CN104710570A - Diolefin polymer and preparation method and vulcanized rubber - Google Patents
Diolefin polymer and preparation method and vulcanized rubber Download PDFInfo
- Publication number
- CN104710570A CN104710570A CN201310684457.4A CN201310684457A CN104710570A CN 104710570 A CN104710570 A CN 104710570A CN 201310684457 A CN201310684457 A CN 201310684457A CN 104710570 A CN104710570 A CN 104710570A
- Authority
- CN
- China
- Prior art keywords
- diene polymer
- formula
- molecular weight
- structural unit
- butadiene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a diolefin polymer and preparation method and vulcanized rubber obtained by vulcanization of the diolefin polymer. The diolefin polymer is a polymer with a structure as shown in the formula (I) TiZ4, wherein Z is a copolymer chain containing a styrene constitutional unit and a butadiene constitutional unit. The diolefin polymer provided by the invention has excellent mechanical properties.
Description
Technical field
The vulcanized rubber that the present invention relates to a kind of diene polymer, a kind of preparation method of diene polymer, the diene polymer prepared by the method and diene polymer sulfuration is obtained.
Background technology
The building-up reactions of existing solution polymerized butadiene styrene rubber mainly adopts anionic solution polymerization method.Such as, take hexanaphthene as solvent, lithium alkylide or rare earth are catalyzer, by anionic solution polymerization method synthesis solution polymerized butadiene styrene rubber.The main purposes of solution polymerized butadiene styrene rubber is used as tire product.Tire product develops into radial from bias tyre, and then to high-performance meridian tire and green radial, more and more higher requirement be it is also proposed to performance, both having required low rolling resistance is beneficial to energy-conservation, require again very high wet-sliding resistant performance to ensure vehicle driving safety, also require good wear resisting property and intensity simultaneously.
Add wide molecular weight distribution with batch-type solution polymerized butadiene styrene rubber many employings linked reaction of vinylbenzene and butadiene copolymer Reactive Synthesis at present, molecular weight, from unimodal narrow ditribution, becomes bimodal wide distribution, to reach the effect improving processing characteristics.At present the main coupling agent adopted is halogenide that is stanniferous or Siliciumatom, and using more is silicon tetrachloride, tin tetrachloride etc.But the mechanical property of the solution polymerized butadiene styrene rubber synthesized by above-mentioned coupling agent need to improve.
Summary of the invention
The vulcanized rubber that the object of this invention is to provide a kind of new diene polymer, a kind of preparation method of diene polymer, the diene polymer prepared by the method and diene polymer sulfuration is obtained.Diene polymer of the present invention has excellent mechanical property.
The present inventor is surprised to find that, when preparing styrene-butadiene copolymer rubber by compound shown in formula II being used as coupling agent, can improve the mechanical property of styrene-butadiene copolymer rubber significantly, thus completing the present invention.
To achieve these goals, the first invention of the present invention provides a kind of diene polymer, and wherein, described diene polymer is the polymkeric substance of structure shown in formula (I);
TiZ
4formula (I),
In formula (I), Z is the copolymer chain containing styrol structural unit and butadiene structural units.
Second invention of the present invention provides the preparation method of above-mentioned diene polymer, and the method comprises the following steps:
(1) under anionic polymerisation condition, under the existence of organic lithium initiator, make vinylbenzene and divinyl carry out copolymerization in a solvent, obtain polymerisate;
(2) under linked reaction condition, the polymerisate that step (1) is obtained and coupling agent react;
Wherein, described coupling agent is the compound of structure shown in formula II,
TiY
4formula II,
In formula II, Y is halogen.
3rd invention of the present invention provides the diene polymer prepared by the preparation method of above-mentioned diene polymer.
4th invention of the present invention provides the vulcanized rubber above-mentioned diene polymer sulfuration obtained.
