CN1927925A - Preparation method of large particle size butyronitrile latex - Google Patents
Preparation method of large particle size butyronitrile latex Download PDFInfo
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Abstract
The great grain size butyronitrile latex is prepared through adding component B in 1-10 weight portions into component A in 90-99 weight portions and through special agglomeration, and features its double peak. The component A is latex prepared with vinyl cyanide monomer in 5-10 weight portions, other polymerisable monomer in 0-5 weight portions and diene monomer in 80-95 weight portions and through fast emulsion polymerization. The component B is agglomeration latex capable of increasing the grain size of the polymer and comprises acylate monomer in 70-95 weight portions and acrylic acid monomer in 5-30 weight portions. The great grain size butyronitrile latex is prepared through emulsion polymerization, and has average grain size of 70-140 nm, grain size distribution coefficient smaller than 1.0, polymerization conversion rate not lower than 98 wt%, polymerization period 5-8 hr and gel content not lower than 78 wt%.
Description
Technical field
The present invention relates to a kind of preparation method of large particle size butyronitrile latex, or rather, the present invention adopts emulsion and synthetic a kind of method that can be used for the substrate latex of modified resin preparation of agglomeration technique two-step approach, belongs to macromolecular material synthetic technology category.
Background technology
Generally speaking, two-phase polymer is shock-resistant higher, required rubber content is higher, rubber particles is bigger, but the general deterioration of tensile strength of raising glue amount material, the needed synthetic technology of increase particle diameter be more complicated relatively again, the method that latex obtains big particle diameter is a lot, can obtain the latex of big particle diameter by the control of polymerization technique, also can obtain large grain size latex by the method and the technology of physics.Its physics agglomeration method commonly used has: powerful paddling process, freezing agglomeration technique, pressure agglomeration technique or the like; And the most frequently used chemical agglomeration method has: ionogen method, organic solvent method, acid and acid anhydrides method, polymer latex method or the like.
Common letex polymerization will be done the polymer latex particle diameter greatly to more than the 300nm, and the way of generally taking has the increase reaction times, but the required reaction times generally be not less than 48 hours, influence the raising of production efficiency; Use the seed latex method, be confined to and the particle diameter of this method accomplished about 250nm to continue to increase relatively more difficult than being easier to.The pressure agglomeration technique needs bigger energy and patent equipment; Freezing agglomeration technique power consumption is more, and particle diameter is accomplished more than the 300nm very difficult; The stability of other some agglomeration technique agglomerating latex is generally not good enough.After the eighties, bibliographical information many latex class agglomerants, but it is formed and agglomeration method is the top secret of industry always.
Patented technology EP 0,433,710 propose the method for the synthetic big particle diameter polybutadiene latex of a kind of emulsion method, after it is in polymerization process or polymerization finishes, in per 100 parts of polymeric latexs, add 0.1～10 part of agglomerating latex, be characterized in polymerization process, carrying out agglomeration.Patent claims that this method is insensitive to temperature and stir speed (S.S.), can not cause the instability in certain stage, the adding accelerated reaction process greatly of agglomerating latex, and forms round particle, but the particle diameter agglomeration is to 330nm.
And at patent EP 0,143, provided a kind of particle agglomeration method of rubber latex in 858, the particle diameter agglomeration is controlled with latex (AgAg) in the latex, and this latex (AgAg) with nodulizing is a kind of polymkeric substance of typical nucleocapsid structure, and it comprises 50～95% rubbery kernel, and 50～5% graft shell, shell is made up of 80～99.5% acrylate and 0.5～20% vinyl unsaturated acid, and latex particle size is about 200nm after the agglomeration.
All seldom mention agglomeration amplification technique process and equipment in the disclosed patent of each company, the mostly rough elder generation that says synthesizes the latex (in 20 hours, about 100nm) of small particle size at short notice, and its reaction conversion ratio generally is higher than 90%, and gel content meets the requirements.Then agglomerant is added, need to begin violent stirring, relax then, the agglomeration later stage adds stablizer, and the accent pH value is that agglomerating latex is stable.These methods are owing to exist many variations, and technique is very strong, therefore formed numerous patents that differ from one another.However, the control of size and distribution thereof in the latex agglomeration process, the shelf stability of latex after the agglomeration, subject studies such as the grafting stability of agglomerating latex still remain further perfect.
Therefore, how preparing big particle diameter polymer latex easily, will be that the people in the industry needs the problem studied for a long time.This research is exactly on the basis of these researchs of forefathers, has invented a kind of preparation method's technology of large particle size butyronitrile latex.
Summary of the invention
In order to solve the problem that exists on the prior art, it is simple to the invention provides a kind of method, and particle diameter amplifies convenient, and the agglomerating latex building-up reactions is steady, and latex stores the large particle size butyronitrile latex preparation method who has good stability with grafting after the agglomeration.
