CN110204656A - A kind of emulsion polymerisation process - Google Patents
A kind of emulsion polymerisation process Download PDFInfo
- Publication number
- CN110204656A CN110204656A CN201910503550.8A CN201910503550A CN110204656A CN 110204656 A CN110204656 A CN 110204656A CN 201910503550 A CN201910503550 A CN 201910503550A CN 110204656 A CN110204656 A CN 110204656A
- Authority
- CN
- China
- Prior art keywords
- emulsifier
- parts
- reaction
- acid
- latex
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention relates to a kind of emulsion polymerisation process for preparing big partial size polydiene latex.It is controlled using V-shape pH, acids agglomerant is added during emulsion polymerization monomer conversion 10-85% reduces system pH to 4-9, and after the completion of acids agglomerant is added and pH is increased to 9.5-13 by conversion ratio 50-90%, addition alkaloids.It is wherein reduced the stage in pH, the stability of partial emulsifier is corrupted such that small particle emulsion particle occurs poly- and and increases partial size.In pH boost phase, the emulsifier being destroyed is regenerated, and enhances system stability.This emulsion polymerisation process can obtain the large grain size latex of 200-500nm, and partial size growth rate is greater than 20nm/h.
Description
Technical field
The invention belongs to macromolecule preparation field, in particular to a kind of lotion for preparing big partial size polydiene latex is poly-
Conjunction method.
Background technique
ABS resin is by styrene, acrylonitrile grafting to big partial size polybutadiene latex (partial size is 250~350nm)
Ternary graft copolymer.Big partial size polybutadiene latex is the core component and skeleton of ABS resin, and it is tough that it gives ABS resin
Property, directly affect the performance of ABS resin.Synthesizing big partial size polybutadiene latex has two kinds of one-step method and two step method (agglomeration technique)
Method.
The polybutadiene latex usual reaction time of one-step synthesis method partial size 300nm is longer, partial size growth rate about 5-
10nm/h, as described in CN200910237011.0, one-step method big partial size polybutadiene latex partial size produced 250~
350nm, polymerization time about 25~70 hours.
After the eighties, one-step method is gradually agglomerated (two step method) substitution.Agglomeration technique first synthesizes latex of polybutadiene in small grain size
(partial size is 60~150nm), then big partial size polybutadiene latex is zoomed into agglomerant agglomeration.
The agglomeration technique first step synthesizes polybutadiene in small grain size latex, it usually needs 10 hours or so reaction time obtained
Average grain diameter is the small grain size latex of 100nm, and partial size growth rate is about 10nm/h.CA123290A discloses a kind of polymerization work
Skill is reacted 13 hours at 70 DEG C, and product average grain diameter is 120nm；CN00107134.3 discloses a kind of polymerization technique, in 8-
The latex of polybutadiene in small grain size that partial size is 80-120nm is made in 11 hours.CN200410080805.8 discloses a kind of polymerization
Technique, using the emulsifier being mixed by potassium rosinate and potassium oleate, it is 100-120nm's that partial size is made in 7-10 hours
Latex of polybutadiene in small grain size.
Agglomerant is added from the small grain size latex of about 100nm in agglomeration technique second step, obtains the large grain size latex of about 300nm.
The common agglomerant of chemical agglomeration method is acetic acid.CN200510059339.X discloses a kind of agglomeration method, using including acetic acid
0.5-2.5 parts (butt), 0.4-2.5 parts of regenerative agent (butt), 0-0.2 parts of regulator (butt) and the different behaviour of use
Make method, the small particles latex of average grain diameter 80-120nm, pH8-13 is zoomed into the big particle latex of 300-700nm.
On average, agglomeration technique obtains the large grain size latex of about 300nm by two steps, about 11-15 hours time.
Based on known process, polymerization and agglomeration carry out respectively in the preparation process of polybutadiene latex.It is poly-
Close reaction it is different with the process conditions of agglomeration process, emulsion polymerization process needs emulsion particle number N in maintenance system, with acquisition compared with
Fast rate of polymerization Rp, and agglomeration process is the process for being greatly reduced N；Emulsion polymerization process needs to maintain certain emulsifier
Concentration cE, to guarantee that emulsion particle can be stabilized in system, excessively unstable rule has that cohesion is slagged tap；And agglomeration
Process then needs to reduce emulsifier concentration cE, the stability of emulsion particle is destroyed, is gathered simultaneously to bring it about.Therefore, it was polymerizeing
It is extremely difficult that agglomeration process is integrated in journey.
