CN1544481A - High conversion rate rubber latex preparation method - Google Patents
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- CN1544481A CN1544481A CNA2003101152338A CN200310115233A CN1544481A CN 1544481 A CN1544481 A CN 1544481A CN A2003101152338 A CNA2003101152338 A CN A2003101152338A CN 200310115233 A CN200310115233 A CN 200310115233A CN 1544481 A CN1544481 A CN 1544481A
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Abstract
The invention relates to a process for preparing high conversion rate latex by using aliphatic conjugated diolefin hydrocarbon, aromatic vinyl compound as main monomer, wherein C3-C5 vinyl non-saturated carboxylic acid can be added, the emulsifier includes abietic acid saponin and aliphatic acid saponin, the oil solubility hydroperoxides and ferrous salt form redox initiation system, alkyl sulfhydrate is used as the molecular weight modifier. The rubber latex with conversion rate over 90% can be prepared through intermittent emulsion polymerization at the polymerization temperature between 10-55 deg. C.
Description
Technical field
The present invention relates to a kind of preparation method of latex of high conversion, particularly be suitable for the manufacture method of road asphalt properties-correcting agent with synthetic latex especially styrene-butadiene latex.
Background technology
Along with developing rapidly of world's road construction, generally begin to adopt the method that in pitch, adds properties-correcting agent to improve the bituminous physicals in the world.Properties-correcting agent commonly used has rubber-like, resene and thermoplastic elastomer.For many years, the research of asphalt modification is constantly carried out in countries in the world, has delivered a large amount of relevant patents.Domestic main achievement in research concentrates on materials such as the general-purpose plastics of selecting for use market common, rubber and carries out the improved field of pitch complete processing, does not retrieve to adopt latex to carry out the patent of asphalt modification aspect.Relevant article has Jiang Xizhi, Dan Zhiyi etc. to be published in " styrene butadiene latex modified asphalt performance research " on " pavement construction material ", and wherein adopting solid content is the styrene-butadiene latex of 20-23%; Wang Chun is published in " the utilizing High Solid Content SBR Latex modification heated bitumen " on " Chinese architecture waterproof " the 1st phase of calendar year 2001 for a long time, and the solid content that has wherein adopted the special process exploitation is 70% styrene-butadiene latex; The red grade of the Zhao Ji of Qilu Petrochemical rubber plant is published in " industrial trial of SBR latex for paving " on " China Synthetic Rubber Industry " o. 11th in 2000, and wherein adopting solid content is that the 1502 styrene-butadiene rubber(SBR) rubber cements of 20-23% carry out the visbreaking agglomeration technique and concentrate that to produce solid content be 45% SBR latex for paving.Latex synthetic technology with rubber performance adopts the low-temperature oxidation reduction method to produce more, in order to keep rubber performance, often will control its transformation efficiency and be no more than 70%, such as 1500 and 1502 rubber.Also some rubber-like latex adopts pyroprocess to synthesize, but its transformation efficiency is not high.External polymer modified asphalt technical development early has more than 50 year history so far, and the modifying asphalt patent of delivering is more, but great majority are modified technique aspects, as US6074469, US5710196, JP62-100555, WO0077098 etc.Patent quantity about synthetic latex properties-correcting agent is few, and US5534568 has announced divinyl, vinylbenzene and the butoxymethyl acrylamide method of copolymerization properties-correcting agent under certain condition; US5837756 has announced divinyl, vinylbenzene reacted in organolithium and polar solvent and has made the polymkeric substance that number-average molecular weight is 30000-85000; US5583173 has announced that low soap method carries out divinyl and styrene emulsion copolymerization and obtain transformation efficiency greater than 50% polymkeric substance; EP936232 has announced that it is 51000 polymkeric substance that in organolithium and polar solvent successive polymerization divinyl and vinylbenzene make number-average molecular weight; US6136899 announced synthetic high molecular in the US5583173 patent and low-molecular-weight latex has been mixed with properties-correcting agent, and the gained modifying asphalt has anti-rut, low temperature resistant advantage.The complicated process of preparation of the synthetic latex properties-correcting agent that these patents are announced, gained latex transformation efficiency is low.
Summary of the invention
The objective of the invention is to invent a kind of transformation efficiency greater than rubber-like latex preparation technology 90%, that be used for asphalt modification.
For realizing the object of the invention, the technology of employing is: with aliphatics conjugated diene, aromatic ethenyl thing is main monomer, and can add C
3～C
5The vinyl unsaturated carboxylic acid, emulsifying agent comprises RA rosin acid, fatty acid soaps etc., redox class initiator system with oil soluble superoxide and ferrous salt formation, molecular weight regulator can be selected the alkyl sulfhydryl class for use, under the temperature condition that changes (ladder-elevating temperature mode), adopt the intermittent feeding mode in batches add auxiliary agent, synthetic a kind of rubber-like, transformation efficiency is greater than 90% latex.Specifically:
Set of monomers becomes (add-on in aliphatics conjugated diene and aromatic ethenyl thing is 100 weight parts, and is as follows) 65～75 parts of aliphatics conjugated dienes, 25～35 parts of aromatic ethenyl things, C
3～C
5Vinyl unsaturated carboxylic acid 0-3 part, wherein the aliphatics conjugated diene comprises divinyl, aromatic ethenyl compound comprises vinylbenzene, alpha-methyl styrene, C
3～C
5The vinyl unsaturated carboxylic acid comprise vinylformic acid, methacrylic acid, methylene-succinic acid and their mixture, emulsifying agent is disproportionated rosin acid soap, fatty acid soaps etc., can select for use a certain, also can be several composite, the emulsifying agent consumption is 4.0～7.0 parts; Adopt the disposable adding of monomer, add molecular weight regulator more than three times, add emulsifying agent more than four times, initiator carries out the intermittent type letex polymerization, polymerization temperature is 5～55 ℃, but after adding emulsifying agent, initiator three times ladder-elevating temperature.
The method of special recommendation of the present invention is:
Monomer is once added, the add-on first of emulsifying agent is the 85-98% of total add-on, and molecular weight regulator add-on first is 70～85% of total add-on, and the add-on first of initiator is 20～35% of total add-on, sustained reaction 3～6 hours, temperature of reaction are 5～25 ℃; The add-on second time of emulsifying agent is 0.2～6% of total add-on, and the add-on second time of initiator is 15～30% of total add-on, and sustained reaction 3～5 hours, temperature of reaction are 5～30 ℃, preferably 10～20 ℃; The add-on for the third time of emulsifying agent is 0.2～3% of total add-on, and the add-on for the third time of initiator is 10～25% of total add-on, and sustained reaction 3～5 hours, temperature of reaction are 5～35 ℃, preferably 10～32 ℃; The 4th add-on of emulsifying agent is 0.2～3% of total add-on, and the 4th add-on of initiator is 10～30% of total add-on, and sustained reaction 3～5 hours, temperature of reaction are 5～45 ℃, preferably 10～42 ℃; The 5th add-on of emulsifying agent is 0～3% of total add-on, and the 5th add-on of initiator is 0～30% of total add-on,, sustained reaction 3～5 hours, temperature of reaction are 35～55 ℃, preferably 38～52 ℃; Molecular weight regulator add-on for the second time is 4～15% of total add-on, molecular weight regulator add-on for the third time is 4～15% of total add-on, the 4th add-on of molecular weight regulator is 0～8% of total add-on, the adding mode of molecular weight regulator does not limit especially, different according to reaction control, can add with different batches emulsifying agent, initiator.When transformation efficiency reaches 90.0% when above, add the processing that outgases behind terminator, the anti-aging agent, preferably adopt the processing that outgases of vacuum flashing removal method.
The best mode of control reaction temperature is to adopt the form of cascade raising temperature to carry out polyreaction after adding emulsifying agent for the third time.Come controls reaction speed and rubber performance better with the temperature of reaction gradient.
Initiator can be the oil soluble di-isopropylbenzene hydroperoxide among the present invention, hydrogen phosphide cumene and ferrous sulfate or EDTA ferrisodium salt constitute redox class initiator system, wherein the oxygenant consumption is preferably 0.2～0.8 part, the reductive agent consumption is preferably 0.01～0.30 part, molecular weight regulator can be lauryl mercaptan of using always etc., its add-on is preferably 0.3～0.8 part, required ionogen in all the other letex polymerizations, sequestrants etc. all can be used, ionogen can be a Repone K, potassiumphosphate, sequestrant can be disodium EDTA (an EDTA disodium), potassium pyrophosphate etc.
Emulsifying agent among the present invention can be a kind of, also can be composite class.Can adopt nilox resin acid potash soap during single use, preferably improve the consumption of single soap this moment.But in order to make styrene-butadiene latex of the present invention have good rubber performance and suitable speed of response simultaneously, mixed emulsifier is preferably used in suggestion, be that nilox resin acid potash soap and fatty acid soaps are composite, the compound proportion of emulsifying agent is disproportionated rosin acid soap preferably: fatty acid soaps is 2～3: 1.
By a batch adding emulsifying agent, oxygenant, reductive agent and molecular weight regulator etc., reduced the generation of gel among the present invention, made institute's synthetic latex have suitable structural gel content and mooney viscosity; Simultaneously by adding auxiliary agent in batches, the may command speed of response obtains the higher and latex of rubber performance excellence of transformation efficiency; In removing latex, during residual monomer, can adopt the vacuum flashing removal method, add terminator and anti-aging agent simultaneously, can reduce residual monomer in the latex effectively, and make the latex performance variation little.
The latex that uses the present invention to produce when mixing with pitch, can not produce the intensive pot phenomenon of overflowing, and the performance of modified bitumen excellence that makes can satisfy the request of national standard of urban road laying.
The testing method of latex adopts conventional method of analysis, and wherein the SH/T1154-92 standard is adopted in the test of total solid substance, and the SH/T1150-9210. standard is adopted in the test of pH value; The SH/T1152-92 standard is adopted in the test of viscosity; The SH/T1156-92 standard is adopted in capillary test; What structural gel was tested is the content of 48 hours toluene insolubleses, and the mooney viscosity testing standard is with the rubber testing method, and the SH/T1153-92 standard is adopted in the test of macroscopical gel.
Embodiment
Embodiment 1
Use the 10L polymeric kettle, at first vacuumize, use nitrogen replacement again, drop into de-salted water successively, (wherein nilox resin acid potash soap is 3.56 parts for emulsifier solution, 1.5 parts of fatty acid soaps), (wherein the reductive agent ferrous sulfate is 0.16 part for reductive agent, electrolyte solution, 0.5 part in Repone K, 0.07 part of EDTA disodium), 30 parts of vinylbenzene, 0.35 part of molecular weight regulator lauryl mercaptan, add 70 parts of divinyl then, open and stir, when keeping temperature of reaction to be 10 ℃, add oxidizing agent solution (0.09 part of di-isopropylbenzene hydroperoxide).10 ± 1 ℃ of control reaction temperature are kept reaction 4 hours, add and add liquid for the first time, 0.08 part in oxygenant, 0.06 part of emulsifying agent nilox resin acid potash soap, 0.05 part of molecular weight regulator.Keep reaction 6 hours, add and to add liquid for the second time, wherein oxygenant is 0.09 part, 0.06 part of emulsifying agent nilox resin acid potash soap, and 0.1 part of molecular weight regulator improves temperature of reaction to 25 ℃ then.Keep reaction 7 hours, add for the third time material, wherein oxygenant is 0.1 part, and 0.06 part of emulsifying agent nilox resin acid potash soap improves temperature of reaction to 45 ℃ then.Transformation efficiency reaches 90% when above, and stopped reaction adds terminator and anti-aging agent, in degassing still vacuum tightness is-0.10Mpa, under the condition that the still temperature is 40 ℃, outgases to remove residual monomer, and the degassing time is 1.5 hours.Finished product after filtering at last.
The physical index of latex is:
Transformation efficiency 93.31%; PH value 10.65; Viscosity 78mPas; Surface tension 56.5mN/m; Particle diameter 105m; Structural gel 15.4%, mooney viscosity 65, macroscopical gel 0.017%.
Embodiment 2
Cinnamic consumption is increased to 35 parts by 30 parts among the embodiment 1,65 parts of divinyl, the consumption of first molecular weight regulator lauryl mercaptan is increased to 0.5 part, add 5.06 parts of emulsifying agent nilox resin acid potash soaps again, (wherein the reductive agent ferrous sulfate is 0.16 part, 0.5 part in Repone K for reductive agent, electrolyte solution, 0.07 part of EDTA disodium), open and stir, when keeping temperature of reaction to be 15 ℃, add oxidizing agent solution (0.08 part of hydrogen phosphide cumene).15 ± 1 ℃ of control reaction temperature are kept reaction 5 hours, add and add liquid for the first time, 0.07 part in oxygenant, 0.06 part of emulsifying agent nilox resin acid potash soap, 0.04 part of molecular weight regulator.Keep reaction 5 hours, add and to add liquid for the second time, wherein oxygenant is 0.08 part, 0.06 part of emulsifying agent nilox resin acid potash soap, and 0.08 part of molecular weight regulator improves temperature of reaction to 30 ℃ then.Keep reaction 5 hours, add for the third time material, wherein oxygenant is 0.09 part, and 0.06 part of emulsifying agent nilox resin acid potash soap improves temperature of reaction to 40 ℃ then.Transformation efficiency reaches 90% when above, and stopped reaction adds terminator and anti-aging agent, in degassing still vacuum tightness is-0.10Mpa, under the condition that the still temperature is 40 ℃, outgases to remove residual monomer, and the degassing time is 1.5 hours.Obtain finished product at last after filtering.The latex of being produced still satisfies physical index and processing requirement.
Embodiment 3.
The vinylbenzene consumption is adjusted into 25.0 parts, and aggregated oxidant amount consumption is adjusted into 0.43 part, and other auxiliary agent is identical with example one with technology.Promptly add 0.3 part of molecular weight regulator first, (wherein nilox resin acid potash soap is 3.58 parts for emulsifier solution, 1.5 parts of fatty acid soaps), (wherein the reductive agent ferrous sulfate is 0.16 part for reductive agent, electrolyte solution, 0.5 part in Repone K, 0.07 part of EDTA disodium), adds 75 parts of divinyl then, open and stir, when keeping temperature of reaction to be 18 ℃, add oxidizing agent solution (0.13 part of di-isopropylbenzene hydroperoxide).18 ± 1 ℃ of control reaction temperature are kept reaction 5 hours, add and add liquid for the first time, and wherein oxygenant is 0.09 part, 0.08 part of emulsifying agent nilox resin acid potash soap, 0.04 part of molecular weight regulator.Keep reaction 6 hours, add and to add liquid for the second time, wherein oxygenant is 0.09 part, 0.08 part of emulsifying agent nilox resin acid potash soap, and 0.04 part of molecular weight regulator improves temperature of reaction to 35 ℃ then.Keep reaction 6 hours, add for the third time material, wherein oxygenant is 0.12 part, 0.08 part of emulsifying agent nilox resin acid potash soap, and 0.05 part of molecular weight regulator improves temperature of reaction to 50 ℃ then.Transformation efficiency reaches 90% when above, and stopped reaction adds terminator and anti-aging agent, in degassing still vacuum tightness is-0.10Mpa, under the condition that the still temperature is 40 ℃, outgases to remove residual monomer, and the degassing time is 1.5 hours.Finished product after filtering at last.Reaction times is 23 hours, and transformation efficiency reaches more than 90%.Still in the scope that requires, use properties can reach the Technology requirement to the physical index of the latex of being produced.
Embodiment 4
Prescription with reference to embodiment 1, but emulsifier system is adjusted into single emulsifying agent, promptly add 5.56 parts of nilox resin acid potash soaps first, (wherein reductive agent EDTA iron is received 0.02 part of salt for reductive agent, electrolyte solution, 0.5 part in Repone K), 30 parts of alpha-methyl styrenes, 0.3 part of molecular weight regulator lauryl mercaptan, the vinylformic acid that adds 1 part simultaneously, add 70 parts of divinyl then, open and stir, when keeping temperature of reaction to be 15 ℃, add oxidizing agent solution (0.08 part of di-isopropylbenzene hydroperoxide).15 ± 1 ℃ of control reaction temperature, keep reaction 4 hours, add and add liquid for the first time, 0.07 part in oxygenant, 0.06 part of emulsifying agent nilox resin acid potash soap is kept reaction 5 hours, add then and add for the second time liquid, wherein oxygenant is 0.07 part, 0.06 part of emulsifying agent nilox resin acid potash soap, 0.05 part of molecular weight regulator.Keep reaction 5 hours, add and to add liquid for the third time, wherein oxygenant is 0.08 part, 0.06 part of emulsifying agent nilox resin acid potash soap, and 0.1 part of molecular weight regulator improves temperature of reaction to 30 ℃ then.Keep reaction 5 hours, add the 4th time and add liquid, wherein oxygenant is 0.1 part, and 0.06 part of emulsifying agent nilox resin acid potash soap improves temperature of reaction to 40 ℃ then.Transformation efficiency reaches 90% when above, and stopped reaction adds terminator and anti-aging agent, in degassing still vacuum tightness is-0.10Mpa, under the condition that the still temperature is 40 ℃, outgases to remove residual monomer, and the degassing time is 1.5 hours.Finished product after filtering at last.Resulting latex polymerization excellent in stability, every performance index are close with embodiment 1, can satisfy the requirement of asphalt modification.
Comparative Examples 1
Adopting the method for embodiment 1, is 15 parts and adjust the vinylbenzene consumption, and the divinyl consumption is 85 parts, although also can synthesize stability latex preferably, but polymerization rate is slower, and institute's synthetic latex structures gel content is too low, and pitch softening point does not reach requirement after being used for asphalt modification.
Comparative Examples 2
Adopting the method for embodiment 1, is 45 parts and adjust the vinylbenzene consumption, and the divinyl consumption is 55 parts, and then institute's synthetic latex structures gel content and mooney viscosity are too high, can't satisfy the requirement of asphalt modification.
Comparative Examples 3
Prescription and synthetic method with reference to embodiment 4, adopt vinylbenzene to replace alpha-methyl styrene, adopting single disproportionated rosin acid soap is emulsifying agent, and first emulsifying agent consumption is reduced to 3.5 parts, and later on each additional amount is 0.06 part, then polymerization rate is slower, when the reaction times reached 28 hours, polymerisation conversion just reached 80%, and the latex stability that synthesizes is not good enough, the macroscopic view gel content reaches 1%, can't be used for asphalt modification.
Comparative Examples 4
Prescription and synthetic method with reference to embodiment 1, adopt 30 parts of vinylbenzene, 70 parts of divinyl add 5.0 parts of emulsifying agent disproportionated rosin acid soaps first, 0.4 part of molecular weight regulator, reductive agent, electrolyte solution (wherein the reductive agent ferrous sulfate is 0.16 part, 0.5 part in Repone K, 0.07 part of EDTA disodium), open and stir, when keeping temperature of reaction to be 10 ℃, add oxidizing agent solution (0.09 part of di-isopropylbenzene hydroperoxide, 0.06 part of emulsifying agent nilox resin acid potash soap).10 ± 1 ℃ of control reaction temperature are kept reaction 6 hours, add and add liquid for the first time, 0.10 part in oxygenant, 0.06 part of emulsifying agent nilox resin acid potash soap, 0.05 part of molecular weight regulator.Keep reaction 6 hours, add and to add liquid for the second time, wherein oxygenant is 0.10 part, 0.06 part of emulsifying agent nilox resin acid potash soap, and 0.1 part of molecular weight regulator improves temperature of reaction to 35 ℃ then.Keep reaction 7 hours, polymerisation conversion can only reach 65%, can't make the latex of high conversion.
The synthesizing formula of table 1 latex
| Starting material | Embodiment | Comparative example | |||||
| ??1 | ???2 | ???3 | ???4 | ???1 | ???2 | ???3 | |
| Vinylbenzene alpha-methyl styrene divinyl vinylformic acid | ??30.0 ??- ??70.0 ??- | ??35.0 ??- ??65.0 ??- | ??25.0 ??- ??75.0 ??- | ??- ??30.0 ??70.0 ??1.0 | ??15.0 ??- ??85.0 ??- | ??45.0 ??- ??55.0 ??- | ??30.0 ??- ??70.0- ??1.0 |
| Disproportionated rosin acid soap fatty acid soaps di-isopropylbenzene hydroperoxide hydrogen phosphide cumene ferrous sulfate NaFeEDTA sodium salt lauryl mercaptan EDETATE SODIUM | ??3.74 ??1.50 ??0.36 ??- ??0.16 ??- ??0.50 ??0.07 | ??5.24 ??- ??- ??0.32 ??0.16 ??0.62 ??0.07 | ??3.82 ??1.50 ??0.43 ??- ??0.16 ??- ??0.43 ??0.07 | ??5.80 ??- ??0.40 ??- ??- ??0.02 ??0.45 ??- | ??3.74 ??1.50 ??0.36 ??- ??0.16 ??- ??0.50 ??0.07 | ??3.74 ??1.50 ??0.36 ??- ??0.16 ??- ??0.50 ??0.07 | ??3.80 ??- ??0.40 ??- ??- ??0.02 ??0.45 ??- |
Table 2 latex performance and pitch physical and chemical index
| The latex performance | Embodiment | Comparative Examples | |||||
| ????1 | ????2 | ????3 | ????4 | ????1 | ????2 | ????3 | |
| Transformation efficiency/% | ??93.31 | ??92.88 | ??95.40 | ??95.17 | ??90.24 | ??93.40 | ??80.34 |
| Surface tension/mN/m | ??56.5 | ??58.6 | ??62.4 | ??60.7 | ??61.5 | ??59.5 | ??59.4 |
| The pH value | ??10.65 | ??10.88 | ??10.92 | ??10.39 | ??10.74 | ??10.78 | ??10.02 |
| Viscosity/mPa.s | ??78.0 | ??92.5 | ??67.5 | ??58.0 | ??48.5 | ??55.0 | ??38.0 |
| Mooney viscosity | ??65 | ??73 | ??58 | ??65 | ??42 | ??128 | ??- |
| Structural gel/% | ??15.4 | ??12.87 | ??4.76 | ??10.55 | ??1.55 | ??45.24 | ??- |
| Polymerization stability | Good | Good | Good | Good | Better | Better | Relatively poor |
| Ductility (5 ℃, cm) | ??＞100 | ??＞100 | ??＞100 | ??＞100 | ??＞80 | ??37 | ??- |
| Softening temperature/℃ | ??53.5 | ??56.5 | ??51.5 | ??54.0 | ??43.5 | ??52.0 | ??- |
| Penetration degree/0.1mm | ??108 | ??110 | ??103 | ??118 | ??110 | ??97 | ??- |
Annotate: ductility, softening temperature and penetration degree are the physical and chemical index of being surveyed behind No. 110 asphalt modifications.Latex to the polymerization stability difference will not be tested.
Claims (11)
1. the preparation method of the latex of a high conversion, with aliphatics conjugated diene, aromatic ethenyl thing is main monomer, use initiator, emulsifying agent, molecular weight regulator to carry out emulsion polymerization prepared latex, it is characterized in that the add-on in aliphatics conjugated diene and aromatic ethenyl thing is 100 weight parts, set of monomers becomes: 65～75 parts of aliphatics conjugated dienes, 25～35 parts of aromatic ethenyl things, C
3～C
50～3 part of vinyl unsaturated carboxylic acid, the emulsifying agent consumption is 4.0～7.0 parts; Adopt the disposable adding of monomer, add molecular weight regulator more than three times, add emulsifying agent more than four times, initiator carries out the intermittent type letex polymerization, polymerization temperature is 10～55 ℃, when transformation efficiency reaches 90.0% when above, add the processing that outgases of terminator, anti-aging agent.
2. latex preparation method according to claim 1 is after it is characterized in that adding emulsifying agent, initiator for the third time, the back batch of polymerization that progressively heats up.
3. latex preparation method according to claim 1, it is characterized in that monomer is once added, the add-on first of emulsifying agent is the 85-98% of total add-on, molecular weight regulator add-on first is 70～85% of total add-on, the add-on first of initiator is 20～35% of total add-on, sustained reaction 3～6 hours, temperature of reaction are 5～25 ℃; The add-on second time of emulsifying agent is 0.2～6% of total add-on, and the add-on second time of initiator is 15～30% of total add-on, and sustained reaction 3～5 hours, temperature of reaction are 5～30 ℃; The add-on for the third time of emulsifying agent is 0.2～3% of total add-on, and the add-on for the third time of initiator is 10～25% of total add-on, and sustained reaction 3～5 hours, temperature of reaction are 5～35 ℃; The 4th add-on of emulsifying agent is 0.2～3% of total add-on, and the 4th add-on of initiator is 10～30% of total add-on, and sustained reaction 3～5 hours, temperature of reaction are 5～45 ℃; The 5th add-on of emulsifying agent is 0～3% of total add-on, and the 5th add-on of initiator is 0～30% of total add-on, and sustained reaction 3～5 hours, temperature of reaction are 35～55 ℃; Molecular weight regulator add-on for the second time is 4～15% of total add-on, and molecular weight regulator add-on for the third time is 4～15% of total add-on, and the 4th add-on of molecular weight regulator is 0～8% of total add-on; When transformation efficiency reaches 90.0% when above, add the processing that outgases behind terminator, the anti-aging agent.
4. latex preparation method according to claim 1 is characterized in that the aliphatics conjugated diene is a divinyl.
5. latex preparation method according to claim 1 is characterized in that the aromatic ethenyl thing comprises vinylbenzene, alpha-methyl styrene.
6. latex preparation method according to claim 1 is characterized in that C
3～C
5The vinyl unsaturated carboxylic acid comprise vinylformic acid, methacrylic acid, methylene-succinic acid and their mixture.
7. according to claim 1 or 2 or 3 described latex preparation methods, it is characterized in that emulsifying agent is disproportionated rosin acid soap, fatty acid soaps, wherein one or more are composite.
8. latex preparation method according to claim 7 is characterized in that emulsifying agent is meant disproportionated rosin acid soap and fatty acid soaps is composite to form.
9. latex preparation method according to claim 8, the compound proportion that it is characterized in that emulsifying agent is a disproportionated rosin acid soap: fatty acid soaps is 2～3: 1.
10. latex preparation method according to claim 1 has also been used sequestrant when it is characterized in that polymerization, sequestrant is a disodium EDTA, and its add-on is 0.05～0.1 part of monomer total amount.
11. latex preparation method according to claim 1 is characterized in that the degassing is handled to be meant and to adopt the processing that outgases of vacuum flashing removal method.
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| CN100429246C (en) * | 2006-07-04 | 2008-10-29 | 中国石油天然气集团公司 | Preparation method of new type latex |
| CN100429249C (en) * | 2005-07-07 | 2008-10-29 | 中国石油天然气集团公司 | Technology for preparing carboxyl butylbenzene latex |
| CN101423586B (en) * | 2007-11-01 | 2011-09-07 | 中国石油天然气股份有限公司 | Method for producing high conversion rate butadiene-acrylonitrile copolymer rubber |
| CN105085786A (en) * | 2015-08-26 | 2015-11-25 | 常州海霸橡胶有限公司 | Preparation method of low-compression permanent-deformation carboxylic acrylate rubber |
| CN106749916A (en) * | 2016-11-30 | 2017-05-31 | 黄河三角洲京博化工研究院有限公司 | A kind of emulsified asphalt is modified and uses the preparation method of styrene-butadiene latex |
| CN111925662A (en) * | 2020-08-24 | 2020-11-13 | 山东京博中聚新材料有限公司 | Polystyrene emulsion for modified emulsified asphalt and preparation method and application thereof |
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| CN113512148A (en) * | 2021-08-04 | 2021-10-19 | 福建亮晶晶新材料有限公司 | Preparation method of special styrene-butadiene latex for road asphalt modification |
| CN114456316A (en) * | 2020-11-07 | 2022-05-10 | 中国石油化工股份有限公司 | Method for improving emulsion polymerized styrene butadiene rubber conversion rate |
| CN115703847A (en) * | 2021-08-04 | 2023-02-17 | 中国石油天然气股份有限公司 | Method for concentrating styrene-butadiene latex |
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2003
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| CN100429249C (en) * | 2005-07-07 | 2008-10-29 | 中国石油天然气集团公司 | Technology for preparing carboxyl butylbenzene latex |
| CN100429246C (en) * | 2006-07-04 | 2008-10-29 | 中国石油天然气集团公司 | Preparation method of new type latex |
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| CN105085786A (en) * | 2015-08-26 | 2015-11-25 | 常州海霸橡胶有限公司 | Preparation method of low-compression permanent-deformation carboxylic acrylate rubber |
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| CN113512148A (en) * | 2021-08-04 | 2021-10-19 | 福建亮晶晶新材料有限公司 | Preparation method of special styrene-butadiene latex for road asphalt modification |
| CN115703847A (en) * | 2021-08-04 | 2023-02-17 | 中国石油天然气股份有限公司 | Method for concentrating styrene-butadiene latex |
| CN115703847B (en) * | 2021-08-04 | 2024-03-01 | 中国石油天然气股份有限公司 | Method for concentrating styrene-butadiene latex |
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