Purpose of the present invention can reach by following measure:
A kind of preparation method of large particle size butyronitrile latex, this method comprises the steps:
1) step of preparation small particle size nitrile rubber A, A is the diene monomer by 80～95 weight parts, with 5～20 weight parts vinyl cyanide base monomer, and 0～5 weight part other monomer of Gong polymeric, the equal particle size range of body that obtains by letex polymerization is the polymer latex A of 80～180nm;
2) preparation has the step of polymer latex B of nodulizing, B be by 70～95 weight parts acrylic ester monomer .5～30 weight parts acrylic monomer, adopt the polymer latex B of the equal particle size range of emulsion process polymeric body at 70～140nm;
3) step of the big particle diameter butyronitrile polymer latex C of preparation, C be 90～99 weight parts A latex, under 20～45 ℃ temperature condition, use specific process conditions add 1～10 weight part agglomerating latex B and the large grain size latex of the be exclusively used in polymer modifiers graft base of the equal particle diameter side 220～1000nm of body that makes with double-peak feature, and its size distribution index is 1～2.
Wherein, latex A be by 5～10 weight parts vinyl cyanide base monomer, and 0～5 weight part other monomer of Gong polymeric, with above-mentioned diene monomer 80～95 weight parts mix monomer, through quick letex polymerization system or latex, the equal particle diameter of its typical latex body is 100～140nm, the size distribution index is less than 1.0, polymerisation conversion 〉=97%, polymerization time 9～12 hours, gel content 65～72%.
Agglomerating latex B be by 70～95 weight parts acrylic ester monomer, 5～30 weight parts acrylic monomer, adopt the polymer latex of the equal particle size range of emulsion process polymerization adult at 70～140nm, its size distribution index is also less than 1.0, polymerisation conversion 〉=98%, polymerization time 5～8 hours, gel content 〉=78%.
Described diene monomer is a divinyl.
Described vinyl cyanide base monomer is the acrylic monomer preferably, and described acrylic monomer is vinyl cyanide or Alpha-Methyl acrylonitrile monemer preferably.
Described is styrenic monomers for other monomer of polymeric, described styrenic monomers is styrene monomer, α-Jia Jibenyixidanti, α-chloro-styrene monomer or P-vinyl toluene monomer preferably, and described styrenic monomers is styrene monomer preferably.
Described acrylic monomer is an acrylonitrile monemer.
Emulsifying agent is compound saponification system in the step (1), selects the compound saponification system of compound saponification system, potassium oleate and lipid acid potassium of rosined soap and Sodium dodecylbenzene sulfonate or the compound saponification system of potassium stearate and lipid acid potassium for use.
The molecular weight regulator that in step (1), has also added 0.25～0.65 weight part: tert-dodecyl mercaptan.
For making patent working and reaching the desired effect of invention, gordian technique of the present invention also is the control techniques of B latex to A latex agglomeration process:
Invention requires: the pH value that will treat agglomerating latex during agglomeration transfers between 8.5～11, pH value is recalled between 11～12 after the agglomeration, and the tangible agglomerant of nodulizing need not be treated agglomerating latex adjustment pH value, the adjusting of pH value can be used any commercially available alkaloids, such as sodium hydroxide, potassium hydroxide or the like, but for to avoid the destruction of alkali lye to latex, employed concentration of lye is preferable with 3～5%;
Add small amount of electrolyte, can effectively improve the particle diameter of latex, ionogen can be sodium-chlor, Repone K, yellow soda ash, sodium bicarbonate or the like, and consumption 0.1～0.2 weight part is preferable;
The adding of back stablizer, studies show that and to add the back stablizer, to guarantee the stability of latex, the chemical substance of the emulsifying agent unanimity that the back stablizer that is suitable for adopts when generally selecting for use with latex polymerization is for well, it is more satisfactory that consumption is controlled at 0.1～0.4 weight part ratio, and optimum amount is selected 0.22～0.30 weight part;
The agglomerant consumption, directly related with the amount of acid in the agglomerant latex, with respect to the amount for the treatment of agglomerating latex, the agglomerant usage quantity is 2.5 weight parts, recommending use range is 2.2～3.0 weight parts;
About mixing speed 200rpm, the amount of the deionized water of dilution agglomerant need be adjusted to the solid content that makes agglomeration finish back latex and be in 30～40% during agglomeration.
The preparation of large particle size butyronitrile latex of the present invention has comprised three processes: the preparation of small particle size nitrile rubber A; Have the polymer latex B's of nodulizing; The preparation of large particle size butyronitrile latex C.
Particularly, the technology of preparing of small particle size nitrile rubber A is as follows, A is the diene monomer by 80～95 weight parts, with 5～20 weight parts vinyl cyanide base monomer, and other monomer of Gong the polymeric of 0～5 weight part, the equal particle size range of body that obtains by letex polymerization is the polymer latex of 80～180nm.
The synthetic technology of small particle size nitrile rubber of the present invention, adopt water soluble starter, use 50～80 ℃ temperature of reaction, discover the increase along with amount of initiator, speed of response is accelerated, and transformation efficiency improves, exothermic heat of reaction is concentrated, remove the heat difficulty, initiator amount is recommended to select 0.2～0.5% preferably, and operable initiator has Potassium Persulphate, ammonium persulfate.