Summary of the invention
The purpose of the present invention is to provide a kind of emulsion polymerisation process, anti-by using polymerization is integrated in same reaction kettle
Monomer conversion and 200- that one-step method obtains > 90% within the time of average about 10h should be reached with the means of agglomeration process
The big partial size polydiene emulsion products of the partial size of 500nm, partial size growth rate are greater than 20nm/h.
In order to achieve the goal above, the invention adopts the following technical scheme:
The present invention provides a kind of emulsion polymerisation process for preparing big partial size polydiene latex, comprising the following steps:
(1) reaction kettle is added in the first reaction solution, is warming up to 55-85 DEG C, the first reaction solution pH >=10, preferably 10-12；Its
In the first reaction solution include monomer, emulsifier, chain-transferring agent, optional electrolyte, initiator, deionized water；
(2) when monomer conversion reaches 10-85%, preferably 50-70%, acids agglomerant, which is added, reduces reaction system pH
To 4-9, preferably 5-7；
(3) as monomer conversion 50-90%, preferably 70-90%, alkaloids is added and increase reaction system pH to 9.5-
13, preferably 10-12；
(4) after monomer conversion > 90%, preferably > 95% after, reaction complete discharging obtains big partial size polydiene latex
Product.
In a kind of emulsion polymerisation process preparing big partial size polydiene latex of the present invention, wherein the first reaction
Liquid constituent mass dosage is as follows:
100 parts of monomer
1.8-9 parts of emulsifier, preferably 3-5 parts
0.25-0.5 parts of chain-transferring agent, preferably 0.3-0.45 parts
0-2 parts of electrolyte, preferably 0.3-1.25 parts
0.2-0.6 parts of initiator, preferably 0.25-0.3 parts
90-240 parts of deionized water, preferably 140-200 parts
Emulsifier described in step (1) of the invention is selected from complex emulsifier, includes emulsification in compound emulsifying agent
Agent S and emulsifier I；S represents sensitive, and the emulsifier performance of emulsifier S is sensitive to pH, and I represents inert, emulsifier I's
Emulsifiability is insensitive to pH；Wherein emulsifier S is selected from carboxylic acid type anion emulsifier, corresponds to pKa > 5 of carboxylic acid, preferably selects
From one of disproportionated rosin acid, stearic acid, palmitic acid, the sodium salt of oleic acid or sylvite or a variety of；The emulsifier I be selected from it is non-from
Sub- emulsifier, preferably one of isomery alcohol ether or a variety of；The mass ratio that emulsifier S accounts for whole emulsifiers is 30-100%, excellent
Selecting 50-80%, emulsifier I to account for the mass ratio of whole emulsifiers is 0-70%, preferably 20-50%.
Monomer described in step (1) of the invention includes one of butadiene, styrene, isoprene or a variety of, institute
It states initiator and is selected from one of potassium peroxydisulfate, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide or a variety of, chain-transferring agent is uncle
Lauryl mercaptan, the electrolyte are selected from one of sodium salt, sylvite, sodium hydroxide, potassium hydroxide or a variety of.
Heat initiation or Redox Initiator, emulsion polymerization when using Redox Initiator can be used in step (1) of the present invention
In raw material accordingly comprising as cause auxiliary agent reducing substances such as ferrous salt and reducing sugar etc., ferrous salt such as ferrous sulfate with
Frerrous chloride, reducing sugar such as glucose and lactose.The dosage for causing auxiliary agent is 0.1-1 parts, in terms of 100 parts of monomer masses.
Acids agglomerant described in step (2) of the present invention is selected from organic acid or acid anhydrides one of of the pKa between 1-5
Or it is a variety of, it is preferably selected from one of acetic acid, acetic anhydride, lactic acid, benzoic acid, salicylic acid or a variety of, alkali described in step (3)
Substance be selected from inorganic base or hydrolysis in alkalinity inorganic salts, be preferably selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
One of potassium phosphate is a variety of.
The present invention further preferably in monomer conversion 40-70%, adds the second reaction solution, and the second reaction solution includes cream
One of agent S, chain-transferring agent, initiator are a variety of, and the dosage for adding emulsifier S is 0.1-1 parts, add chain-transferring agent use
Amount is 0.05-0.2 parts, and adding initiator amount is 0.05-0.5 parts, in terms of 100 parts of monomer masses.
