CN104109210B - A kind of chain-transfer agent and its preparation method and application - Google Patents
A kind of chain-transfer agent and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of chain-transfer agent, a kind of preparation method of chain-transfer agent, the chain-transfer agent prepared by the method and the application of described chain-transfer agent in alkene letex polymerization.The random copolymers that described chain-transfer agent is the olefin unit and at least two kinds of conjugated diene structural units containing at least one with structure shown in formula I, the number-average molecular weight of described random copolymers is not more than 20000; R
1-R
3identical or different, and be independently H or C separately
1-C
5alkyl.Adopt described chain-transfer agent can not only obtain the narrower and polymkeric substance that floe content is lower of molecular weight distribution, the mechanical property of the rubber containing described polymkeric substance can also be improved.In addition, described chain-transfer agent is non-mercaptan type chain transfer agent, does not have foul odour, has prospects for commercial application.
Description
Technical field
The present invention relates to a kind of chain-transfer agent, a kind of preparation method of chain-transfer agent, the chain-transfer agent prepared by the method and the application of described chain-transfer agent in olefinic polyreaction.
Background technology
Radical polymerization has that monomer source is extensive, production technique is simple, preparation method is various, industrialization low cost and other advantages, one of most important reaction having become synthetic polymer.But in radical polymerization process, some elementary reactions can make polymerization process be difficult to control, and so just may obtain the wider polymkeric substance of molecular weight distribution, thus directly affect the mechanical property, thermal property etc. of described polymkeric substance, limit its application.Therefore, synthesize the chain-transfer agent that can control the molecular weight of polymkeric substance and distribution thereof, make to obtain the narrower polymkeric substance of molecular weight distribution and there is good application prospect and practical value.
Research shows, different sulfur alcohol compounds has different chain transfer activities, is also not quite similar to the ability of regulation and control of molecular weight.At present, in the preparation process of free-radical emulsion polymerization styrene-butadiene rubber(SBR)/paracril, tert-dodecyl mercaptan is generally adopted to regulate molecular weight and the distribution thereof of synthetical glue as chain-transfer agent.But, sulfur alcohol compound all has special maladorous smell, irritant to skin, respiratory mucosa, has anesthetic action to central nervous system, certain impact can be produced on the health of execute-in-place workman, and the feature of environmental protection of produced rubber can be had influence on.For these problems, those skilled in the art have also been developed some novel chain-transfer agents.
Such as, CN101735184A discloses a kind of trithiocarbonate chain transfer agent utilizing maleic anhydride, alkyl alcohol and dithiocarbonic anhydride to synthesize, also disclose the reversible addition cracking chain tra nsfer radical polymerization that this chain-transfer agent can be used for methyl acrylic ester, styrenic, acrylic monomer simultaneously, and to disclose this chain-transfer agent can be hydrophilic or oil loving, and may be used for the techniques such as emulsion, body, solution, dispersion polymerization.
Summary of the invention
The object of this invention is to provide a kind of new chain-transfer agent, a kind of preparation method of chain-transfer agent, the chain-transfer agent prepared by the method and the application of described chain-transfer agent in olefinic polyreaction.
The invention provides a kind of chain-transfer agent, wherein, the random copolymers that described chain-transfer agent is the olefin unit and at least two kinds of conjugated diene structural units containing at least one with structure shown in formula I, the number-average molecular weight of described random copolymers is not more than 20000;
Wherein, R
1-R
3identical or different, and be independently H or C separately
1-C
5alkyl.
The invention provides a kind of preparation method of chain-transfer agent, wherein, under the method is included in the existence of initiator and under olefinic polyreaction condition, olefinic monomer and at least two kinds of conjugated dienes at least one with structure shown in formula II carry out polyreaction in a solvent, make to obtain number-average molecular weight and be not more than 20000, be preferably 1000-20000, more preferably 2000-12000, be more preferably the random copolymers of 4000-8000;
Wherein, R
1-R
3identical or different, and be independently H or C separately
1-C
5alkyl.
Present invention also offers the chain-transfer agent prepared by aforesaid method.
In addition, present invention also offers the application of above-mentioned chain-transfer agent in olefinic polyreaction.