Invent used emulsifying agent and can adopt independent potassium oleate, disproportionation rosin soap, total amount is to be no less than 3.5% of monomer total amount, can once add, and also can add in batches; Preferred add 80% earlier, during reaction conversion ratio 70% left and right sides, add remainingly 20% again, add and to be once, also successive.Invent preferred emulsification system and be to use the compound soap system: the assembled scheme of recommendation can be one of rosined soap+Sodium dodecylbenzene sulfonate/potassium oleate+lipid acid potassium/potassium stearate+lipid acid potassium, its compound soap total amount is for being no less than 3.5%, can once add, also can add in batches, its compound ratio is generally main soap and accounts for 70～95%, and auxiliary soap accounts for 5～30% for good.3.5% emulsifying agent that is less than the monomer total amount often causes reaction system to the later stage bad stability, occurs a small amount of precipitate in the latex, and this does not normally wish to take place.
Can regulate the gel content of latex easily by the amount of molecular weight regulator tert-dodecyl mercaptan, gel content influences the secondary reuse of material, and proper consumption is 0.25～0.65 weight part.
The viscosity of latex, contain admittedly, particle diameter, gel content be important basic indexes and parameters, in order to obtain preferable latex characteristic, first-selected contains general employing about 38～45% admittedly, particle diameter 100～130nm, viscosity 80～200mpa.s after synthetic.The use of small amount of electrolyte solution for the k value of adjusting latex very effectively, the invention be recommended in use in the synthesizing formula 0.5～1.0 weight part Repone K, certainly also can adopt other inorganic salt to adjust the viscosity of system, the effect when improving the further agglomeration of latex.
Used 5～15% vinyl cyanide as second monomer in the latex building-up process, also can use 0～5% styrene monomer copolymerization with it with butadiene copolymer.To be this type of monomeric adding played critical effect to the raising of speed of response in its most useful contribution, its mechanism thinks that this interpolymerization has played the effect as the emulsifying agent unanimity, reduced the consumption of soap in the prescription, making polymerization cycle shorten to 9～12 hours can finish.
The technology of preparing of polymer latex B that the present invention has nodulizing is as follows: B be by 70～95 weight parts acrylic ester monomer, 5～30 weight parts acrylic monomer, adopt the polymer latex of the equal particle size range of emulsion process polymeric body at 70～140nm.
The technology of invention adopts n-butyl acrylate and acrylate copolymer emulsion as agglomerant, experiment shows that acrylic acid adding makes the fierceness of abnormal reaction, so suitable process conditions is the key of synthetic this type of latex, emulsification system is preferably consistent with the synthetic emulsification system that uses of small grain size latex in addition.Inventing preferred acrylic acid consumption is 5～30 weight parts, and it is not obvious to be less than its nodulizing of 5 weight parts, and then nodulizing is strong excessively to surpass 30 weight parts, causes the instability of agglomerating latex easily.Make agglomeration process stable and good agglomeration result arranged, the size of control agglomerant latex is very important, the particle diameter result who thirsts for wishes that 70～140nm is best, controlling suitable water-oil ratio can make synthetic latex keep suitable particle diameter, viscosity, the water-oil ratio of recommendation generally use 1.2～2.5% are preferable.
The control of agglomerant latex synthesis reaction temperature is very important, and owing to polymerization exotherm is bigger, temperature is easy to out of control, and invention makes reaction very steady by increase water ratio, reduction batch charging coefficient, change feed way, and the technology circulation ratio is splendid.
The technology of preparing of large particle size butyronitrile latex C of the present invention, be actually the nitrile rubber agglomeration process of small particle size and effective control of result, C be by 90～99 weight parts A latex, at normal temperature or be not higher than under 45 ℃ the temperature condition, use specific process conditions add 1～10 weight part agglomerating latex B and the equal particle diameter of body that makes is the large grain size latex of the be exclusively used in polymer modifiers graft base with double-peak feature of 220～1000nm.
Physical data is only simply introduced agglomeration: after adding agglomerating latex, and first violent stirring, the back is relaxed and is stirred; Do not carry and add the back stablizer, regulate pH value then and make gordian technique measure that particle diameter settles out etc.
Main points of the present invention are: transfer during agglomeration between (treating agglomerating latex) pH value to 8.5～11, pH value is recalled between 11～12 after the agglomeration, and the tangible agglomerant of nodulizing need not be treated agglomerating latex and adjusts pH value.The adjusting of pH value can be used any commercially available alkaloids, such as sodium hydroxide, potassium hydroxide or the like.For avoiding the destruction of alkali lye to latex, the general concentration of lye 3～5% that uses gets final product.