Of the present invention by compound shown in formula II is prepared styrene-butadiene as coupling agent, the mechanical property of styrene-butadiene can be significantly improved.Such as, known by embodiment 1-6 described later and comparative example 1-2, the coupling agent of the application of the invention, relative to the existing coupling agent of use (silicon tetrachloride or tin tetrachloride), the styrene-butadiene vulcanized rubber that it obtains, 300% stress at definite elongation, tensile strength at yield and tear strength are all better than the styrene-butadiene vulcanized rubber using existing coupling agent to obtain, and suitable with the styrene-butadiene vulcanized rubber using existing coupling agent to obtain in hardness and tensile yield.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The diene polymer that first invention of the present invention provides is the polymkeric substance of structure shown in formula (I);
TiZ
4formula (I),
In formula (I), Z is the copolymer chain containing styrol structural unit and butadiene structural units.
The present invention is not particularly limited the number-average molecular weight of described diene polymer with the copolymer chain containing styrol structural unit and butadiene structural units, such as, the number-average molecular weight of described diene polymer can be 150,000-20 ten thousand, and molecular weight distribution is 1.3-1.6; The described number-average molecular weight containing the copolymer chain of styrol structural unit and butadiene structural units can be 100,000-15 ten thousand, and molecular weight distribution is 1.0-1.1; Preferably, the number-average molecular weight of described diene polymer can be 17.5 ten thousand-19 ten thousand, and molecular weight distribution is 1.4-1.45; The described number-average molecular weight containing the copolymer chain of styrol structural unit and butadiene structural units can be 11.5 ten thousand-12.5 ten thousand, and molecular weight distribution is 1.03-1.05.Described number-average molecular weight and molecular weight distribution can adopt the model purchased from Shimadzu Corporation be LC-10AT gel permeation chromatograph (GPC) measure obtain, wherein, being moving phase with THF, take Narrow distribution polystyrene as standard specimen, and probe temperature is 25 DEG C.
According to the present invention, styrol structural unit in the described copolymer chain containing styrol structural unit and butadiene structural units and the content of butadiene structural units can carry out selecting and changing in wider scope, and can control by the dosage according to actual needs by material in preparation process, such as, the weight ratio of described styrol structural unit and butadiene structural units can be 0.1-0.5:1, is preferably 0.2-0.4:1.
Second invention of the present invention provides the preparation method of above-mentioned diene polymer, and the method comprises the following steps:
(1) under anionic polymerisation condition, under the existence of organic lithium initiator, make vinylbenzene and divinyl carry out copolymerization in a solvent, obtain polymerisate;
(2) under linked reaction condition, the polymerisate that step (1) is obtained and coupling agent react;
Wherein, described coupling agent is the compound of structure shown in formula II,
TiY
4formula II,
In formula II, Y is halogen.
According to method of the present invention, in formula II, Y is halogen, and preferably, Y is chlorine or bromine, and more preferably, Y is chlorine.
According to method of the present invention, in step (1), the consumption of described vinylbenzene and divinyl can carry out selecting and adjusting in wider scope, and such as, the weight ratio of described vinylbenzene and divinyl can be 0.1-0.5:1, is preferably 0.2-0.4:1.
According to method of the present invention, described organic single-lithium initiator can be such as the organic single-lithium initiator shown in formula III,
R
2li formula III,
In formula III, R
2for C
1-C
6alkyl, C
3-C
12cycloalkyl, C
7-C
14aralkyl or C
6-C
12aryl.
Described C
1-C
6alkyl comprise C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl and n-hexyl.
Described C
3-C
12the specific examples of cycloalkyl can include but not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propyl cyclohexyl and 4-normal-butyl cyclohexyl.
Described C
7-C
14the specific examples of aralkyl can include but not limited to: phenyl methyl, phenylethyl, phenyl n-propyl, phenyl normal-butyl, phenyl t-butyl, propyloxy phenyl base, phenyl n-pentyl and phenyl normal-butyl.
Described C
6-C
12the specific examples of aryl can include but not limited to: phenyl, naphthyl, 4-aminomethyl phenyl and 4-ethylphenyl.
Described organic lithium initiator is specifically as follows but is not limited to: one or more in lithium ethide, n-propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, n-pentyl lithium, hexyllithium, cyclohexyl lithium, phenyl lithium, 2-naphthyl lithium, 4-butyl phenyl lithium, 4-tolyl lithium and 4-butylcyclohexyl lithium, be preferably n-Butyl Lithium and/or s-butyl lithium, more preferably n-Butyl Lithium.
