 3 initiators among the embodiment 1)
Table 10 micmstructure of polymer data sheet
Embodiment numbers 89 10 11 12 13A section Cv (wt%) 31.92 59.79 68.34 66.79 37.7 30.6
St (wt%) 29.3 27.94 30.0 30.0 0 0B section Cv (wt%) 39.19 81.3 73.64 77.05 76.03 65.84
St(wt％)????34.3??5.88??5.11??5.11??40.72?45.92A-B????Cv(wt％)????32.6??75.99?72.3??74.52?51.97?42.97
St(wt％)????29.8??12.5??12.5??12.5??20.36?22.96
Molecular weight distributing index 2.27 2.30 2.12 2.50 2.32 2.08
Bivariate distribution index (σ) 4.8 7.9 17.5 15.3 55.0 58.1
Table 11 Comparative Examples micmstructure of polymer data sheet
Comparative Examples is numbered 89 10 11 12 13A section Cv (wt%) 22.81 19.73 21.57 32.12 30.84 29.95
St (wt%) 000 16.9 17.9 0B section Cv (wt%) 53.38 49.68 64.87 54.77 49.35 60.1 8
St(wt％)????50.13?22.93?31.0??44.31?44.54?45.38A-B????Cv(wt％)????34.87?34.93?46.21?49.07?43.83?40.94
St (wt%) 25.67 13.5 19.5 38.27 36.85 23.10 molecular weight distributing index 2.05 2.13 2.18 2.40 2.12 1.95 bivariate distribution indexes (σ) 59.7 34.9 46.2 28.3 20.4 54.9
Polymkeric substance rubber unvulcanizate prescription is as the prescription of cross-linked rubber among the organic single-lithium embodiment, its physical and mechanical properties and dynamic properties such as table 12 and 13.
Table 12 polymer physics mechanical property and dynamic mechanical
Embodiment numbers 89 10 11 12 13 tensile strength, (Mpa) 21.4 20.9 21.7 19.0 22.1 21.1300% stretching strength, (Mpa) 10.5 10.2 9.4 7.0 8.0 8.5 specific elongation rates, (%) 491 495 520 668 612 592 permanent deformations, (%) 13 11 13 18 17 15 Shao Er hardness, 63 62 62 62 66 62 tearing strengths, (kN/m) 58 60.5 56.5 54.5 57.6 58.5tan δ 0 ℃ 0.3919 0.5999 0.5771 0.4331 0.3947 0.3414
50℃?????????0.0713?0.0992??0.1006?0.1049??0.0995?0.1017
Data can be found out from table: compare with prior art diblock solution polymerized butadiene styrene rubber with common randomly solution polymerized butadiene-styrene rubber with low, with method of the present invention at opposed polarity conditioning agent system synthetic diblock solution polymerized butadiene styrene rubber, when the different block microtextures of polymkeric substance adhere to specification and bivariate distribution index when meeting specialized range, its physical and mechanical properties is good, rolling resistance is lower, wet-sliding resistant performance is higher, and low-rolling-resistance and high wet-sliding resistant equalization performance obviously improve; But when bivariate distribution index overshoot scope, it is balanced that its rolling resistance and wet-sliding resistant performance are difficult to reach, and causes the rubber over-all properties to reduce.
Claims (20)
1. conjugated diene and monovinylarene diblock solution polymerized rubber is characterized in that:
(a) the A section is the random copolymerization section of conjugated diolefin homopolymerization section or conjugated diene and monovinylarene, and wherein monovinylarene content is 0-30% weight, and contents of ethylene is a 10-70% weight in the conjugated diene chain link.
(b) the B section is the random copolymerization section of conjugated diene and monovinylarene, and wherein monovinylarene content is 5-60% weight, and contents of ethylene is a 10-80% weight in the conjugated diene chain link;
(c) the A section accounts for the 10-90% of multipolymer weight;
(d) monovinylarene content is 5-40% weight in the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, and contents of ethylene is a 15-80% weight in the conjugated diene chain link;
(e) according to the difference of the structure regulator that adds in the polymerization, the bivariate distribution index of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock changes between 0～90.
2. solution polymerized rubber according to claim 1 is characterized in that the difference according to the structure regulator that adds in the polymerization, and the bivariate distribution index of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock changes between 5-80.
3. solution polymerized rubber according to claim 1 is characterized in that the structure regulator that adds in the polymerization is a tetrahydrofuran (THF), and the bivariate distribution index is 1～30.
4. solution polymerized rubber according to claim 3 is characterized in that the structure regulator that adds in the polymerization is a tetrahydrofuran (THF), and the bivariate distribution index is 3-20.
5. solution polymerized rubber according to claim 1 is characterized in that the structure regulator that adds in the polymerization is a diethylene glycol dimethyl ether, and the bivariate distribution index is 5-45.
6. solution polymerized rubber according to claim 5 is characterized in that the structure regulator that adds in the polymerization is a diethylene glycol dimethyl ether, and the bivariate distribution index is 10-40.
7. solution polymerized rubber according to claim 1 is characterized in that the structure regulator that adds in the polymkeric substance is a N,N,N, and the bivariate distribution index is 5-35.
8. solution polymerized rubber according to claim 7 is characterized in that the structure regulator that adds in the polymerization is a N,N,N, and the bivariate distribution index is 10-30.