Ionogen: a small amount of adding can effectively improve the particle diameter of latex, but this is different from and directly adds the ionogen agglomeration technique.The ionogen of recommending can be sodium-chlor, Repone K, yellow soda ash, sodium bicarbonate or the like, and general consumption 0.1～0.2% gets final product.
Back stablizer: do not mention in the physical data add the back stablizer, but studies show that must add the back stablizer, to guarantee the stability of latex.The chemical substance of the emulsifying agent unanimity that the back stablizer that is suitable for adopts when generally selecting for use with latex polymerization is for well, and it is 0.1～0.4% more satisfactory that consumption is controlled at.
The agglomerant consumption: experiment is found, amount with acid in the agglomerant latex is directly related, amount with respect to latex, general agglomerant usage quantity is 2.5% (recommending use range is 2.2～3.0%), soap 0.22～0.30%, about rotating speed 200rpm, containing admittedly after the amount of deionized water is adjusted to agglomeration is finished is 30～35% during agglomeration.
In sum, content of the present invention comprises: the preparation of (1) small particle size nitrile rubber A, A is the diene monomer by 80～95 weight parts, vinyl cyanide base monomer with 5～20 weight parts, and other monomer of Gong the polymeric of 0～5 weight part, the equal particle size range of body that obtains by letex polymerization is the polymer latex of 80～180nm; (2) have the preparation of the polymer latex B of nodulizing, B is by 70～95 parts by weight of acrylic esters monomers, and 5～30 parts by weight of acrylic class monomers adopt the polymer latex of the equal particle size range of emulsion process polymeric body at 70～140nm; (3) preparation of large particle size butyronitrile latex C, C is the A latex of 90～99 weight parts, at normal temperature or be not higher than under 45 ℃ the temperature condition, use specific process conditions to add 1～10% agglomerating latex B and the equal particle diameter of body that makes is the large grain size latex of the be exclusively used in polymer modifiers graft base with double-peak feature of 220～1000nm; It is characterized in that: A=90 among the large grain size latex C (%)～99%; B=1～10% uses proprietary agglomeration step and prescription, and the equal particle diameter of body that makes the large particle size butyronitrile latex with double-peak feature is 220～1000nm, and its size distribution index is 1～2.
Embodiment
For the purpose of invention better is described, the following examples have been made concrete illustrations to foregoing invention:
Embodiment 1
Synthesizing of 1-A, small particle size nitrile rubber
Adopt the 30L polymermaking autoclave, successively water is joined then in the withstand voltage polymeric kettle, use nitrogen replacement four times, each dwell time is 1 minute.Be evacuated then, add divinylic monomer.Open and stir, begin after 10 minutes to heat up.In one hour, temperature is risen to 67 ℃, once contain admittedly every survey in 2.0 hours, and calculating monomer conversion, after polyreaction 9-11 hour, transformation efficiency reaches 99%, cooling discharge, just can be contained admittedly and be not less than 45.8%, particle diameter is the latex of polybutadiene in small grain size about 114nm, and its gel content is 72%, and polymerization formula is as follows:
Raw material umber charging capacity (g)
Divinyl 90 9900
Vinyl cyanide 10 1100
Potassium Persulphate 0.25 27.5
Potassium oleate 5.0 550
Sodium dodecylbenzene sulfonate 0.2 22.0
Potassium hydroxide 0.04 4.4
Tert-dodecyl mercaptan 0.5 55.0
Sodium sulfate 1.5 165.0
De-salted water 118.0 12980
1-B, has the preparation of the polymer latex of nodulizing
Adopt the 30L polymermaking autoclave, successively water, oil phase are added polymeric kettle then, open and stir, begin to warm to 75 ℃ of isothermal reaction 5h after 10 minutes, what obtain transformation efficiency 95%, pH value about 6.0 contains carboxylic acid group's polymer agglomerant, and latex particle size is 114nm, and polymerization formula is as follows:
Raw material umber charging capacity (g)
N-ethyl propenoate 70.0 5600
Methacrylic acid 30.0 2400
Potassium oleate 2.0 160
Uncle-Dodecyl Mercaptan 0.3 24
Sodium dodecylbenzene sulfonate 0.2 16
Potassium Persulphate (1%) 0.5 40
Naphthalenesulfonic acid-formaldehyde condensate 0.3 24
Deionized water 200 16000
1-C, the agglomeration of small particle size nitrile rubber is amplified.
Step 1: treat the adjustment of agglomerating latex 1-A.
Prepare latex stoste by following prescription, be warmed up to 40 ℃, mixed 10 minutes.
1-A small grain size latex 100 (butt)
Ionogen (Repone K) 0.1
Potassium oleate 0.3
Potassium stearate 0.3
Adjust and finish to measure its solid content, be used for calculating the agglomerant consumption.
Step 2: dilution agglomerant 1-B.
The agglomerant diluted formulations
Embodiment 1-B latex 3 weight parts (butt is equivalent to treat agglomerating latex)
7 times in water is to the amount of agglomerant
Stir and pH value is adjusted between the 5-7 (using 4% sodium hydroxide solution).