The present inventor finds, in olefinic polyreaction process, adopt existing sulfur alcohol compound can produce a large amount of condensation products and implode thing (general designation throw out) as chain-transfer agent, therefore, regularly must clear up the throw out in conversion unit, substantially increase production cost thus and reduce the output of qualified polymerisate.And employing the invention provides the content that chain-transfer agent significantly can reduce throw out in polymerisate, thus extend cleaning and the turnaround of equipment, reduce production cost.The present inventor also finds, adopts chain-transfer agent provided by the invention, can also obtain the polymkeric substance that molecular weight distribution is narrower, and improves the mechanical property of the rubber containing described polymkeric substance.In addition, chain-transfer agent provided by the invention is non-mercaptan type chain transfer agent, does not have foul odour, avoids the harm to site operation personnel, has prospects for commercial application.
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 random copolymers that described chain-transfer agent provided by the invention is the olefin unit and at least two kinds of conjugated diene structural units containing at least one with structure shown in formula I, the number-average molecular weight of described random copolymers is not more than 20000;
Wherein, R
1-R
3identical or different, and be independently H or C separately
1-C
5alkyl.
Described C
1-C
5the specific examples of alkyl 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 and neo-pentyl.
According to the present invention, as long as there are the olefin unit of structure shown in formula I and at least two kinds of conjugated diene structural units containing at least one and the random copolymers chain-transfer agent that number-average molecular weight is not more than 20000 just can realize object of the present invention although adopt, but in order to make described chain-transfer agent, there is better chain tra nsfer performance, the number-average molecular weight of described random copolymers is preferably 1000-20000, more preferably 2000-12000, is more preferably 4000-8000.Described number-average molecular weight 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, as mentioned above, a kind of olefin unit and two kinds of conjugated diene structural units with structure shown in formula I can be contained in described random copolymers, also a kind of olefin unit and more than three kinds conjugated diene structural units with structure shown in formula I can be contained, the olefin unit of structure shown in formula I and two or more conjugated diene structural unit can also be had containing two or more, under preferable case, the olefin unit that described random copolymers has a structure shown in formula I by a kind of and two kinds of conjugated diene structural units form.Further, although the content of the olefin unit and conjugated diene structural unit with structure shown in formula I can carry out selecting and changing in wider scope, and can be adjusted by the add-on of material in preparation process, but more effectively suppress the generation of throw out to enable the chain-transfer agent obtained and prepare the narrower polymkeric substance of molecular weight distribution, preferably, with the olefin unit with structure shown in formula I of 100 weight parts for benchmark, the total content of two kinds of conjugated diene structural units can be 100-400 weight part, be more preferably 150-250 weight part.In addition, the weight ratio between two kinds of conjugated diene structural units is preferably 0.8-2:1.
According to the present invention, described conjugated diene structural unit be derived from conjugated diene structural unit namely, the structural unit formed by conjugate diene polymerization.Described conjugated diene refers to the various unsaturated acyclic hydrocarbons containing conjugated double bond (that is ,-C=C-C=C-) in molecular structure.The various conjugated dienes that described conjugated diene can be commonly used for this area, be not particularly limited, and choose reasonable can be carried out according to practical situation, such as, described conjugated diene can be selected from divinyl, isoprene, cyclopentadiene, 1, at least two kinds in 3-pentadiene, Vinylstyrene, 1,3-hexadiene and 2,3-dimethylbutadiene.
Under the preparation method of chain-transfer agent provided by the invention is included in the existence of initiator and under olefinic polyreaction condition, olefinic monomer and at least two kinds of conjugated dienes at least one with structure shown in formula II carry out polyreaction in a solvent, make to obtain number-average molecular weight and be not more than 20000, be preferably 1000-20000, more preferably 2000-12000, is more preferably the random copolymers of 4000-8000;
Wherein, R
1-R
3identical or different, and be independently H or C separately
1-C
5alkyl.
Described C
1-C
5alkyl according to reasonably selecting above, will be able to repeat no more at this.
Particularly, the olefinic monomer with structure shown in formula II can be selected from 2,4-phenylbenzene-4-methyl-2-amylene, 2,4-phenylbenzene-4-methyl-2-hexene, 2,4-phenylbenzene-4-methyl-2-heptene, 2, one or more in 4-phenylbenzene-4-methyl-2-octene and 2,4-phenylbenzene-4-methyl-2-nonene.