When step (1) uses redox initiation system, the second reaction solution further preferably includes as initiation auxiliary agent
Reducing substances.
The present invention still more preferably use ladder temperature control method control reaction temperature, 55-75 DEG C of initial reaction temperature,
After monomer conversion is greater than 70%, 75-85 DEG C is increased the temperature to.
Latex products made from the emulsion polymerisation process of the present invention for preparing big partial size polydiene glue, feature
It is, latex average grain diameter is 200nm-500nm, preferably 250-400nm.
Present invention simultaneously provides a kind of acrylonitrile-butadiene-styrene (ABS) graft copolymerizations prepared by the latex products
Object, and its preparing the application in ABS (acrylic nitrile-butadiene-styrene).
The present invention uses the means that polymerization reaction and agglomeration process are integrated in same reaction kettle, reaches one-step method average
The polydiene emulsion products of > 90% monomer conversion and the partial size of 200-500nm are obtained in the time of about 10h.And it selects
It has selected appropriate mode and agglomeration process is integrated into polymerization process, so that (1) polymerization rate Rp is not reduced or reduced and can connect
By；(2) partial size increases to target zone；(3) partial size growth rate is greater than 20nm/h.
The present invention carries out emulsion polymerization first, and after monomer conversion is more than or equal to 10%, enough numbers are generated in system
Small particle emulsion particle, then carry out agglomeration, make the agglomeration of small particle emulsion particle and quickly increase partial size；And it is preferably converted in monomer
Rate starts to carry out agglomeration when being more than or equal to 50%, and the influence to polymerization rate Rp is minimum at this time；At the latest in monomer conversion
85%, preferably 70% when, carries out agglomeration, and the aggregate of several small grain size latexes formed in agglomeration process is merged
For an entirety.
It is not recommended that agglomeration is carried out when monomer conversion is less than 10%, because agglomeration causes polymerization rate Rp to decline
Drawback has exceeded the benefit that agglomeration causes product cut size to increase.
It is feasible that agglomeration is carried out when conversion ratio is greater than 85%, if following two negative effects can receive: (1) turning
When rate reaches 90%, partial size may not yet rise to acceptability limit, this problem can be made up by extending ag-glomeration time, but be caused
The increased negative effect of total production time；(2) gained large grain size latex is inherently the aggregate of several small grain size latexes
A rather than entirety.
When monomer conversion reaches 10-85%, acids agglomerant is further added into polymerization system by the present invention, reduces
System pH to reduce the concentration of effective component in compound emulsifying agent, therefore destroys small particle emulsion particle stability, so that
Small particle emulsion particle is poly- and and increases partial size.Since emulsifier effective component concentration is lower, product cut size is higher after agglomeration, in order to
Control latex average grain diameter is 200nm-500nm, needs accordingly to control the concentration of compound emulsifying agent effective component；Therefore the present invention
PH is adjusted by V-shape in clustering integration agglomeration process and controls emulsifier effective component concentration.
The present invention is further to prevent regional area in clustering integration agglomeration process (mainly sour feed zone is attached
The appearance of super large partial size emulsion particle beyond target zone caused by closely) acid concentration is excessively high, emulsifier effective concentration is too low is (out
Slag) problem, use the compound emulsifier system of emulsifier S and emulsifier I.By to anionic emulsifying in complex emulsifier
The adjusting of the usage ratio of agent S and nonionic emulsifier I, so that the emulsion particle surface in the excessively high regional area of acid concentration is still
Have a certain amount of nonionic emulsifier I (acids agglomerant is invalid to nonionic emulsifier I), play control partial size, prevent excessively it is attached
It is poly- to lead to the problem of slagging tap.
The present invention reaction rate and adjusts the product mix to improve, it is preferred to use in monomer conversion 40-70%, mends
Add the method for the second reaction solution.Second reaction solution includes one of emulsifier S, chain-transferring agent, initiator or a variety of.Wherein mend
The effect for improving polymerization rate can be played by adding emulsifier and adding initiator respectively.It adds chain-transferring agent and plays adjusting
The effect of molecular structure.
The present invention preferably improves reaction temperature to 75-85 DEG C to improve reaction rate after conversion ratio is greater than 70%.