9. solution polymerized rubber according to claim 1 is characterized in that the structure regulator that adds in the polymerization is tetrahydrofuran (THF)/glycol dimethyl ether or tetrahydrofuran (THF)/N,N,N, and the bivariate distribution index is 30-80.
10. solution polymerized rubber according to claim 1 is characterized in that the structure regulator that adds in the polymerization is tetrahydrofuran (THF)/tert.-butoxy potassium/diethylene glycol dimethyl ether, and the bivariate distribution index is 10-40.
11. solution polymerized rubber according to claim 1 is characterized in that described conjugated diene contains 4～12 carbon atoms; Described monovinylarene contains 8-20 carbon atom.
12. solution polymerized rubber according to claim 11 is characterized in that described conjugated diene is a 1,3-butadiene; Described monovinylarene is a vinylbenzene.
13. the method for synthetic each described solution polymerized rubber of claim 1-12 may further comprise the steps successively:
(1) inert solvent, conjugated diene, the monovinylarene that will react required adds in the reactor, the organic lithium initiator that adds significant quantity then, in the presence of initiator, carry out the polymerization of A section, make A section polymerisation conversion reach 97-100%, wherein the adding weight ratio of conjugated diene and mono vinyl arenes monomer is 100: 0-70: 30;
(2) add conjugated diene, monovinylarene and nonessential structure regulator and carry out the polymerization of B section, wherein the concrete amount that adds of conjugated diene and mono vinyl arenes monomer is calculated by the σ value of weight the present invention when regulation of two sections of the added two kinds of amount of monomer of A section and A of the present invention, B according to the present invention and is definite and control;
(3) treat that not necessarily B section transformation efficiency reaches 100% back adding coupling agent and carries out linked reaction, after linked reaction finishes;
(4) termination reaction.
14. method according to claim 13 is characterized in that described polyreaction inert solvent is selected from the mixture of aliphatic hydrocarbon, naphthenic hydrocarbon or naphthenic hydrocarbon and aliphatic hydrocarbon.
15. method according to claim 13 is characterized in that structure regulator is selected from ether compound, tertiary amine compound, alkoxyl group potassium compound and composition thereof.
16. method according to claim 15 is characterized in that described ether compound is selected from tetrahydrofuran (THF), diethylene glycol dimethyl ether; Tertiary amine compound is selected from N,N,N; The alkoxyl group potassium compound is selected from tert.-butoxy potassium, uncle's pentyloxy potassium.
17. method according to claim 13 is characterized in that the A section, the used structure regulator of B section polymerization can be identical, also can be different.
18. method according to claim 13 is characterized in that the rubber solutions polymerization temperature is 0-150 ℃.
19. method according to claim 13, coupling agent are selected from silicon tetrachloride, tin tetrachloride, diethylene adipate, dimethyl adipate, isocyanic ester etc.
20. requirement according to claim 19, coupling agent are tin tetrachloride.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558412A (en) * | 2013-10-17 | 2015-04-29 | 中国石油化工股份有限公司 | Monovinyl arene-conjugated diene copolymer composition as well as preparation method and application thereof |
| CN104693388A (en) * | 2014-12-31 | 2015-06-10 | 大连海事大学 | Preparation method for wide temperature region damping rubber of gradual change block structure through anion method |
| CN101903409B (en) * | 2007-12-14 | 2015-11-25 | 朗盛艾拉托麦罗斯巴西有限公司 | For the preparation of a kind of 1, the method of 3-divinyl and cinnamic multipolymer, this multipolymer containing random segments, is followed thereafter and is had block that is a kind of and this main chain different structure in its main chain, this block is homopolymerization or copolymerization, functionalized, and thus obtained product |
| CN106256843A (en) * | 2015-06-19 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of olefin copolymer and its preparation method and application |
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| CN117567685A (en) * | 2024-01-16 | 2024-02-20 | 新疆独山子石油化工有限公司 | High-wear-resistance solution polymerized styrene-butadiene rubber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101903409B (en) * | 2007-12-14 | 2015-11-25 | 朗盛艾拉托麦罗斯巴西有限公司 | For the preparation of a kind of 1, the method of 3-divinyl and cinnamic multipolymer, this multipolymer containing random segments, is followed thereafter and is had block that is a kind of and this main chain different structure in its main chain, this block is homopolymerization or copolymerization, functionalized, and thus obtained product |
| CN104558412A (en) * | 2013-10-17 | 2015-04-29 | 中国石油化工股份有限公司 | Monovinyl arene-conjugated diene copolymer composition as well as preparation method and application thereof |
| CN104693388A (en) * | 2014-12-31 | 2015-06-10 | 大连海事大学 | Preparation method for wide temperature region damping rubber of gradual change block structure through anion method |
| CN106256843A (en) * | 2015-06-19 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of olefin copolymer and its preparation method and application |
| CN106256843B (en) * | 2015-06-19 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of olefin copolymer and its preparation method and application |
| CN111072879A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Block copolymer, block copolymer composition, preparation method of block copolymer, vulcanized rubber, application of vulcanized rubber, tire tread and tire |
| CN117567685A (en) * | 2024-01-16 | 2024-02-20 | 新疆独山子石油化工有限公司 | High-wear-resistance solution polymerized styrene-butadiene rubber and preparation method thereof |
| CN117567685B (en) * | 2024-01-16 | 2024-04-16 | 新疆独山子石油化工有限公司 | High-wear-resistance solution polymerized styrene-butadiene rubber and preparation method thereof |
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