The consumption of the present invention to described organic lithium initiator is not particularly limited, and can carry out appropriate selection according to the molecular size range of subject polymer.Those skilled in the art should it is easily understood that when needing to prepare the larger olefin copolymer of molecular weight, can reduce the consumption of organic lithium initiator, but now rate of polymerization also correspondingly can reduce; When needing the olefin copolymer preparing molecular weight, the consumption of organic lithium initiator can be increased, but now rate of polymerization also correspondingly can increase.
According to method of the present invention, relative to 100g polymerization single polymerization monomer, described organic lithium initiator is in lithium, and the consumption of described organic lithium initiator can be 0.01-10mmol, is preferably 0.25-2.5mmol.
The present invention is not particularly limited described anionic polymerisation condition, can be that the routine of this area is selected.As a rule, described anionic polymerisation condition comprises temperature, pressure and time.Wherein, described temperature and pressure all can carry out selecting and changing in wider scope, in order to more be conducive to the carrying out of polyreaction, described temperature is preferably 10-160 DEG C, is more preferably 40-110 DEG C, and described pressure is preferably 0.05-0.5MPa, is more preferably 0.1-0.3MPa.As a rule, the prolongation of described polymerization time is conducive to the raising of the transformation efficiency of reactant and the yield of reaction product, but the amplitude that the long transformation efficiency to reactant of polymerization time and reaction product yield improve is also not obvious, therefore, consider polymerization efficiency and effect, the described time is preferably 20-80 minute, is more preferably 25-45 minute.
In the present invention, described pressure all refers to gauge pressure.
According to the present invention, described solvent can be various can, as the organic substance of reaction media, such as, can be varsol and/or ether solvent.Described varsol can be C
5-C
7naphthenic hydrocarbon, one or more in aromatic hydrocarbons and isoparaffin.The specific examples of described varsol can include but not limited to: one or more in benzene, toluene, hexane, hexanaphthene, pentane, heptane, hexane and hexanaphthene.Described ether solvent can be C
4-C
15monoether and/or polyether.The specific examples of described ether solvent can include but not limited to: tert-butoxyethoxy ethane and/or tetrahydrofuran (THF).Wherein, these solvents can be used alone, also can be used in combination.The consumption of described solvent reasonably can be selected according to the consumption of monomer, and such as, the consumption of described solvent can make the total concn of described vinylbenzene and divinyl be 1-30 % by weight, is preferably 5-20 % by weight.
In addition, as well known to those skilled in the art, the water of trace may be there is in described solvent.But the terminator of water belongs with yin ionic polymerization, it can by prototropy and terminating chain reaction of propagation, and therefore, in order to make described anionic polymerisation to carry out smoothly, solvent preferably dewaters by the present invention.The described mode dewatered can for add water-removal agent in described solvent.The kind of described water-removal agent is known to the skilled person, such as, can be the 5A molecular sieve purchased from Dalian Kang Yu Chemical Co., Ltd..
According to method of the present invention, under preferable case, can also structure regulator be added in the anionic polymerisation process of step (1), effectively can control the microtexture of described polymerisate like this.Described structure regulator can be existing various can the material of microtexture of telomerized polymer, comprise containing one or more in oxygen, nitrogenous, sulfur-bearing and phosphorous compound, particularly, described structure regulator can be selected from one or more in ether, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, dioxane, crown ether, tetrahydrofurfuryl alcohol ether, triethylamine, Tetramethyl Ethylene Diamine, HMPA, potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate (ABS) potassium and sodium alkyl benzene sulfonate.As a rule, the mol ratio of described structure regulator and organic single-lithium initiator can be 1-100:1, is preferably 5-50:1.
According to method of the present invention, described coupling agent is the compound of structure shown in above-mentioned formula II,
In the present invention, the consumption of described coupling agent is also not particularly limited, as long as the polymkeric substance of structure shown in formula I can be generated.Such as, in described coupling agent and organic lithium initiator, the mol ratio of lithium is 0.05-0.25:1; Preferably, in described coupling agent and organic lithium initiator, the mol ratio of lithium is 0.1-0.2:1.