The beneficial effects of the present invention are integrate polymerization process and agglomeration process, on the one hand eliminate agglomeration kettle, Ke Yijie
Plant investment is saved, on the other hand reduces lotion connecting time, and agglomeration progress synchronous with polymerization, reaches one-step method average
The big partial size polydiene latex that > 90% monomer conversion and the partial size of 200-500nm are obtained in the time of about 10h produces
Product, partial size growth rate are greater than 20nm/h.
Specific embodiment
Illustrate that technical solution of the present invention, embodiment give specific embodiment and tool with specific embodiment below
The operating process of body, but protection scope of the present invention is not limited to following embodiments.
The nonionic emulsifier Lutensol To-3, To-5, To-7 are purchased from BASF, respectively isomerous tridecanol -3
(oxyethylene group) ether, isomerous tridecanol -5 (oxyethylene group) ether, isomerous tridecanol -7 (oxyethylene group) ether.Spend from
Sub- water is self-control.Other raw materials come from Aladdin Reagent Company.
Partial size is tested by Malvern Nano-ZS90 type particle size analyzer, and result is volume average particle size.
Embodiment 1
(1) the first reaction solution, including 95 parts of butadiene, 5 parts of styrene, 1.5 parts of potassium oleate, disproportionated rosin acid potassium 1.5 are taken
Part, 0.45 part of tert-dodecylmercaotan, 0.3 part of potassium peroxydisulfate, 0.3 part of potassium carbonate, 145 parts of deionized water be added to reaction kettle
In, the first reaction solution pH11 is warming up to 67 DEG C of progress polymerization reactions；
(2) when reacting to monomer conversion 85%, benzoic acid solution, adjustment reaction pH to 9 is added；
(3) potassium hydroxide solution is added when monomer conversion 90%, pH is adjusted to 12；
(4) when conversion ratio 98%, reaction is completed, and obtains the large grain size latex of emulsion particle diameter 305nm.Total reaction time 12
Hour, convert into partial size growth rate 25nm/h.
Embodiment 2
(1) the first reaction solution, including 95 parts of butadiene, 5 parts of styrene, 0.35 part of potassium oleate, disproportionated rosin acid potassium are taken
1.09 parts, 0.36 part of Lutensol To-7,0.25 part of tert-dodecylmercaotan, 0.6 part of potassium peroxydisulfate, 0.4 part of potassium carbonate, sulphur
1.5 parts of sour potassium, 0.1 part of potassium hydroxide, 90 parts of deionized water be added in reaction kettle, the first reaction solution pH12 is warming up to 65 DEG C
Carry out polymerization reaction；
(2) when reacting to monomer conversion 10%, solution of acetic anhydride, adjustment reaction pH to 4 is added；
(3) solution of potassium carbonate is added in monomer conversion 50%, and pH is adjusted to 9.5；Add the second reaction solution, including oleic acid
0.2 part of potassium, 0.5 part of disproportionated rosin acid potassium, 0.1 part of tert-dodecylmercaotan；
(4) when conversion ratio 91%, reaction is completed, and obtains the large grain size latex of emulsion particle diameter 500nm.Total reaction time 14
Hour, convert into partial size growth rate 36nm/h.
Embodiment 3
(1) the first reaction solution, including 95 parts of butadiene, 5 parts of isoprene, 2.4 parts of disproportionated rosin acid potassium, Lutensol are taken
1.0 parts of To-3,0.3 part of tert-dodecylmercaotan, 0.3 part of potassium peroxydisulfate, 0.44 part of potassium carbonate, 0.06 part of potassium hydroxide, go from
140 parts of sub- water is added in reaction kettle, the first reaction solution pH11.5, is warming up to 67 DEG C of progress polymerization reactions；
(2) when conversion ratio 70%, acetum, adjustment reaction pH to 6 is added；
(3) potassium hydroxide solution is added in conversion ratio 75%, and pH is adjusted to 11；Reaction temperature is increased to 75 DEG C；
(4) when conversion ratio 98%, reaction is completed, and obtains the large grain size latex of emulsion particle diameter 320nm.Total reaction time 10
Hour, convert into partial size growth rate 32nm/h.