According to the present invention, in the preparation process of described chain-transfer agent, described initiator can have the olefinic monomer of structure shown in formula II and the initiator of conjugate diene polymerization for existing various can initiation, such as, can be organic lithium initiator.Single organic lithium initiator of described organic lithium initiator can be such as molecular formula be RLi, wherein, R is the alkyl of straight or branched, cycloalkyl or aryl.Particularly, described single organic lithium initiator can be selected from lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium and naphthyl lithium one or more, be preferably n-Butyl Lithium and/or s-butyl lithium.In addition, the present invention also can adopt dilithium initiator, as trimethylene two lithium and/or tetramethylene two lithium.The consumption of the present invention to described initiator is not particularly limited, and reasonably can select according to the size of the molecular weight of design.Those skilled in the art should it is easily understood that when needing to prepare the larger chain-transfer agent of molecular weight, can reduce the consumption of initiator, but now rate of polymerization also correspondingly can reduce; When needing the chain-transfer agent preparing molecular weight, the consumption of initiator can be increased, but now rate of polymerization also correspondingly can increase.Therefore, the molecular size range of olefin polymer considering rate of polymerization and obtain, have the olefinic monomer of structure shown in formula II and the gross weight of conjugated diene for benchmark with 100 weight parts, the consumption of described initiator is preferably 0.2-0.4 weight part, is more preferably 0.25-0.33 weight part.
According to the present invention, as mentioned above, in the preparation process of described chain-transfer agent, the olefinic monomer that can have a structure shown in formula II by a kind of and two kinds of conjugated dienes carry out polyreaction in a solvent, the olefinic monomer that also can have a structure shown in formula II by a kind of and more than three kinds conjugated dienes carry out polyreaction in a solvent, the olefinic monomer that can also have a structure shown in formula II by two or more and two or more conjugated diene carry out polyreaction in a solvent, preferably, the olefinic monomer having a structure shown in formula II by a kind of and two kinds of conjugated dienes carry out polyreaction in a solvent.Further, although the consumption of the olefinic monomer and conjugated diene with structure shown in formula II can carry out selecting and changing in the larger context, and can according to expecting that the chain-transfer agent that will obtain reasonably is selected, but more effectively suppress the generation of throw out to enable the chain-transfer agent obtained and prepare the narrower polymkeric substance of molecular weight distribution, preferably, with the olefinic monomer with structure shown in formula II of 100 weight parts for benchmark, total consumption of two kinds of conjugated dienes can be 100-400 weight part, is preferably 150-250 weight part.In addition, the weight ratio between two kinds of conjugated dienes is preferably 0.8-2:1.
The condition of the present invention to described olefinic polyreaction is not particularly limited, as long as can make to obtain, containing at least one, there are the olefin unit of structure shown in formula I and at least two kinds of conjugated diene structural units and the number-average molecular weight random copolymers that is less than 20000, usually, the condition of described polyreaction comprises polymerization temperature, polymerization pressure and polymerization time.Wherein, described polymerization temperature and polymerization pressure all can carry out selecting and changing in wider scope, and in order to more be conducive to the carrying out of polyreaction, described polymerization temperature is preferably 40-100 DEG C, is more preferably 50-80 DEG C; Described polymerization pressure is preferably 0.2-0.6MPa, is more preferably 0.3-0.5MPa.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, described polymerization time is preferably 20-60 minute, is more preferably 30-60 minute.
In the present invention, described pressure all refers to gauge pressure.
According to the present invention, in the preparation process of described chain-transfer agent, described solvent can be existing various can, as the material 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 the olefinic monomer and conjugated diene with structure shown in formula II be 20-40 % by weight, is preferably 20-35 % by weight.
According to the present invention, under normal circumstances, the preparation method of described chain-transfer agent also comprises after the reaction was completed, by the solvent removal in reaction system.The method removing described solvent is known to the skilled person, and will repeat no more at this.
Present invention also offers the chain-transfer agent prepared by aforesaid method.
In the present invention, the chain-transfer agent prepared by aforesaid method refers to the solid reaction product after except desolventizing.Except the random copolymers containing the olefin unit shown in formula I and conjugated diene structural unit, this solid reaction product generally also may comprise other a small amount of diene polymer, as having homopolymer and/or the conjugated diolefin homopolymerization thing of the olefinic monomer of structure shown in formula II, can know these those skilled in the art, will repeat no more at this.
In addition, present invention also offers the application of described chain-transfer agent in olefinic polyreaction.
Below will be described the present invention by embodiment.