The good agglomerant (best about 10 seconds time) in 30 seconds of dilution is added in the latex stoste of getting ready, stirring after 30 minutes sampling and analyzing particle diameter with the particle diameter instrument, size distribution be very beautiful bimodal, and the peak shape distribution is better.Wherein, d (0.1)=0.169um; D (0.5)=0.394um; D (0.9)=1.158um.Show equal D (3,2)=0.328um; The equal D of body (4,3)=0.551um, first peak value are 0.187um, and second peak value is 0.634um, span: 1.78.
The latex pH value adjusts to 10.5～11 after using 4% sodium hydroxide solution with agglomeration at last.
Embodiment 2
Synthesizing of 2-A, small particle size nitrile rubber
Adopt the 30L polymermaking autoclave, successively water is joined then in the withstand voltage polymeric kettle, use nitrogen replacement four times, each dwell time is 1 minute.Be evacuated then, add divinylic monomer.Open and stir, begin after 10 minutes to heat up.In one hour, temperature is risen to 67 ℃, once contain admittedly every survey in 2.0 hours, and calculating monomer conversion, after polyreaction 9-11 hour, transformation efficiency reaches 99%, cooling discharge, just can be contained admittedly and be not less than 46.2%, particle diameter is the latex of polybutadiene in small grain size about 132nm, and its gel content is 69%, and polymerization formula is as follows:
Raw material umber charging capacity (g)
Divinyl 95.0 10450
Alpha-Methyl acrylonitrile monemer 5.0 550
α-Jia Jibenyixidanti 2.5 275
Potassium Persulphate 0.25 27.5
Potassium oleate 3.5 385
Sodium dodecylbenzene sulfonate 0.2 22.0
Potassium hydroxide 0.04 4.4
Tert-dodecyl mercaptan 0.5 55.0
Sodium sulfate 1.5 165.0
De-salted water 118.0 12980
2-B, has the preparation of the polymer latex of nodulizing
Adopt the 30L polymermaking autoclave, successively water, oil phase are added polymeric kettle then, open and stir, begin to warm to 75 ℃ of isothermal reaction 5h after 10 minutes, what obtain transformation efficiency 95%, pH value about 6.0 contains carboxylic acid group's polymer agglomerant, and latex particle size is 120nm, and polymerization formula is as follows:
Raw material umber charging capacity (g)
N-ethyl propenoate 95.0 7600
Methacrylic acid (or vinylformic acid) 5.0 400
Potassium oleate 2.0 160
Uncle-Dodecyl Mercaptan 0.3 24
Sodium dodecylbenzene sulfonate 0.2 16
Potassium Persulphate (1%) 0.5 40
Naphthalenesulfonic acid-formaldehyde condensate 0.3 24
Deionized water 200 16000
2-C, the agglomeration of small particle size nitrile rubber is amplified.
Step 1: treat the step 1 of the adjustment of agglomerating latex 2-B with embodiment 1-C.
Step 2: dilution agglomerant 2-B.
The agglomerant diluted formulations
Embodiment 2-B 2.5% (butt is equivalent to treat agglomerating latex)
7 times in water is to the amount of agglomerant
Stir and pH value is adjusted between the 5-7 (using 4% sodium hydroxide solution).
The good agglomerant (best about 10 seconds time) in 30 seconds of dilution is added in the latex stoste of getting ready, stirring after 30 minutes sampling and analyzing particle diameter with the particle diameter instrument, size distribution be very beautiful bimodal, and the peak shape distribution is better.Wherein, d (0.1)=0.178um; D (0.5)=0.453um; D (0.9)=0.910um.Show equal D (3,2)=0.348um; The equal D of body (4,3)=0.499um, first peak value are 0.211um, and second peak value is greater than 0.717um, specific surface area 17.3.The equal particle diameter ratio of meso-position radius and body is more approaching, span: 1.614.
The latex pH value adjusts to 10.5～11 after using 4% sodium hydroxide solution with agglomeration at last.
Embodiment 3
Synthesizing of 3-A, small particle size nitrile rubber
Adopt the 30L polymermaking autoclave, successively water is joined then in the withstand voltage polymeric kettle, use nitrogen replacement four times, each dwell time is 1 minute.Be evacuated then, add divinylic monomer.Open and stir, begin after 10 minutes to heat up.In one hour, temperature is risen to 67 ℃, once contain admittedly every survey in 2.0 hours, and calculating monomer conversion, after polyreaction 9-11 hour, transformation efficiency reaches 99%, cooling discharge, just can be contained admittedly and be not less than 45.3%, particle diameter is the latex of polybutadiene in small grain size about 142nm, and its gel content is 67%, and polymerization formula is as follows:
Raw material umber charging capacity (g)
Divinyl 80.0 8800
Vinyl cyanide 20 2200
Vinylbenzene 5.0 550
Potassium Persulphate 0.25 27.5
Potassium oleate 3.5 385
Sodium dodecylbenzene sulfonate 0.2 22.0
Potassium hydroxide 0.04 4.4
Tert-dodecyl mercaptan 0.5 55.0
Sodium sulfate 1.5 165.0
De-salted water 118.0 12980
3-B, has the preparation of the polymer latex of nodulizing
Prescription 2-B with embodiment 2.
3-C, the agglomeration of small particle size nitrile rubber is amplified.
Step 1: the adjustment for the treatment of agglomerating latex 3-B is with embodiment 1 step 1.
Step 2: dilution agglomerant 3-B is with embodiment 2 step 2.
The good agglomerant (best about 10 seconds time) in 30 seconds of dilution is added in the latex stoste of getting ready, stirring after 30 minutes sampling and analyzing particle diameter with the particle diameter instrument, size distribution be very beautiful bimodal, and the peak shape distribution is better.Wherein, d (0.1)=0.178um; D (0.5)=0.453um; D (0.9)=0.910um.Show equal D (3,2)=0.348um; The equal D of body (4,3)=0.499um, first peak value are 0.211um, and second peak value is greater than 0.717um, specific surface area 17.3.The equal particle diameter ratio of meso-position radius and body is more approaching, span: 1.614.
The latex pH value adjusts to 10.5～11 after using 4% sodium hydroxide solution with agglomeration at last.
Embodiment 4
Synthesizing of 4-A, small particle size nitrile rubber
With embodiment 1.
4-B, has the preparation of the polymer latex of nodulizing
Adopt the 30L polymermaking autoclave, successively water, oil phase are added polymeric kettle then, open and stir, begin to warm to 75 ℃ of isothermal reaction 5h after 10 minutes, what obtain transformation efficiency 95%, pH value about 6.0 contains carboxylic acid group's polymer agglomerant, and latex particle size is 127nm, and polymerization formula is as follows:
Raw material umber charging capacity (g)
N-ethyl propenoate 95.0 7600
Methacrylic acid (or vinylformic acid) 5.0 400
Potassium oleate 2.0 160
Uncle-Dodecyl Mercaptan 0.3 24
Sodium dodecylbenzene sulfonate 0.2 16
Potassium Persulphate (1%) 0.5 40
Naphthalenesulfonic acid-formaldehyde condensate 0.3 24
Deionized water 200 16000
4-C, the agglomeration of small particle size nitrile rubber is amplified.
Step 1: the adjustment for the treatment of agglomerating latex is with embodiment 1 step 1.
Step 2: dilution agglomerant 4-B.
The agglomerant diluted formulations
Agglomerant 4-B 9% (butt is equivalent to treat agglomerating latex)
7 times in water is to the amount of agglomerant
Stir and pH value is adjusted between the 5-7 (using 4% sodium hydroxide solution).
The agglomerant that dilution is good (best about 10 seconds time) in 30 seconds adds in the latex stoste of getting ready, stir sampling particle diameter instrument analysis particle diameter after 30 minutes, size distribution presents three peaks, and peak shape distributes better, but the same two peak-to-peaks distance in the 3rd peak is far away, d (0.1)=0.196um; D (0.5)=0.454um; D (0.9)=28.235um.Show equal D (3,2)=0.400um; The equal D of body (4,3)=8.129um, first peak value are 0.211um, and second peak value is 0.915um, and the 3rd peak value is 100-200um, specific surface area 15.0, span: 61.707.The 3rd peak value former appears because agglomerant agglomeration effect on the weak side due to.
Embodiment 5
Synthesizing of 5-A, small particle size nitrile rubber
With embodiment 1.
5-B, has the preparation of the polymer latex of nodulizing
Adopt the 30L polymermaking autoclave, successively water, oil phase are added polymeric kettle then, open and stir, begin to warm to 75 ℃ of isothermal reaction 5h after 10 minutes, what obtain transformation efficiency 95%, pH value about 6.0 contains carboxylic acid group's polymer agglomerant, and latex particle size is 103nm, and polymerization formula is as follows:
Raw material umber charging capacity (g)
N-ethyl propenoate 70.0 5600
Methacrylic acid (or vinylformic acid) 30.0 2400
Potassium oleate 2.0 160
Uncle-Dodecyl Mercaptan 0.3 24
Sodium dodecylbenzene sulfonate 0.2 16
Potassium Persulphate (1%) 0.5 40
Naphthalenesulfonic acid-formaldehyde condensate 0.3 24
Deionized water 200 16000
5-C, the agglomeration of small particle size nitrile rubber is amplified.
Step 1: the adjustment for the treatment of agglomerating latex is with embodiment 1 step 1.
Step 2: dilution agglomerant 5-B.
The agglomerant diluted formulations
Agglomerant 5-B 1% (butt is equivalent to treat agglomerating latex)
7 times in water is to the amount of agglomerant
Stir and pH value is adjusted between the 5-7 (using 4% sodium hydroxide solution).
The agglomerant that dilution is good (best about 10 seconds time) in 30 seconds adds in the latex stoste of getting ready, and stirring took a sample after 30 minutes analyzes particle diameter with the particle diameter instrument, and size distribution presents three peaks, the peak shape wider distribution.Wherein, d (0.1)=0.210um:d (0.5)=33.066um; D (0.9)=211.556um.Show equal D (3,2)=0.727um; The equal D of body (4,3)=75.178um, first peak value are 0.211um, and second peak value is greater than 100um, specific surface area 8.25, span: 6.392.Because the agglomerant effect is too strong, a small amount of macroscopic condensation product particle occurred.
Embodiment 6
Synthesizing of 6-A, small particle size nitrile rubber
1-A with embodiment 1.
6-B, has the preparation of the polymer latex of nodulizing
2-B with embodiment 2.
6-C, the agglomeration of small particle size nitrile rubber is amplified.
Step 1: the adjustment for the treatment of agglomerating latex is with embodiment 1 step 1.
Step 2 dilution agglomerant 6-B.
Agglomerant 6-B is diluted to the series prescription:
Agglomerant 6-B dilutes by 1.5,2.0,2.5,3.0% (butt is equivalent to treat agglomerating latex) concentration.
7 times in water is to the amount of agglomerant
Stir and pH value is adjusted between the 5-7 (using 4% sodium hydroxide solution).
The agglomerant series (best about 10 seconds time) in 30 seconds that dilution is good adds respectively in the latex stoste of getting ready, stirs sampling particle diameter instrument analysis particle diameter after 30 minutes.
The serial experiment result is respectively:
Bimodal during agglomerant B-6 consumption 1.5%, peak shape distributes slightly wide, has the particle of minute quantity particle diameter greater than 3um, and the agglomeration effect is better.D (0.1)=0.173um wherein; D (0.5)=0.414um; D (0.9)=1.063um.Show equal D (3,2)=0.341um; The equal D of body (4,3)=3.150um, first peak value are 0.211um, and second peak value is 0.717um, specific surface area 17.6.The minute quantity particle diameter causes meso-position radius and the equal particle diameter of body span: 2.151 to occur than large deviation greater than the particle of 3um.
Bimodal during agglomerant B-6 consumption 2.0%, size distribution result is bimodal, and peak shape distributes pretty good, and agglomeration is satisfactory for result.d(0.1)＝0.178um；d(0.5)＝0.453um；d(0.9)＝0.910um。Show equal D (3,2)=0.348um; The equal D of body (4,3)=0.499um, first peak value are 0.211um, and second peak value is greater than 0.717um, specific surface area 17.3.The equal particle diameter ratio of meso-position radius and body is more approaching, span: 1.614.
Bimodal during agglomerant B-6 consumption 2.5%, peak shape distributes fine, and agglomeration is satisfactory for result.D (0.1)=0.183um wherein; D (0.5)=0.567um; D (0.9)=1.094um.Show equal D (3,2)=0.390um; The equal D of body (4,3)=0.598um, first peak value are 0.211um, and second peak value is 0.810um, specific surface area 15.4, span: 1.608.
Bimodal during agglomerant B-6 consumption 3.0%, peak shape distributes fine, and the agglomeration effect is very desirable.D (0.1)=0.201um wherein; D (0.5)=0.644um; D (0.9)=1.060um.Show equal D (3,2)=0.450um; The equal D of body (4,3)=0.641um, first peak value are 0.211um, and second peak value is 0.810um, specific surface area 13.3, span: 1.333
Below only preferred example of the present invention summarized, known the professional and technical personnel in this field, all changes of doing according to individual example, modification, decomposition etc. all belong to the scope of this patent claim protection.
Claims (12)
1. the preparation method of a large particle size butyronitrile latex is characterized in that this method comprises the steps:
(1) step of preparation small particle size nitrile rubber A, A is the diene monomer by 80～95 weight parts, with 5～20 weight parts vinyl cyanide base monomer, and 0～5 weight part other monomer of Gong polymeric, the equal particle size range of body that obtains by letex polymerization is the polymer latex A of 80～180nm;
(2) preparation has the step of polymer latex B of nodulizing, B be by 70～95 weight parts acrylic ester monomer, 5～30 weight parts acrylic monomer, adopt the polymer latex B of the equal particle size range of emulsion process polymeric body at 70～140nm;
(3) step of preparation large particle size butyronitrile latex polymer latex C, C be 90～99 weight parts A latex, under 20～45 ℃ temperature condition, use specific process conditions add 1～10 weight part agglomerating latex B and the equal particle diameter of body that makes is the large grain size latex of the be exclusively used in polymer modifiers graft base with double-peak feature of 220～1000nm, and its size distribution index is 1～2.
2. according to the preparation method of claim 1, it is characterized in that latex A be by 5～10 weight parts vinyl cyanide base monomer, and 0～5 weight part other monomer of Gong polymeric, with above-mentioned diene monomer 80～95 weight parts mix monomer, the latex of making through quick letex polymerization, the equal particle diameter of its typical latex body is 100～140nm, the size distribution index is less than 1.0, polymerisation conversion 〉=97%, polymerization time 9～12 hours, gel content 65～72%.
3. according to the preparation method of claim 1, it is characterized in that agglomerating latex B be by 70～95 weight parts acrylic ester monomer, 5～30 weight parts acrylic monomer, adopt the polymer latex of the equal particle size range of emulsion process polymerization adult at 70～140nm, its size distribution index is also less than 1.0, polymerisation conversion 〉=98%, polymerization time 5～8 hours, gel content 〉=78%.
4. preparation method according to claim 1 and 2 is characterized in that described diene monomer is a divinyl.
5. preparation method according to claim 1 and 2 is characterized in that described vinyl cyanide base monomer is the acrylic monomer.
6. preparation method according to claim 5 is characterized in that described acrylic monomer is vinyl cyanide or Alpha-Methyl acrylonitrile monemer.
7. preparation method according to claim 1 and 2 is characterized in that described is styrenic monomers for other monomer of polymeric.
8. preparation method according to claim 7 is characterized in that described styrenic monomers is styrene monomer, α-Jia Jibenyixidanti, α-chloro-styrene monomer or P-vinyl toluene monomer.
9. preparation method according to claim 8 is characterized in that described styrenic monomers is a styrene monomer.
10. according to the preparation method of claim 1, it is characterized in that described acrylic monomer is an acrylonitrile monemer.
11, preparation method according to claim 1, it is characterized in that emulsifying agent is compound saponification system in the step (1), select the compound saponification system of compound saponification system, potassium oleate and lipid acid potassium of rosined soap and Sodium dodecylbenzene sulfonate or the compound saponification system of potassium stearate and lipid acid potassium for use.
12, preparation method according to claim 1, its feature have also added the molecular weight regulator of 0.25～0.65 weight part in step (1): tert-dodecyl mercaptan.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103342864A (en) * | 2013-07-19 | 2013-10-09 | 上海锦湖日丽塑料有限公司 | Electroplating ABS (Acrylonitrile Butadiene Styrene) resin with high binding force and preparation method thereof |
| CN105038074A (en) * | 2015-05-28 | 2015-11-11 | 安徽同丰橡塑工业有限公司 | Agglomeration graft modified powder nitrile butadiene rubber preparation method |
| CN103497282B (en) * | 2013-09-27 | 2016-02-10 | 安庆华兰科技有限公司 | A kind of preparation method of agglomeration graft modification Powdered acrylonitrile-butadiene rubber |
| CN112480437A (en) * | 2020-11-13 | 2021-03-12 | 天津大沽化工股份有限公司 | Preparation method of large-particle-size high-solid-content styrene-butadiene latex |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE1213984B (en) * | 1963-12-05 | 1966-04-07 | Huels Chemische Werke Ag | Process for agglomerating synthetic rubber dispersions |
| IN142236B (en) * | 1973-08-30 | 1977-06-11 | Mitsubishi Rayon Co | |
| CA1193036A (en) * | 1981-10-09 | 1985-09-03 | Kazuo Kishida | Process for producing impact resistant graft resins including an agglomerated rubber |
| CA1217291A (en) * | 1983-12-01 | 1987-01-27 | Kazuo Kishida | Thermoplastic resin composition having excellent impact resistance and heat resistance |
| US5336720A (en) * | 1991-06-05 | 1994-08-09 | Rohm And Haas Company | Impact resistant polymers |
| DE4344992A1 (en) * | 1993-12-30 | 1995-07-06 | Huels Chemische Werke Ag | Aqueous, highly concentrated synthetic rubber dispersion and its production |
| CN1670048A (en) * | 2005-03-02 | 2005-09-21 | 东营九洲奥华化工有限责任公司 | Method for preparing carboxylated NBR latex |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103342864A (en) * | 2013-07-19 | 2013-10-09 | 上海锦湖日丽塑料有限公司 | Electroplating ABS (Acrylonitrile Butadiene Styrene) resin with high binding force and preparation method thereof |
| CN103342864B (en) * | 2013-07-19 | 2016-05-11 | 上海锦湖日丽塑料有限公司 | A kind of electroplating ABS resin with high-bond and preparation method thereof |
| CN103497282B (en) * | 2013-09-27 | 2016-02-10 | 安庆华兰科技有限公司 | A kind of preparation method of agglomeration graft modification Powdered acrylonitrile-butadiene rubber |
| CN105038074A (en) * | 2015-05-28 | 2015-11-11 | 安徽同丰橡塑工业有限公司 | Agglomeration graft modified powder nitrile butadiene rubber preparation method |
| CN112480437A (en) * | 2020-11-13 | 2021-03-12 | 天津大沽化工股份有限公司 | Preparation method of large-particle-size high-solid-content styrene-butadiene latex |
| CN112480437B (en) * | 2020-11-13 | 2023-04-18 | 天津大沽化工股份有限公司 | Preparation method of large-particle-size high-solid-content styrene-butadiene latex |
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