Embodiment 4
(1) take the first reaction solution, including 100 parts of butadiene, 2.3 parts of potassium oleate, 0.4 part of disproportionated rosin acid potassium,
6.3 parts of Lutensol To-5,0.5 part of tert-dodecylmercaotan, 0.25 part of potassium peroxydisulfate, 240 parts of deionized water be added to it is anti-
It answers in kettle, the first reaction solution pH10, is warming up to 67 DEG C of progress polymerization reactions；
(2) when butadiene is reacted to conversion ratio 30%, lactic acid solution, adjustment reaction pH to 5 is added；
(3) sodium hydroxide solution is added in conversion ratio 70%, and pH is adjusted to 13；When conversion ratio 80%, reaction temperature is mentioned
Height is to 85 DEG C；
(4) when conversion ratio 95%, reaction is completed, and obtains the large grain size latex of emulsion particle diameter 200nm.Total reaction time 8
Hour, convert into partial size growth rate 25nm/h.
Embodiment 5
(1) the first reaction solution, including 92.5 parts of butadiene, 7.5 parts of styrene, 1.3 parts of potassium oleate, disproportionated rosin acid potassium are taken
1.2 parts, 2.5 parts of Lutensol To-5,0.45 part of tert-dodecylmercaotan, 0.2 part of isopropyl benzene hydroperoxide, ferrous sulfate
0.008 part, 0.35 part of glucose, 0.25 part of potassium carbonate, 0.75 part of potassium sulfate, 0.25 part of sodium pyrophosphate, 200 parts of deionized water plus
Enter into reaction kettle, the first reaction solution pH11, is warming up to 55 DEG C of progress polymerization reactions；
(2) when conversion ratio 50%, salicylic acid solution, adjustment reaction pH to 7 is added；Add the second reaction solution, including over cure
0.3 part of sour potassium, 0.2 part of ferrous sulfate；
(3) sodium carbonate liquor is added in conversion ratio 70%, and pH is adjusted to 10；
(4) when conversion ratio 93%, reaction is completed, and obtains the large grain size latex of emulsion particle diameter 280nm.Total reaction time 7
Hour, convert into partial size growth rate 40nm/h.
Comparative example 1
(1) 95 parts of butadiene, 5 parts of styrene, 1.5 parts of potassium oleate, 1.5 parts of disproportionated rosin acid potassium, tertiary dodecyl sulphur are taken
0.45 part of alcohol, 0.3 part of potassium peroxydisulfate, 0.3 part of potassium carbonate, 145 parts of deionized water be added in reaction kettle, be warming up to 67 DEG C of progress
Polymerization reaction；
(2) when conversion ratio 97%, reaction is completed, and obtains the small grain size latex of emulsion particle diameter 105nm.Reaction time 12 is small
When.
(3) small grain size latex is transferred to agglomeration kettle, the used time 30 minutes, is added into 100 parts of (dry weight) small grain size latexes
2.1 parts of (dry weight) acetums, the used time 10 minutes, stirring 10 minutes, was then added 2 parts of (dry weight) potassium hydroxide after the completion of being added
Solution stirs 10 minutes.Obtain emulsion particle diameter 300nm large grain size latex.The agglomeration used time 1 hour.
(4) partial size growth rate 23nm/h.
Comparative example 2
(1) 95 parts of butadiene, 5 parts of styrene, 0.75 part of potassium oleate, 1.75 parts of disproportionated rosin acid potassium, tertiary dodecyl are taken
0.35 part of mercaptan, 0.6 part of potassium peroxydisulfate, 0.4 part of potassium carbonate, 1.5 parts of potassium sulfate, 0.1 part of potassium hydroxide, 90 parts of deionized water plus
Enter into reaction kettle, is warming up to 65 DEG C of progress polymerization reactions；
(2) when conversion ratio 92%, reaction is completed, and obtains the small grain size latex of emulsion particle diameter 130nm.Reaction time 15 is small
When.
(3) small grain size latex is transferred to agglomeration kettle, the used time 30 minutes, is added into 100 parts of (dry weight) small grain size latexes
1.88 parts of (dry weight) acetums, the used time 10 minutes, stirring 10 minutes, was then added 1.79 parts of (dry weight) hydrogen-oxygens after the completion of being added
Change potassium solution, stirs 10 minutes.Obtain emulsion particle diameter 380nm large grain size latex.The agglomeration used time 1 hour.
(4) partial size growth rate 24nm/h.