In following examples and comparative example, the model of the number-average molecular weight of polymkeric substance and WATERS company of the molecular weight distribution employing U.S. is gel permeation chromatograph (GPC) mensuration of ALLIANCE2690, and wherein, THF is moving phase, Narrow distribution polystyrene is standard specimen, and temperature is 25 DEG C.The mooney viscosity of polymkeric substance adopts the model purchased from Japan be the mooney viscosity instrument of SHIMADZUSMV-300 and measure by the method that GB/T1232-92 specifies.In polymkeric substance, the content of throw out adopts following methods to measure: reaction product polyreaction obtained carries out filtering (adopting 200 order Stainless Steel Cloths to filter), and by dry for the solid product obtained, obtaining quality is m
1throw out, content (the % by weight)=m of described throw out
1÷ m
0× 100%, wherein, m
0refer in polymerization process the total mass adding monomer.
Preparation example 1
This preparation example is for illustration of chain-transfer agent provided by the invention and preparation method thereof.
By 140g2,4-phenylbenzene-4-methyl-2-amylene (i.e. R
1-R
3be methyl), 50g isoprene, 90g divinyl and 2000g hexanaphthene to add in 5L polymeric kettle and to mix, then the temperature of mixture is risen to 50 DEG C, control pressure is 0.3MPa, and add 32.2mL n-Butyl Lithium (BuLi) and carry out polymerization 60min, obtain chain-transfer agent a, its number-average molecular weight is 4000.
Preparation example 2
This preparation example is for illustration of chain-transfer agent provided by the invention and preparation method thereof.
By 180g2,4-phenylbenzene-4-methyl-2-amylene (i.e. R
1-R
3be methyl), 300g cyclopentadiene, 420g divinyl and 2000g hexanaphthene to add in 5L polymeric kettle and to mix, then the temperature of mixture is risen to 80 DEG C, control pressure is 0.5MPa, and add 16.2mL n-Butyl Lithium (BuLi) and carry out polyase 13 0min, obtain chain-transfer agent b, its number-average molecular weight is 8000.
Preparation example 3
This preparation example is for illustration of chain-transfer agent provided by the invention and preparation method thereof.
By 180g2,4-phenylbenzene-4-methyl-2-amylene (i.e. R
1-R
3be methyl), 100g Vinylstyrene, 230g divinyl and 2000g hexanaphthene to add in 5L polymeric kettle and to mix, then the temperature of mixture is risen to 60 DEG C, control pressure is 0.4MPa, and add 24.6mL n-Butyl Lithium (BuLi) and carry out polymerization 40min, obtain chain-transfer agent c, its number-average molecular weight is 6000.
Preparation example 4
This preparation example is for illustration of chain-transfer agent provided by the invention and preparation method thereof.
Chain-transfer agent is prepared according to the method for preparation example 1, unlike, described 2,4-phenylbenzene-4-methyl-2-amylenes 2,4-phenylbenzene-4-methyl-2-nonene (the i.e. R of identical weight part
1and R
2for methyl, R
3for n-pentyl) substitute, obtain chain-transfer agent d, its number-average molecular weight is 12000.
Preparation example 5
This preparation example is for illustration of chain-transfer agent provided by the invention and preparation method thereof.
Chain-transfer agent is prepared according to the method for preparation example 1, unlike, described 2,4-phenylbenzene-4-methyl-2-amylenes 2,4-phenylbenzene-4-methyl-2-heptene (the i.e. R of identical weight part
1and R
2for methyl, R
3for n-propyl) substitute, obtain chain-transfer agent e, its number-average molecular weight is 15000.
Embodiment 1
This embodiment is for illustration of the application of chain-transfer agent provided by the invention in olefinic polyreaction.
41g isproportionated potassium rosinate, 0.87g rongalite, 0.25g sequestrant EDTA, 2kg deionized water, 0.7g naphthalenesulfonic acid-formaldehyde condensate (purchased from Shangyu Zhe Chuan Chemical Co., Ltd., No. CAS is 9084-06-4), 0.053g V-Brite B oxygen scavenger and 4.5g Repone K are mixed and adds in reactor.After nitrogen pump drainage 3 times, mixing speed is controlled at 30 revs/min by greenhouse cooling to 5 DEG C.Vinylbenzene, divinyl, chain-transfer agent a and initiator di-isopropylbenzene hydroperoxide (DIP) being added in oil phase preparing tank joins in aforesaid reaction vessel after mixing, reacts 16 hours at 5 DEG C.Within every 4 hours from polyreaction, add a chain-transfer agent a, the amount at every turn added is 0.4g.Reacted rear cooling discharge, and in reaction product, added 0.23g diethyl hydroxylamine and 0.05g sodium nitrite solution termination reaction, in reaction product, the content of throw out is 2.4 % by weight.Then add the mixed solution devaporation of Repone K and dilute sulphuric acid, obtain emulsion polymerized styrene butadiene rubber G1 after drying, mooney viscosity is 53, and number-average molecular weight is 24.7 ten thousand, and molecular weight distribution is 3.1.