According to method of the present invention, in step (2), described linked reaction condition comprises temperature, pressure and time.Under preferable case, described temperature can be such as 50-120 DEG C, be preferably 60-100 DEG C, and described pressure can be such as 0.01-0.5MPa, be preferably 0.1-0.3MPa, and the described time can be such as 1-100 minute, be preferably 5-60 minute.
According to the present invention, after linked reaction completes, active centre may also still exist.Therefore, terminator should be added to make active centre inactivation in reaction system.The consumption of described terminator can reasonably select according to the consumption of organic single-lithium initiator, and as a rule, the mol ratio of described terminator and organic single-lithium initiator can be 1.0-1.2:1.Described terminator can be the existing various reagent that can make anion active center inactivation, such as, can be selected from one or more in water, methyl alcohol, ethanol and Virahol, be preferably water.
According to the present invention, under preferable case, after linked reaction completes, various additive can also be added in the diene polymer obtained, to give described diene polymer various performance.Described additive can be such as anti-aging agent, has good ageing resistance to make the diene polymer obtained.
The present invention is not particularly limited for the kind of described anti-aging agent, can be the selection of this area routine.Such as, described anti-aging agent can be phenols and/or amines antioxidants.Particularly, described anti-aging agent can be anti-aging agent, the four [3-(3 of Irganox1520 for being purchased from the trade mark of Switzerland's vapour Bagong department, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, 2,6-ditertbutylparacresol, tert-butyl catechol and 2, one or more in 2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol).By four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester used in combination time, the content of tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is not preferably higher than 50 % by weight; By 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is when combinationally using, and the content of tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is not preferably higher than 50 % by weight.
According to method of the present invention, the consumption of described anti-aging agent also can be the conventional amount used of this area.Such as, with the weight of described diene polymer for benchmark, the consumption of described anti-aging agent can be 0.005-2 % by weight, be preferably 0.1-0.5 % by weight.
According to method of the present invention, after adding anti-aging agent, the methods such as described diene polymer can be precipitated by purifying, centrifugation, filtration, decant, hot water cohesion are precipitated out from solution, also air-extraction can be adopted the removal of solvents in reaction system, all can know these those skilled in the art, will repeat no more at this.
In addition, present invention also offers the diene polymer prepared by aforesaid method.
In the present invention, the diene polymer prepared by aforesaid method refers to the solid reaction product after except desolventizing.Except the diene polymer shown in formula I, this solid reaction product generally also may comprise other a small amount of diene polymers.Can know these those skilled in the art, will repeat no more at this.
Present invention also offers a kind of vulcanized rubber, diene polymer sulfuration of the present invention obtains by this vulcanized rubber.
Described vulcanized rubber by being mixed with vulcanizing agent by described diene polymer, and can carry out sulfuration and obtains.Described vulcanizing agent for the conventional various diene polymer generation crosslinking reactions that can make, can form the material of tridimensional network.Particularly, described vulcanizing agent can be selected from sulphur, selenium, tellurium, benzoyl peroxide, urethanum and 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane.
The consumption of described vulcanizing agent can carry out appropriate selection according to the application scenario of the vulcanized rubber finally obtained.Usually, relative to diene polymer described in 100 weight parts, the consumption of described vulcanizing agent can be 1-2 weight part.
Described vulcanized rubber can also contain various auxiliary agent, to improve the performance of this vulcanized rubber or to give this vulcanized rubber with new performance.The various auxiliary agents that above-mentioned various auxiliary agent can be commonly used for this area, its consumption can use with the consumption that this area is conventional, is not repeated at this.
Below will be described the present invention by embodiment, but the present invention is not limited in following embodiment.
In following examples and comparative example:
(1) number-average molecular weight of diene polymer and the copolymer chain containing styrol structural unit and butadiene structural units and molecular weight distribution adopt the model purchased from Shimadzu Corporation to be that the gel permeation chromatograph (GPC) of LC-10AT measures and obtains, wherein, take THF as moving phase, take Narrow distribution polystyrene as standard specimen, probe temperature is 25 DEG C.