Comparative example 3
(1) 95 parts of butadiene, 5 parts of isoprene, 0.4 part of potassium oleate, 3 parts of disproportionated rosin acid potassium, tertiary dodecyl sulphur are taken
0.3 part of alcohol, 0.3 part of potassium peroxydisulfate, 0.44 part of potassium carbonate, 0.06 part of potassium hydroxide, 140 parts of deionized water be added to reaction kettle
In, it is warming up to 67 DEG C of progress polymerization reactions；
(2) when conversion ratio 98%, reaction is completed, and obtains the small grain size latex of emulsion particle diameter 100nm.Reaction time 12 is small
When.
(3) small grain size latex is transferred to agglomeration kettle, the used time 30 minutes, is added into 100 parts of (dry weight) small grain size latexes
2.27 parts of (dry weight) acetums, the used time 10 minutes, stirring 10 minutes, was then added 2.16 parts of (dry weight) hydrogen-oxygens after the completion of being added
Change potassium solution, stirs 10 minutes.Obtain emulsion particle diameter 290nm large grain size latex.The agglomeration used time 1 hour.
(4) partial size growth rate 22nm/h.
Comparative example 4
(1) 100 parts of butadiene, 7.5 parts of potassium oleate, 1.5 parts of disproportionated rosin acid potassium, 0.5 part of tert-dodecylmercaotan, mistake are taken
0.25 part of potassium sulfate, 240 parts of deionized water be added in reaction kettle, be warming up to 67 DEG C of progress polymerization reactions；
(2) when conversion ratio 95%, reaction is completed, and obtains the small grain size latex of emulsion particle diameter 60nm.Total reaction time 11
Hour.
(3) small grain size latex is transferred to agglomeration kettle, the used time 30 minutes, is added into 100 parts of (dry weight) small grain size latexes
5.4 parts of (dry weight) acetums, the used time 70 minutes, stirring 10 minutes, was then added 5.14 parts of (dry weight) hydrogen-oxygens after the completion of being added
Change potassium solution, stirs 10 minutes.Obtain emulsion particle diameter 200nm large grain size latex.The agglomeration used time 2 hours.
(4) partial size growth rate 15nm/h.
Comparative example 5
(1) 92.5 parts of butadiene, 7.5 parts of styrene, 2.6 parts of potassium oleate, 2.4 parts of disproportionated rosin acid potassium, tertiary dodecane are taken
0.45 part of base mercaptan, 0.2 part of isopropyl benzene hydroperoxide, 0.008 part of ferrous sulfate, 0.35 part of glucose, 0.25 part of potassium carbonate, sulphur
0.75 part of sour potassium, 0.25 part of sodium pyrophosphate, 200 parts of deionized water be added in reaction kettle, be warming up to 55 DEG C of progress polymerization reactions；
(2) when conversion ratio 94%, reaction is completed, and obtains the small grain size latex of emulsion particle diameter 80nm.Reaction time 10 is small
When.
(3) small grain size latex is transferred to agglomeration kettle, the used time 30 minutes, is added into 100 parts of (dry weight) small grain size latexes
3.15 parts of (dry weight) acetums, the used time 10 minutes, stirring 10 minutes, was then added 3.0 parts of (dry weight) hydrogen-oxygens after the completion of being added
Change potassium solution, stirs 10 minutes.Obtain emulsion particle diameter 260nm large grain size latex.The agglomeration used time 1 hour.
(4) partial size growth rate 24nm/h.
Compare comparative example and embodiment as it can be seen that polymerization reaction time is identical or connects present invention eliminates the investment of agglomeration kettle
Closely, but save material transfer and agglomeration time so that total production time shorten, production efficiency improve.
Claims (10)
1. a kind of emulsion polymerisation process for preparing big partial size polydiene latex, comprising the following steps:
(1) reaction kettle is added in the first reaction solution, is warming up to 55-85 DEG C, the first reaction solution pH >=10, preferably 10-12；Wherein
One reaction solution includes monomer, emulsifier, chain-transferring agent, optional electrolyte, initiator, deionized water；
(2) when monomer conversion reaches 10-85%, preferably 50-70%, acids agglomerant, which is added, reduces reaction system pH to 4-
9, preferably 5-7；
(3) when monomer conversion reaches 50-90%, preferably 70-90%, alkaloids is added and increase reaction system pH to 9.5-
13, preferably 10-12；
(4) after monomer conversion reaches > 90%, preferably > 95% after, reaction complete discharging obtains big partial size polydiene latex
Product.