Embodiment 2
This embodiment is for illustration of the application of chain-transfer agent provided by the invention in olefinic polyreaction.
Emulsion polymerized styrene butadiene rubber is prepared according to the method for embodiment 1, unlike, the chain-transfer agent b of described chain-transfer agent a identical weight part substitutes, in reaction product, the content of throw out is 3.2 % by weight, obtain emulsion polymerized styrene butadiene rubber G2, mooney viscosity is 54, and number-average molecular weight is 26.8 ten thousand, and molecular weight distribution is 3.3.
Embodiment 3
This embodiment is for illustration of the application of chain-transfer agent provided by the invention in olefinic polyreaction.
Emulsion polymerized styrene butadiene rubber is prepared according to the method for embodiment 1, unlike, the chain-transfer agent c of described chain-transfer agent a identical weight part substitutes, in reaction product, the content of throw out is 2.3 % by weight, obtain emulsion polymerized styrene butadiene rubber G3, mooney viscosity is 50, and number-average molecular weight is 24.6 ten thousand, and molecular weight distribution is 3.5.
Embodiment 4
This embodiment is for illustration of the application of chain-transfer agent provided by the invention in olefinic polyreaction.
Emulsion polymerized styrene butadiene rubber is prepared according to the method for embodiment 1, unlike, the chain-transfer agent d of described chain-transfer agent a identical weight part substitutes, in reaction product, the content of throw out is 2.9 % by weight, obtain emulsion polymerized styrene butadiene rubber G4, mooney viscosity is 56, and number-average molecular weight is 32.2, and molecular weight distribution is 3.8.
Embodiment 5
This embodiment is for illustration of the application of chain-transfer agent provided by the invention in olefinic polyreaction.
Emulsion polymerized styrene butadiene rubber is prepared according to the method for embodiment 1, unlike, the chain-transfer agent e of described chain-transfer agent a identical weight part substitutes, in reaction product, the content of throw out is 3.2 % by weight, obtain emulsion polymerized styrene butadiene rubber G5, mooney viscosity is 60, and number-average molecular weight is 35.2 ten thousand, and molecular weight distribution is 3.9.
Comparative example 1
This comparative example is for illustration of the application of reference chain-transfer agent in olefinic polyreaction.
Emulsion polymerized styrene butadiene rubber is prepared according to the method for embodiment 1, unlike, the chain-transfer agent tert-dodecyl mercaptan of described chain-transfer agent a identical weight part substitutes, in reaction product, the content of throw out is 5.1 % by weight, obtain emulsion polymerized styrene butadiene rubber DG1, mooney viscosity is 70, and number-average molecular weight is 49.5 ten thousand, and molecular weight distribution is 6.3.
Comparative example 2
This comparative example is for illustration of the preparation of reference emulsion polymerized styrene butadiene rubber.
Emulsion polymerized styrene butadiene rubber is prepared according to the method for embodiment 1, unlike, in preparation process, do not add chain-transfer agent a, in reaction product, the content of throw out is 5.8 % by weight, obtains emulsion polymerized styrene butadiene rubber DG2, and mooney viscosity is 75, number-average molecular weight is 38.9 ten thousand, and molecular weight distribution is 6.8.
Embodiment 6-10
Embodiment 6-10 is for illustration of the preparation of the vulcanized rubber containing emulsion polymerized styrene butadiene rubber of the present invention.
(1) preparation of rubber unvulcanizate:
Stearic acid (the polite Chemical Co., Ltd. in Hong Kong of the emulsion polymerized styrene butadiene rubber G1-G5 respectively 100 weight parts prepared by embodiment 1-5,1 weight part, SA1801), 10 the weight part medium super abrasion furnace black N220(Tianjin gold autumns real carbon black Chemical Co., Ltd.), 60 weight part white carbon black 115GR(goldschmidt chemical corporation) mix and adopt Haake thermal treatment, wherein, thermal treatment temp is 150 DEG C, rotating speed is 30rpm/min, and the time is 7min.After thermal treatment completes, said mixture is added in mill, and add the zinc oxide (Liuzhou Xin Pin company limited) of 2.5 weight parts, stearic acid (the polite Chemical Co., Ltd. in Hong Kong of 1 weight part, SA1801), the antioxidant 4020 of 2 weight parts and N-cyclohexyl-2-benzothiazole sulfonamide (Hebi Uhoo Rubber Chemicals Co., Ltd. of 1.4 weight parts, CZ) and 0.75 weight part vulkacit D (Guangzhou Li great rubber raw materials trade Co., Ltd, DPG) and 6 weight part silane coupling agent Si69, at 50 ± 5 DEG C mixing 60 minutes, obtain rubber unvulcanizate H1-H5.
(2) sulfuration:
150 DEG C, under 12MPa, rubber unvulcanizate H1-H5 step (1) obtained carries out sulfidizing 40 minutes respectively on vulcanizing press, obtains vulcanized rubber S1-S5.
Comparative example 3-4
Comparative example 3-4 is for illustration of the preparation method of the vulcanized rubber containing reference emulsion polymerized styrene butadiene rubber.
Rubber is prepared according to the method for embodiment 6-10, unlike, described emulsion polymerized styrene butadiene rubber G1-G5 substitutes with the emulsion polymerized styrene butadiene rubber DG1-DG2 obtained by comparative example 1-2 of identical weight part respectively, obtains vulcanized rubber DS1-DS2.
Test case 1-5
Test case 1-5 is for illustration of the test of vulcanized rubber performance provided by the invention.
(1) test of mechanical property:
Vulcanized rubber S1-S5 is made the thick vulcanized rubber sheet of 2mm respectively; And according to the 1 type dumbbell shaped cut-off knife specified in GB/T528-1998, the vulcanized rubber sheet obtained is cut into dumbbell shaped standard film, rubber puller system is adopted (to produce purchased from Japanese Shimadzu Corporation, model is AG-20KNG) carry out the test that described vulcanized rubber sheet carries out mechanical property, wherein, probe temperature is 25 DEG C, pulling speed is 500 mm/min, obtains the tear strength of vulcanized rubber, tensile strength, 300% tensile modulus and tensile yield.Acquired results is as shown in table 1.
(2) anti-deformation nature test:
According to the 1 type dumbbell shaped cut-off knife specified in GB/T528-92, vulcanized rubber S1-S5 being cut into dumbbell shaped standard film, is 25 DEG C at probe temperature, and pulling speed is broken by sample under the condition of 500 mm/min.Sample after tension fracture is placed 3min, then two portions of fracture is coincide together, measure the distance of coincideing between rear two parallel lines, be calculated as follows permanent elongation:
S
b=100(L
t-L
0)/L
0, wherein, S
bfor permanent elongation, %; L
tfor sample coincide the distance between rear two parallel lines, mm; L
0for initial trial length, mm.Acquired results is as shown in table 1.
Contrast test example 1-2
Contrast test example 1-2 is for illustration of the test of reference vulcanized rubber performance.
Test according to the performance of method to vulcanized rubber of test case 1-5, unlike, described vulcanized rubber S1-S5 substitutes with vulcanized rubber DS1-DS2 respectively, and acquired results is as shown in table 1.
Table 1
As can be seen from the result of embodiment and comparative example, adopt chain-transfer agent provided by the invention, the emulsion polymerized styrene butadiene rubber that molecular weight distribution is narrower can not only be obtained, the mechanical property of the vulcanized rubber containing described emulsion polymerized styrene butadiene rubber can also be improved.The analytical results of floe content as can be seen from emulsion polymerized styrene butadiene rubber, by adopting chain-transfer agent provided by the invention, can control the generation of throw out effectively, thus can reduce the cycle of production cost, extension device maintenance.In addition, chain-transfer agent provided by the invention is non-mercaptan type chain transfer agent, does not have foul odour, avoids the harm to site operation personnel, has prospects for commercial application.
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.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (18)
1. a chain-transfer agent, it is characterized in that, the random copolymers that described chain-transfer agent is the olefin unit and at least two kinds of conjugated diene structural units containing at least one with structure shown in formula I, the number-average molecular weight of described random copolymers is not more than 20000;
Wherein, R
1-R
3identical or different, and be independently H or C separately
1-C
5alkyl.
2. chain-transfer agent according to claim 1, wherein, the olefin unit having a structure shown in formula I by a kind of in described random copolymers and two kinds of conjugated diene structural units form.
3. chain-transfer agent according to claim 2, wherein, with the olefin unit with structure shown in formula I of 100 weight parts for benchmark, the total content of two kinds of conjugated diene structural units is 100-400 weight part.
4. chain-transfer agent according to claim 2, wherein, described conjugated diene structural unit is the structural unit derived from conjugated diene, described conjugated diene is selected from divinyl, isoprene, cyclopentadiene, 1,3-pentadiene, Vinylstyrene, 1, two kinds in 3-hexadiene and 2,3-dimethylbutadiene.
5. according to the chain-transfer agent in claim 1-4 described in any one, wherein, the number-average molecular weight of described random copolymers is 1000-20000.
6. chain-transfer agent according to claim 5, wherein, the number-average molecular weight of described random copolymers is 2000-12000.
7. chain-transfer agent according to claim 6, wherein, the number-average molecular weight of described random copolymers is 4000-8000.
8. the preparation method of a chain-transfer agent, it is characterized in that, under the method is included in the existence of initiator and under olefinic polyreaction condition, olefinic monomer and at least two kinds of conjugated dienes at least one with structure shown in formula II carry out polyreaction in a solvent, make to obtain the random copolymers that number-average molecular weight is not more than 20000;
Wherein, R
1-R
3identical or different, and be independently H or C separately
1-C
5alkyl.
9. the preparation method of chain-transfer agent according to claim 8, wherein, the number-average molecular weight of described random copolymers is 1000-20000.
10. the preparation method of chain-transfer agent according to claim 9, wherein, the number-average molecular weight of described random copolymers is 2000-12000.
The preparation method of 11. chain-transfer agents according to claim 10, wherein, the number-average molecular weight of described random copolymers is 4000-8000.
12. preparation methods according to claim 8, wherein, it is 40-100 DEG C that described olefinic polyreaction condition comprises polymerization temperature, and polymerization pressure is 0.2-0.6MPa, and polymerization time is 20-60 minute.
13. preparation methods according to claim 12, wherein, it is 50-80 DEG C that described olefinic polyreaction condition comprises polymerization temperature, and polymerization pressure is 0.3-0.5MPa, and polymerization time is 30-60 minute.
14. preparation methods according to Claim 8 in-13 described in any one, wherein, in the preparation process of described chain-transfer agent, the olefinic monomer having a structure shown in formula II by a kind of and two kinds of conjugated dienes carry out polyreaction in a solvent.
15. preparation methods according to claim 14, wherein, with the olefinic monomer with structure shown in formula II of 100 weight parts for benchmark, total consumption of two kinds of conjugated dienes is 100-400 weight part.
16. preparation methods according to Claim 8 in-13 described in any one, wherein, the olefinic monomer with structure shown in formula II is selected from 2,4-phenylbenzene-4-methyl-2-amylene, 2,4-phenylbenzene-4-methyl-2-hexene, 2, one or more in 4-phenylbenzene-4-methyl-2-heptene, 2,4-phenylbenzene-4-methyl-2-octenes and 2,4-phenylbenzene-4-methyl-2-nonene.
17. chain-transfer agents prepared by the method in claim 8-16 described in any one.
The application of chain-transfer agent in 18. claim 1-7 and 17 described in any one in olefinic polyreaction.
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| CN1103645A (en) * | 1993-12-10 | 1995-06-14 | 久联化学工业股份有限公司 | Water-thinned high molecular emulsoid with high performance |
| CN1128765A (en) * | 1995-02-09 | 1996-08-14 | 久联化学工业股份有限公司 | Aqueous high molecular emulsion |
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| CN1103645A (en) * | 1993-12-10 | 1995-06-14 | 久联化学工业股份有限公司 | Water-thinned high molecular emulsoid with high performance |
| CN1128765A (en) * | 1995-02-09 | 1996-08-14 | 久联化学工业股份有限公司 | Aqueous high molecular emulsion |
| CN101735184A (en) * | 2008-11-11 | 2010-06-16 | 深圳市海川实业股份有限公司 | Trithiocarbonate chain transfer agent and preparation method thereof |
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