(2) in diene polymer, the content of each structural unit is calculated by feed ratio.
In following examples, the testing method of 300% stress at definite elongation, tensile strength at yield, tensile yield, tear strength and hardness measures according to GB/T528-1998 " test of vulcanized rubber or thermoplastic elastomer stress at definite elongation strain property ".
Embodiment 1
Before the polymerization, by the mixed solvent (weight ratio is 88:12) of hexanaphthene and normal hexane with 5A molecular sieve (
3 × 5, purchased from Dalian Kang Yu Chemical Co., Ltd., dry 5 hours at 500 DEG C in advance) soak 1 week.Under high pure nitrogen protection, in 500 liters of polymeric kettles, add the above-mentioned mixed solvent of 195kg, 8kg vinylbenzene successively, 680g conditioning agent tetrahydrofuran (THF) (system content 3000PPM), paradigmatic system is through high-purity N
2after displacement deoxygenation, add 24kg divinyl, stir after 10 minutes, the hexane solution (concentration of n-Butyl Lithium is 0.6mol/L) adding 450mL n-Butyl Lithium carries out polyreaction.Polymerization initiating temperature is 50 DEG C, pressure is 0.1MPa, reacts after 15 minutes and reaches peak temperature (top temperature, lower same) 90 DEG C, peak pressure (top pressure, lower same) 0.28MPa.Continuation reaction samples after 5 minutes and surveys monomer conversion is 100%.
Temperature be 65 DEG C, under pressure is 0.15MPa, in reactor, adding 250mL titanium tetrachloride solution, (concentration is 0.2mol/L, solvent is above-mentioned mixed solvent) carry out linked reaction, linked reaction is after 15 minutes, in polymeric kettle, add 4.8g deionized water carry out termination reaction, then stirring reaction adds 256g anti-aging agent 2,6 ditertiary butyl p cresol after 5 minutes, obtains glue.Glue obtains diene polymer A1 after water vapor accumulation, drying.The number-average molecular weight of described diene polymer A1 is 18.5 ten thousand, and molecular weight distribution is 1.45; In described diene polymer A1, the number-average molecular weight of the copolymer chain containing styrol structural unit and butadiene structural units is 12.1 ten thousand, and molecular weight distribution is 1.04; Containing in the copolymer chain of styrol structural unit and butadiene structural units, the weight ratio of styrol structural unit and butadiene structural units is 0.33:1.
Embodiment 2
Carry out according to the method for embodiment 1, carrying out linked reaction unlike adding 270mL titanium tetrachloride solution (concentration is 0.2mol/L, and solvent is above-mentioned mixed solvent) in reactor, obtaining diene polymer A2.The number-average molecular weight of described diene polymer A2 is 18.0 ten thousand, and molecular weight distribution is 1.43; In described diene polymer A2, the number-average molecular weight of the copolymer chain containing styrol structural unit and butadiene structural units is 11.9 ten thousand, and molecular weight distribution is 1.04; Containing in the copolymer chain of styrol structural unit and butadiene structural units, the weight ratio of styrol structural unit and butadiene structural units is 0.33:1.
Embodiment 3
Carry out according to the method for embodiment 1, carrying out linked reaction unlike adding 135mL titanium tetrachloride solution (concentration is 0.2mol/L, and solvent is above-mentioned mixed solvent) in reactor, obtaining diene polymer A3.The number-average molecular weight of described diene polymer A3 is 17.9 ten thousand, and molecular weight distribution is 1.43; In described diene polymer A3, the number-average molecular weight of the copolymer chain containing styrol structural unit and butadiene structural units is 12.4 ten thousand, and molecular weight distribution is 1.04; Containing in the copolymer chain of styrol structural unit and butadiene structural units, the weight ratio of styrol structural unit and butadiene structural units is 0.33:1.
Embodiment 4
Carrying out according to the method for embodiment 1, is 9.15kg unlike cinnamic add-on, and the add-on of divinyl is 22.85kg, similarly obtains diene polymer A4.The number-average molecular weight of described diene polymer A4 is 18.1 ten thousand, and molecular weight distribution is 1.42; In described diene polymer A4, the number-average molecular weight of the copolymer chain containing styrol structural unit and butadiene structural units is 12.1 ten thousand, and molecular weight distribution is 1.04; Containing in the copolymer chain of styrol structural unit and butadiene structural units, the weight ratio of styrol structural unit and butadiene structural units is 0.4:1.
Embodiment 5
Carrying out according to the method for embodiment 1, is 5.33kg unlike cinnamic add-on, and the add-on of divinyl is 26.65kg, similarly obtains diene polymer A5.The number-average molecular weight of described diene polymer A5 is 18.6 ten thousand, and molecular weight distribution is 1.44; In described diene polymer A5, the number-average molecular weight of the copolymer chain containing styrol structural unit and butadiene structural units is 12.0 ten thousand, and molecular weight distribution is 1.04; Containing in the copolymer chain of styrol structural unit and butadiene structural units, the weight ratio of styrol structural unit and butadiene structural units is 0.2:1.
Comparative example 1
Carry out according to the method for embodiment 1, carrying out linked reaction unlike adding 250mL silicon tetrachloride solution (concentration is 0.2mol/L, and solvent is above-mentioned mixed solvent) in reactor, obtaining diene polymer D1.The number-average molecular weight of described diene polymer D1 is 18.1 ten thousand, and molecular weight distribution is 1.45; In described diene polymer D1, the number-average molecular weight of the copolymer chain containing styrol structural unit and butadiene structural units is 12.3 ten thousand, and molecular weight distribution is 1.04; Containing in the copolymer chain of styrol structural unit and butadiene structural units, the weight ratio of styrol structural unit and butadiene structural units is 0.33:1.
Comparative example 2
Carry out according to the method for embodiment 1, carrying out linked reaction unlike adding 250mL tin tetrachloride solution (concentration is 0.2mol/L, and solvent is above-mentioned mixed solvent) in reactor, obtaining diene polymer D2.The number-average molecular weight of described diene polymer D2 is 17.9 ten thousand, and molecular weight distribution is 1.44; In described diene polymer D2, the number-average molecular weight of the copolymer chain containing styrol structural unit and butadiene structural units is 12.6 ten thousand, and molecular weight distribution is 1.04; Containing in the copolymer chain of styrol structural unit and butadiene structural units, the weight ratio of styrol structural unit and butadiene structural units is 0.33:1.
Embodiment 6
The diene polymer obtained in embodiment 1-5 and comparative example 1-2 is carried out sulfuration according to following formula respectively, and obtain vulcanized rubber S1-S6 and DS1-DS2, mechanical property of vulcanized rubber is in table 1.Wherein, mixing formula is: diene polymer 100g, sulphur 1.7g, stearic acid 2g, antioxidant D (N-phenyl-2-naphthylamine) 1g, aromatic hydrocarbon oil 5g, carbon black (N330) 45g, zinc oxide 5g, CZ(N-cyclohexyl-2-[4-morpholinodithio sulphenamide) 1g.
Table 1
| S1 | S2 | S3 | S4 | S5 | DS1 | DS2 | |
| 300% stress at definite elongation (MPa) | 18 | 18 | 17 | 19 | 17 | 16 | 15 |
| Tensile strength at yield (MPa) | 25 | 26 | 25 | 27 | 25 | 20 | 22 |
| Tensile yield (%) | 480 | 490 | 500 | 470 | 510 | 480 | 500 |
| Tear strength (kNm -1) | 34 | 35 | 33 | 36 | 33 | 30 | 30 |
| Hardness (shore A) | 73 | 75 | 73 | 76 | 72 | 74 | 73 |
Known by above-mentioned table 1, the vulcanized rubber S1-S5 obtained by method of the present invention, relative to vulcanized rubber DS1 and DS2 adopting silicon tetrachloride and tin tetrachloride to obtain as coupling agent, 300% stress at definite elongation, tensile strength at yield and tear strength are all better than DS1 and DS2, and suitable with DS1 and DS2 in hardness and tensile yield.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Claims (12)
1. a diene polymer, is characterized in that, described diene polymer is the polymkeric substance of structure shown in formula (I);
TiZ
4formula (I),
In formula (I), Z is the copolymer chain containing styrol structural unit and butadiene structural units.
2. diene polymer according to claim 1, wherein, the number-average molecular weight of described diene polymer is 150,000-20 ten thousand, and molecular weight distribution is 1.3-1.6; The described number-average molecular weight containing the copolymer chain of styrol structural unit and butadiene structural units is 100,000-15 ten thousand, and molecular weight distribution is 1.0-1.1.
3. diene polymer according to claim 1 and 2, wherein, contain in the copolymer chain of styrol structural unit and butadiene structural units described, the weight ratio of described styrol structural unit and butadiene structural units is 0.1-0.5:1, is preferably 0.2-0.4:1.
4. a preparation method for diene polymer, the method comprises the following steps:
(1) under anionic polymerisation condition, under the existence of organic lithium initiator, make vinylbenzene and divinyl carry out copolymerization in a solvent, obtain polymerisate;
(2) under linked reaction condition, the polymerisate that step (1) is obtained and coupling agent react;
It is characterized in that, described coupling agent is the compound of structure shown in formula II,
TiY
4formula II,
In formula II, Y is halogen.
5. method according to claim 4, wherein, Y is chlorine or bromine; Preferably, Y is chlorine.
6. the method according to claim 4 or 5, wherein, in described coupling agent and organic lithium initiator, the mol ratio of lithium is 0.05-0.25:1; Preferably, in described coupling agent and organic lithium initiator, the mol ratio of lithium is 0.1-0.2:1.
7. according to the method in claim 4-6 described in any one, wherein, described organic lithium initiator is the compound of structure shown in formula III,
R
2li formula III,
In formula III, R
2for C
1-C
6alkyl, C
3-C
12cycloalkyl, C
7-C
14aralkyl or C
6-C
12aryl;
Preferably, described organic lithium initiator is n-Butyl Lithium and/or s-butyl lithium.
8. according to the method in claim 4-7 described in any one, wherein, the weight ratio of described vinylbenzene and described divinyl is 0.1-0.5:1, is preferably 0.2-0.4:1.
9. according to the method in claim 4-8 described in any one, wherein, described linked reaction condition comprises: coupling temperature is 50-120 DEG C, and coupling pressure is 0.01-0.5MPa, and coupling time is 1-100min.
10. according to the method in claim 4-9 described in any one, wherein, the method is also included in the anionic polymerisation process of step (1) and adds structure regulator.
11. diene polymers prepared by the method in claim 4-10 described in any one.
12. 1 kinds of vulcanized rubbers, the diene polymer sulfuration in claim 1-3 and 11 described in any one obtains by this vulcanized rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310684457.4A CN104710570A (en) | 2013-12-13 | 2013-12-13 | Diolefin polymer and preparation method and vulcanized rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310684457.4A CN104710570A (en) | 2013-12-13 | 2013-12-13 | Diolefin polymer and preparation method and vulcanized rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104710570A true CN104710570A (en) | 2015-06-17 |
Family
ID=53410336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310684457.4A Pending CN104710570A (en) | 2013-12-13 | 2013-12-13 | Diolefin polymer and preparation method and vulcanized rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104710570A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349441A (en) * | 2015-07-22 | 2017-01-25 | 中国石油化工股份有限公司 | Styrene-butadiene block copolymer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644324A (en) * | 1970-02-02 | 1972-02-22 | Firestone Tire & Rubber Co | Polymers and copolymers of butadiene etc. having relatively wide molecular-weight distribution |
| CN1568333A (en) * | 2001-10-11 | 2005-01-19 | 株式会社普利司通 | Synthesis and use of chain-coupled polymeric sulfide compounds in rubber formulations |
| CN1644597A (en) * | 2004-12-27 | 2005-07-27 | 华东理工大学 | Styrene block copolymer reacting and extruding polymerization |
| WO2011066710A1 (en) * | 2009-12-02 | 2011-06-09 | 华东理工大学 | Reactive extrusion polymerization method for styrene/diene block copolymer |
| CN102101902A (en) * | 2009-12-21 | 2011-06-22 | 中国石油化工股份有限公司 | Method for preparing irregular copolymer of conjugated diene and vinyl arene |
-
2013
- 2013-12-13 CN CN201310684457.4A patent/CN104710570A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644324A (en) * | 1970-02-02 | 1972-02-22 | Firestone Tire & Rubber Co | Polymers and copolymers of butadiene etc. having relatively wide molecular-weight distribution |
| CN1568333A (en) * | 2001-10-11 | 2005-01-19 | 株式会社普利司通 | Synthesis and use of chain-coupled polymeric sulfide compounds in rubber formulations |
| CN1644597A (en) * | 2004-12-27 | 2005-07-27 | 华东理工大学 | Styrene block copolymer reacting and extruding polymerization |
| WO2011066710A1 (en) * | 2009-12-02 | 2011-06-09 | 华东理工大学 | Reactive extrusion polymerization method for styrene/diene block copolymer |
| CN102101902A (en) * | 2009-12-21 | 2011-06-22 | 中国石油化工股份有限公司 | Method for preparing irregular copolymer of conjugated diene and vinyl arene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349441A (en) * | 2015-07-22 | 2017-01-25 | 中国石油化工股份有限公司 | Styrene-butadiene block copolymer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101817911B (en) | Star block copolymer prepared from isoprene, butadiene and styrene, and preparation method and application thereof | |
| CN106589247B (en) | Low cis polybutadiene rubber and its preparation method and application | |
| JPH09291121A (en) | Butene/butadiene copolymer, its production, and vulcanized rubber | |
| CN104945817A (en) | Itaconate/butadiene copolymer type bioengineering rubber and preparation method thereof | |
| CN104114589A (en) | Method for producing branched conjugated diene polymer | |
| CN113072750B (en) | High-strength rubber composite material with excellent processability and preparation method thereof | |
| JP5459116B2 (en) | Polybutadiene rubber, process for producing the same, and composition | |
| Huang et al. | Mechanical reinforcement of isoprene rubbers via metal-coordinated crosslink of carboxyl-terminated telechelic polymers | |
| JPH0345099B2 (en) | ||
| CN104710570A (en) | Diolefin polymer and preparation method and vulcanized rubber | |
| CN104628896A (en) | Method for improving coupling efficiency of solution polymerized styrene-butadiene rubber | |
| CN104292408A (en) | Two-stage material-feeding random gradually-varied butylbenzene co-polymer and preparation method thereof | |
| CN104558329B (en) | A kind of diene's polymer and its preparation method and application | |
| CN106928415A (en) | Composite coupler and application and monovinylarene-conjugated diene copolymer composition and preparation method and tire | |
| CN106146734B (en) | A kind of coupling agent and its application and atactic butadiene styrene copolymer and preparation method thereof | |
| CN106832485B (en) | A kind of polybutadiene rubber and its preparation method and application | |
| CN106715479B (en) | Conjugated-diolefin (co) polymer shares catalyst, conjugated diolefin polymer, modified conjugated diene polymer, polybutadiene and the composition comprising aforementioned substances | |
| CN104558416A (en) | Rubber composition and vulcanized rubber | |
| CN102863576B (en) | Compound structure modifier for preparing 3,4-isoprene rubber and method for preparing 3,4-isoprene rubber by using same | |
| JP2017132959A (en) | Rubber composition and tire | |
| CN106977656B (en) | Dendritic polydiene rubber and preparation method thereof | |
| CN114058077B (en) | SBS thermoplastic elastomer, preparation method thereof, anti-aging agent and application thereof | |
| CN104558412A (en) | Monovinyl arene-conjugated diene copolymer composition as well as preparation method and application thereof | |
| CN106700128B (en) | Rubber antioxidant and its application and solution polymerized butadiene styrene rubber and preparation method thereof | |
| JP2014145064A (en) | Rubber composition for clinch apex and pneumatic tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150617 |
|
| RJ01 | Rejection of invention patent application after publication |