2. according to the method described in claim 1, wherein the first reaction solution constituent mass dosage is as follows:
3. the method according to claim 1, wherein emulsifier described in step (1) is selected from compound emulsifying agent
System includes emulsifier S and emulsifier I in compound emulsifying agent；Wherein emulsifier S is selected from carboxylic acid type anion emulsifier, right
PKa > 5 for answering carboxylic acid are preferably selected from one of disproportionated rosin acid, stearic acid, palmitic acid, the sodium salt of oleic acid or sylvite or more
Kind；The emulsifier I is selected from nonionic emulsifier, preferably one of isomery alcohol ether or a variety of；Emulsifier S accounts for whole emulsifiers
Mass ratio be 30-100%, preferably 50-80%, emulsifier I account for whole emulsifiers mass ratio be 0-70%, preferably 20-
50%.
4. the method according to claim 1, wherein monomer described in step (1) includes butadiene, benzene second
One of alkene, isoprene are a variety of, and the initiator is selected from potassium peroxydisulfate, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide
One of hydrogen is a variety of, and chain-transferring agent is tert-dodecylmercaotan, the electrolyte be selected from sodium salt, sylvite, sodium hydroxide,
One of potassium hydroxide is a variety of.
5. the method according to claim 1, wherein step (1) can be used heat cause or Redox Initiator, when
Using when Redox Initiator in emulsion polymerization raw material it is corresponding also comprising causing auxiliary agent；The dosage for causing auxiliary agent is 0.1-1 parts, with
100 parts of monomer mass meters.
6. the method according to claim 1, wherein acids agglomerant described in step (2) is selected from pKa in 1-
One of organic acid and its acid anhydrides between 5 are a variety of, be preferably selected from acetic acid, acetic anhydride, lactic acid, benzoic acid, in salicylic acid
It is one or more, alkaloids described in step (3) be selected from inorganic base or hydrolysis in alkalinity inorganic salts, be preferably selected from hydrogen
One of sodium oxide molybdena, potassium hydroxide, sodium carbonate, potassium carbonate, potassium phosphate are a variety of.
7. the method according to claim 1, wherein add the second reaction solution when monomer conversion 40-70%,
Second reaction solution includes one of emulsifier S, chain-transferring agent, initiator or a variety of, and the dosage for adding emulsifier S is 0.1-1
Part, adding chain-transferring agent dosage is 0.05-0.2 parts, and adding initiator amount is 0.05-0.5 parts, in terms of 100 parts of monomer masses.
8. the method according to claim 1, wherein the method using ladder temperature control controls reaction temperature, initially
55-75 DEG C of reaction temperature, after monomer conversion is greater than 70%, increase the temperature to 75-85 DEG C.
9. latex products made from a kind of method according to claim 1-7, which is characterized in that latex is averaged grain
Diameter is 200nm-500nm, preferably 250-400nm.
10. a kind of acrylonitrile-butadiene-phenylethene grafted copolymer prepared by latex products according to any one of claims 8, and its
Preparing the application in ABS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910503550.8A CN110204656B (en) | 2019-06-12 | 2019-06-12 | Emulsion polymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910503550.8A CN110204656B (en) | 2019-06-12 | 2019-06-12 | Emulsion polymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110204656A true CN110204656A (en) | 2019-09-06 |
| CN110204656B CN110204656B (en) | 2021-12-14 |
Family
ID=67792133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910503550.8A Active CN110204656B (en) | 2019-06-12 | 2019-06-12 | Emulsion polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110204656B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642984A (en) * | 2019-10-27 | 2020-01-03 | 天津大沽化工股份有限公司 | Preparation method of polydiene latex for preparing ABS resin |
| CN110655599A (en) * | 2019-10-27 | 2020-01-07 | 天津大沽化工股份有限公司 | Method for preparing large-particle-size latex particles by in-situ weak acid agglomeration method |
| CN113388066A (en) * | 2021-05-07 | 2021-09-14 | 青岛科技大学 | Polybutadiene latex and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760222A (en) * | 2004-10-12 | 2006-04-19 | 中国石油天然气集团公司 | Method for preparing latex of polybutadiene in small grain size |
| CN101125906A (en) * | 2006-08-17 | 2008-02-20 | 中国石油天然气集团公司 | Preparation method for small grainsize polybutadiene latex |
| CN102924840A (en) * | 2012-10-09 | 2013-02-13 | 大连理工大学 | Method for preparing ABS resin from phenylethylene-butadiene-isoprene terpolymer composite latex by emulsion grafting |
| CN103059222A (en) * | 2013-01-06 | 2013-04-24 | 杭州蓝诚实业有限公司 | Preparation method of large-particle-size styrene-butadiene latex |
-
2019
- 2019-06-12 CN CN201910503550.8A patent/CN110204656B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760222A (en) * | 2004-10-12 | 2006-04-19 | 中国石油天然气集团公司 | Method for preparing latex of polybutadiene in small grain size |
| CN101125906A (en) * | 2006-08-17 | 2008-02-20 | 中国石油天然气集团公司 | Preparation method for small grainsize polybutadiene latex |
| CN102924840A (en) * | 2012-10-09 | 2013-02-13 | 大连理工大学 | Method for preparing ABS resin from phenylethylene-butadiene-isoprene terpolymer composite latex by emulsion grafting |
| CN103059222A (en) * | 2013-01-06 | 2013-04-24 | 杭州蓝诚实业有限公司 | Preparation method of large-particle-size styrene-butadiene latex |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642984A (en) * | 2019-10-27 | 2020-01-03 | 天津大沽化工股份有限公司 | Preparation method of polydiene latex for preparing ABS resin |
| CN110655599A (en) * | 2019-10-27 | 2020-01-07 | 天津大沽化工股份有限公司 | Method for preparing large-particle-size latex particles by in-situ weak acid agglomeration method |
| CN113388066A (en) * | 2021-05-07 | 2021-09-14 | 青岛科技大学 | Polybutadiene latex and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110204656B (en) | 2021-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110204656A (en) | A kind of emulsion polymerisation process | |
| EP0568831B1 (en) | Aqueous polymer dispersion | |
| EP0614922B1 (en) | Process for the preparation of an aqueous polymer dispersion | |
| CN102952229B (en) | A kind of pvc resin paste grade and preparation method thereof | |
| CN110305252B (en) | Method for preparing large-particle-size diene rubber latex | |
| JPH07216025A (en) | Preparation of alkali-soluble emulsion copolymer | |
| CN107602769B (en) | Method for synthesizing MBS resin | |
| CN103059222A (en) | Preparation method of large-particle-size styrene-butadiene latex | |
| CN106519118A (en) | Preparing method of styrene-butadiene latex used for modified emulsified asphalt | |
| EP0567819A1 (en) | Aqueous polymer dispersion | |
| CN102863726A (en) | Synthetic method of PVC modifier | |
| KR20080057539A (en) | Method for preparing rubber latex of a small diameter | |
| JP3803544B2 (en) | Method for producing synthetic rubber latex having large particle size | |
| KR101279267B1 (en) | A preparation method of small particle sized polybutadiene latex used for the production of abs | |
| CN102532786B (en) | Preparation method of bimodally-distributed modified ABS (acrylonitrile-butadiene-styrene) resin | |
| CN104017521B (en) | Protein-based wood adhesive of a kind of for shelf-stable and its preparation method and application | |
| EP0186926A2 (en) | Method for the preparation of graft copolymers by emulsion copolymerization | |
| US4771098A (en) | Process for preparing acrylic resin dispersions | |
| CN102251238A (en) | Method for preparing metal surface conditioner | |
| US3956163A (en) | Pigmented detergents | |
| EP0054766B1 (en) | Aqueous dispersions of synthetic rubber containing carboxyl groups, process for their preparation and their use | |
| KR100380015B1 (en) | Method for preparing large-diameter rubber particles | |
| CN110669154B (en) | Method for preparing large-particle-size latex by carbon dioxide agglomeration | |
| JPH05247107A (en) | Preparation of large-particle plastic aqueous dispersion | |
| EP1329464B1 (en) | Agglomeratable rubber latex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20201207 Address after: Room 304, management committee office building, Jinxiang Chemical Industrial Park, xianger Town, Dongpo District, Meishan City, Sichuan Province Applicant after: Wanhua chemical (Sichuan) Co.,Ltd. Applicant after: Wanhua Chemical Group Co.,Ltd. Address before: 264006 No. 17 Tianshan Road, Yantai economic and Technological Development Zone, Shandong Applicant before: Wanhua Chemical Group Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |