CN107936165A - A kind of carboxylic styrene butadiene latex and its preparation process - Google Patents
A kind of carboxylic styrene butadiene latex and its preparation process Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08F2/22—Emulsion polymerisation
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- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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Abstract
The invention discloses a kind of carboxylic styrene butadiene latex and its preparation process, wherein, a kind of carboxylic styrene butadiene latex, including water are mutually expected（First solvent, the first emulsifying agent, acrylic acid, N hydroxymethyl acrylamide, acrylamide, pH adjusting agent）；Oil phase material（Styrene, butadiene, 3 mercaptobutyric acid ethyl esters）；Backing material（Mbs seed latex, neopelex, liquid caustic soda mixture）；Other material（4th solvent, disodium ethylene diamine tetraacetate, initiator mixture, aqueous defoamer, liquid caustic soda, the second emulsifying agent）；First emulsifying agent chooses anion emulsifier；Second emulsifying agent chooses nonionic emulsifier；First solvent and the 4th solvent are soft water.The carboxylic styrene butadiene latex that the present invention obtains has the advantages that high conversion rate, polymerization stability, mechanical stability, chemical stability are good.
Description
Technical field
The present invention relates to carboxylic styrene butadiene latex synthesis technical field, more specifically, it relates to a kind of carboxylic styrene butadiene latex
And its preparation process.
Background technology
Carboxylic styrene butadiene latex is to add a small amount of carboxylic acid and other auxiliary agents with butadiene, styrene, is generated by emulsion polymerization
Copolymer, is a kind of milky aqueous dispersion with bluish violet gloss.
The Chinese patent that application publication number is 104211858 A of CN, data of publication of application is on December 17th, 2014 discloses
A kind of carboxylic styrene butadiene latex, by styrene, butadiene, acrylic acid, seed glue, emulsifying agent, function monomer, sodium pyrophosphate, mercaptan,
The components such as chelating agent ammonium persulfate are made；And preparation process includes：(1) put into respectively 40~80% in composition of raw materials in reaction kettle
Water, 20~40% emulsifying agent, 20~40% acrylic acid, sodium pyrophosphate, function monomer, seed glue and chelating agent；(2) rise
It is interior when 2~4 is small that butadiene and styrene, mercaptan, remaining acrylic acid, composition of raw materials is at the uniform velocity added dropwise after warm to 83~94 DEG C
In 70~80% ammonium persulfate, 5~8% caustic soda and remaining emulsifying agent；(3) after monomer dropping, reaction temperature is improved
Degree to 93~98 DEG C, the reaction was continued 2~3 it is small when；The total conversion that polymerization is participated in when monomer reaches the 98.0% of monomer gross mass
During the above, 65~75 DEG C are cooled to, turns material extremely degassing kettle, adds in remaining ammonium persulfate and composition of raw materials 50~70% burning
Alkali, it is -0.07~-0.09MPa to control degassing kettle vacuum, when vacuum flashing degassing 3.5~4.5 is small, is then proceeded to residue
Caustic soda pH value to 7~9, cool to 35~45 DEG C.
Although the carboxylic styrene butadiene latex prepared by the prior art has preferable mechanical stability and chemistry surely
It is qualitative, but the prior art first, employs mercaptan there is being disadvantageous in that in preparation process, and stink is heavier, influences to give birth to
Produce environment and enterprise's periphery living environment；Secondly, in preparation process, the prior art have selected directly to butadiene and benzene second
The components such as alkene, mercaptan are added dropwise, and it is not abundant enough to easily lead to the polymerization of butadiene and styrene, so as to reduce carboxylic styrene butadiene latex
Conversion ratio, and the polymerization stability of carboxylic styrene butadiene latex that causes to obtain, mechanical stability, chemical stability are poor.
The content of the invention
In view of the deficienciess of the prior art, the purpose of the present invention one is to provide a kind of carboxylic styrene butadiene latex, have compared with
The advantages of high conversion ratio, preferable polymerization stability, mechanical stability, chemical stability.
To achieve the above object one, the present invention provides following technical solution：
A kind of carboxylic styrene butadiene latex, includes the component of following parts by weight：
Water is mutually expected：
First 4060-4155 parts of solvent；
First 55-75 parts of emulsifying agent；
370-388 parts of acrylic acid；
200-230 parts of N hydroxymethyl acrylamide；
125-150 parts of acrylamide；
18-33 parts of pH adjusting agent；
Oil phase material：
6915-6980 parts of styrene；
4005-4100 parts of butadiene；
92-110 parts of 3- mercaptobutyric acid ethyl esters；
Backing material：
210-250 parts of mbs seed latex；
10-16 parts of neopelex；
4000-5200 parts of liquid caustic soda mixture；
Other material：
4th 1400-1600 parts of solvent；
0.3-0.9 parts of disodium ethylene diamine tetraacetate；
1450-1468 parts of initiator mixture；
28-38 parts of aqueous defoamer；
750-880 parts of liquid caustic soda；
Second 39-55 parts of emulsifying agent；
First emulsifying agent chooses anion emulsifier；Second emulsifying agent chooses nonionic emulsifier；Described first is molten
Agent and the 4th solvent are soft water.
More preferably：The carboxylic styrene butadiene latex includes the component of following parts by weight：
Water is mutually expected：
First 4060-4120 parts of solvent；
First 55-70 parts of emulsifying agent；
370-380 parts of acrylic acid；
211-230 parts of N hydroxymethyl acrylamide；
125-140 parts of acrylamide；
22-33 parts of pH adjusting agent；
Oil phase material：
6915-6950 parts of styrene；
4050-4100 parts of butadiene；
92-105 parts of 3- mercaptobutyric acid ethyl esters；
Backing material：
210-240 parts of mbs seed latex；
10-15 parts of neopelex；
4000-4800 parts of liquid caustic soda mixture；
Other material：
4th 1500-1600 parts of solvent；
0.3-0.5 parts of disodium ethylene diamine tetraacetate；
1450-1462 parts of initiator mixture；
28-35 parts of aqueous defoamer；
800-880 parts of liquid caustic soda；
Second 45-55 parts of emulsifying agent.
More preferably：In other described material, initiator mixture includes initiator and the 3rd solvent, the initiator
Ratio of weight and number with the 3rd solvent is 0.08-0.12:1, the 3rd solvent is soft water.
More preferably：The initiator includes at least one of ammonium persulfate, sodium peroxydisulfate.
More preferably：In the backing material, liquid caustic soda mixture includes liquid caustic soda and the second solvent, the liquid caustic soda and second
The ratio of weight and number of solvent is 1-1.5:1, second solvent is soft water.
More preferably：During the water is mutually expected, pH adjusting agent includes NaHCO3、Na3PO4、Na2CO3, in NaOH at least
It is a kind of.
The purpose of the present invention two is to provide a kind of preparation process of carboxylic styrene butadiene latex.
To achieve the above object two, the present invention provides following technical solution：
A kind of preparation process of carboxylic styrene butadiene latex, includes the following steps：
S1, under vacuum, the first solvent of corresponding weight fraction, the first emulsifying agent, acrylic acid, N- hydroxyl first during water is mutually expected
Base acrylamide, acrylamide, pH adjusting agent are uniformly mixed, and are formed water and are mutually expected；
S2, under vacuum, the styrene of corresponding weight fraction, butadiene, 3- mercaptobutyric acids ethyl ester in oil phase material are mixed
Uniformly, oil phase material is formed；
S3, mbs seed latex mix the mbs seed latex of corresponding weight fraction, neopelex, liquid caustic soda in backing material
Compound is uniformly mixed, formed backing material by the mbs seed latex of corresponding weight fraction in backing material, neopelex,
Liquid caustic soda mixture is uniformly mixed, and forms backing material by the mbs seed latex of corresponding weight fraction, detergent alkylate sulphur in backing material
Sour sodium, liquid caustic soda mixture are uniformly mixed, and form backing material；
S4, under vacuum, takes the 4th solvent in other material, the water obtained in step S1 mutually to expect 260 parts, obtains in step S2
555 parts of oil phase material, 150 parts of the initiator mixture obtained is mixed, and is carried out polymerisation and is simultaneously formed the first mixture, is warming up to
At 83-85 DEG C, stop heating, obtain the second mixture；
S5, oil phase material, the remaining initiator water obtained in remaining step S1 is mutually expected, obtained in remaining step S2 mix
Compound is sufficiently mixed with the second mixture obtained in step S4, controlled at 93-95 DEG C, pressure 0.3-0.4MPa, is protected
Temperature；
S6, when conversion ratio reaches more than 99.5%, is de-gassed processing, while add water-based to the material obtained in step S5
Defoamer, is uniformly mixed；Add the liquid caustic soda in other material of corresponding parts by weight, disodium ethylene diamine tetraacetate, the second emulsification
Agent, is sufficiently mixed, and eliminates residual benzene, and the degassing process time is 4-5h；
S7, blowing, filtering, obtains carboxylic styrene butadiene latex.
More preferably：In the step S4, after stopping heating, polymerisation elevated temperature, by adjusting cooling water
Flow, control temperature react 10-15min at 93-95 DEG C.
More preferably：In the step S5, the water obtained in remaining step S1 is mutually expected, is obtained in remaining step S2
Oil phase material, the remaining initiator mixture obtained is added by the way of dropping evenly, and water mutually expects to be added dropwise at the same time with oil phase material
And the time being added dropwise is 4-4.5h；The time for adding of initiator mixture is 4.5-5h.
More preferably：In the step S5, the time of the insulation is 1.5-2h.
Through the above technical solutions, the first solvent, the second solvent, the 3rd solvent, the 4th solvent in the application select
Soft water, helps to reduce the Ca in reaction system2+、Mg2+Ion etc., so that reducing consersion unit the phenomenon of fouling occurs, reduces
The cost of maintenance and repair, it helps improve the purity and quality for the carboxylic styrene butadiene latex that polymerization is formed.
In preparation process, first water is mutually expected, oil phase material, backing material prepare respectively it is spare, then by by soft water, part
Water is mutually expected, the mixing of part oil phase material, part initiator mixture, after remaining water is mutually expected, oil phase material and initiator to be to drip
The mode added is slowly added to, so that polymerisation is more abundant.When being warming up to 83-85 DEG C in step S4, stop heating, polymerization
Reaction can produce substantial amounts of heat and form the first mixture, and the temperature of the first mixture is improved, and be carried out by cooling water
The container where polymerisation is cooled down, by temperature control at 93-95 DEG C, and 10-15min is reacted, polymerisation is fully carried out,
So as to improve the mixing uniformity of the second mixture of acquisition.
In step S5, remaining water is mutually expected that with oil phase material while the time of dropwise addition and dropwise addition be 4-4.5h；It is remaining to draw
The time for adding for sending out agent composition is 4.5h, and maintains the temperature at 93-95 DEG C, keeps the temperature 1.5-2h, pressure 0.3-0.4MPa, has
Help make the polymerisation of styrene and butadiene more abundant.
During the degassing process of step S6, first by 1/3rd or so outlet vacuum tube regulating valve, prevent outlet too fast and
Foam is pulled out；Big regulating valve is progressively opened again until opening completely, and open live (open) steam and carry out stripping degassing when foam is steady.
In addition, adding the liquid caustic soda in other material, disodium ethylene diamine tetraacetate, the second emulsifying agent, can largely eliminate residual benzene.Degassing
Processing time continues 4-5h, and after deaerating by cooling water temperature to 40 DEG C, make the carboxylic styrene butadiene latex of acquisition formed stablize and
The few state of foam volume, then filtered, obtain the carboxylic styrene butadiene latex of high quality.
Wherein, N hydroxymethyl acrylamide is highly soluble in water, the vinyl containing polymerization and condensation in molecular structure
The methylol of performance, as crosslinking agent, helps to promote styrene and butadiene to carry out effective crosslinked action.And N- methylols
Acrylamide and acrylic ester copolymerization, are introduced into methylol, can be crosslinked in a heated condition.And acrylic acid is one
Kind unsaturated carboxylic acid, polymerization speed are fast.Therefore, it is equal in the first emulsifying agent, acrylic acid, N hydroxymethyl acrylamide, acrylamide
Water can be mixed to form in soft water mutually to expect, and can carry out polymerisation with styrene and butadiene.
NaHCO in pH adjusting agent3、Na3PO4、Na2CO3, NaOH have it is preferable and stablize alkalescence effect, will can react
System adjusts to form relatively stable alkaline environment, so that overall have preferably stable environment；Liquid caustic soda in backing material
Mixture, is to mix liquid caustic soda and soft water to obtain, backing material is reduced reaction wind when directly using liquid caustic soda for alkalescence
Danger, and initiator mixture can play more preferable more stable effect in overall system；Other material belong to mutually expect in water, oil
Mutually material is added again after being mutually mixed, and therefore, the addition of liquid caustic soda therein is mainly used for adjusting the pH value of whole system.
3- mercaptobutyric acids ethyl ester in oil phase material compares tert-dodecyl mercaptan, can reduce the smell in whole system, and valency
Lattice are lower, contribute to cost-effective, and it forms sufficient mix with styrene, butadiene.
The selection of first emulsifying agent uses anion emulsifier, its hydrophilic radical carries negative charge, and acrylic acid is anion
Type, acrylamide hydrolyzes under the aqueous environment of alkalescence, in anionic；Anion emulsifier can strengthen acrylic acid, N- hydroxyl first
The surface charge of base acrylamide, acrylamide, so that each component during water is mutually expected adequately and uniformly disperses.Dodecyl
Benzene sulfonic acid sodium salt is anionic surfactant, when water is mutually expected, oil phase material is mixed, can stablize acid, the chemical property of alkali,
Make whole system relatively stable, in the course of the polymerization process, be less prone to pockets of phenomenon.
And the second emulsifying agent then uses nonionic emulsifier, do not dissociated when being dissolved in water, high stability, and be not easy
Influenced be subject to strong electrolyte, be not easy to be influenced by acid, alkali, hydrophilic radical therein is mainly by a certain number of oxy radicals
Form, during mixing, its preferable compatibility, in the polymerization between promoting each component, does not easily cause each group
/ there is agglomeration.
In initiator, ammonium persulfate and sodium peroxydisulfate are respectively provided with the effect that more excellent promotion polymerize, sodium peroxydisulfate
Facilitation is slightly poorer than ammonium persulfate, and the cheaper of ammonium persulfate, if using ammonium persulfate, contributes to reduction to be produced into
This, and it has longer half-life period, helps to promote polymerisation within the longer term.By the way that initiator and soft water are mixed
Close, so that the initiator mixture formed has uniform effect, each component easy to mutually expect with water, in oil phase material etc. is formed
Preferable immixture, so as to promote styrene that sufficient polymerisation occurs with butadiene.
In conclusion the invention has the advantages that：
1. by the backing material being made of respective components being partly pre-mixed, water is mutually expected, oil phase material is mixed, second is formed
Mixture, then the related component of remainder is carried out while mixing is added dropwise, help to make polymerisation further carry out more
Add fully, and make the carboxylic styrene butadiene latex to be formed that there is more preferable polymerization stability, mechanical stability and chemical stability；
2. using the first emulsifying agent, the second emulsifying agent, the mutual complex role of neopelex, coordinate corresponding addition
Mode, makes that the pick resistance of the carboxylic styrene butadiene latex of acquisition is good, and dispersion effect is good, is not easy agglomerating；
3. in degassing process, water-based defoamer is added, it is relatively soluble in the liquid phase of higher temperature, carries out defoaming work rapidly
With, and in degasification process, moreover it is possible to prevent the generation of bubble, be remarkably improved the effect of defoaming suds；
4. using 3- mercaptobutyric acid ethyl esters in the application, help to make styrene form sufficient mix with butadiene, moreover it is possible to subtract
Few smell, and reduce production cost；
5. the reaction time is shorter, production efficiency is helped to improve.
Embodiment
With reference to embodiment, the present invention will be described in detail.
Embodiment 1：A kind of carboxylic styrene butadiene latex, including component it is as shown in table 1, and be made by the steps and obtain
：
S1, under vacuum, the first solvent, odium stearate, acrylic acid, the N- methylols of corresponding weight fraction during water is mutually expected
Acrylamide, acrylamide, pH adjusting agent are uniformly mixed, and are formed water and are mutually expected；
S2, under vacuum, the styrene of corresponding weight fraction, butadiene, 3- mercaptobutyric acids ethyl ester in oil phase material are mixed
Uniformly, oil phase material is formed；
S3, the mbs seed latex of corresponding weight fraction, neopelex, liquid caustic soda mixture in backing material is mixed equal
It is even, form backing material；
S4, under vacuum, takes the 4th solvent in other material, the water obtained in step S1 mutually to expect 260 parts, obtains in step S2
555 parts of oil phase material, 150 parts of the initiator mixture obtained is mixed, and is carried out polymerisation and is simultaneously formed the first mixture, is warming up to
At 83 DEG C, stopping heating, polymerisation elevated temperature, by adjusting cooling water flow, control temperature reacts 15min at 93 DEG C,
Obtain the second mixture；
S5, oil phase material, the remaining initiator water obtained in remaining step S1 is mutually expected, obtained in remaining step S2 mix
Compound is added dropwise to the second mixture obtained in step S4 at the same timeIn,Water mutually expects that with the time for adding of oil phase material be 4h；Initiator
The time for adding of mixture is 4.5h；Controlled at 95 DEG C, pressure 0.4MPa, 1.5h is kept the temperature；
S6, when conversion ratio reaches more than 99.5%, is de-gassed processing, while add water-based to the material obtained in step S5
Defoamer, is uniformly mixed；Add the liquid caustic soda in other material of corresponding parts by weight, disodium ethylene diamine tetraacetate, the second emulsification
Agent, is sufficiently mixed, and eliminates residual benzene, and the degassing process time is 4h；
S7, blowing, filtering, obtains carboxylic styrene butadiene latex.
Wherein, in other material, it is 0.1 that initiator mixture, which includes ratio of weight and number,:1 initiator and soft water, triggers
It is 1 that agent, which includes ratio of weight and number,：1 ammonium persulfate, sodium peroxydisulfate；In backing material, liquid caustic soda mixture includes ratio of weight and number
For 1:1 liquid caustic soda and soft water；In water is mutually expected, pH adjusting agent NaHCO3.Mbs seed latex says limited rubber purchased from Shandong day
Company.
Embodiment 2-5：A kind of carboxylic styrene butadiene latex, with embodiment 1 difference lies in, including the component such as institute of table 1
Show.
Component and its corresponding parts by weight in 1 embodiment 1-5 of table
Embodiment 6：A kind of carboxylic styrene butadiene latex, with embodiment 1 difference lies in, in other material, initiator mixture bag
Ratio of weight and number is included as 0.08:1 initiator and soft water, initiator are ammonium persulfate.
Embodiment 7：A kind of carboxylic styrene butadiene latex, difference lies in initiator mixture includes parts by weight with embodiment 6
Than for 0.12:1 initiator and soft water, initiator are sodium peroxydisulfate.
Embodiment 8：A kind of carboxylic styrene butadiene latex, with embodiment 1 difference lies in, in backing material, liquid caustic soda mixture bag
Ratio of weight and number is included as 1.5:1 liquid caustic soda and soft water.
Embodiment 9：A kind of carboxylic styrene butadiene latex, difference lies in pH adjusting agent Na with embodiment 13PO4、Na2CO3's
Compound, both ratios of weight and number are 1:1.
Embodiment 10：A kind of carboxylic styrene butadiene latex, difference lies in pH adjusting agent NaHCO with embodiment 13、Na3PO4、
Na2CO3Compound, the ratio of weight and number of three is 1:1:1.
Embodiment 11：A kind of carboxylic styrene butadiene latex, difference lies in pH adjusting agent NaHCO with embodiment 13、Na3PO4、
Na2CO3, NaOH compound, four ratio of weight and number is 1:1:1:1.
Embodiment 12：A kind of carboxylic styrene butadiene latex, difference lies in step S4, form the first mixture with embodiment 1
Afterwards, 85 DEG C are warming up to, after stopping heating, adjusts cooling water flow, control temperature reacts 10min at 95 DEG C.
Embodiment 13：A kind of carboxylic styrene butadiene latex, difference lies in step S5, water is mutually expected and oil phase material with embodiment 1
Time for adding be 4.5h；The time for adding of initiator mixture is 5h；Controlled at 93 DEG C, pressure 0.3MPa, insulation
2h。
Embodiment 14：A kind of carboxylic styrene butadiene latex, difference lies in step S6, when conversion ratio reaches with embodiment 1
When more than 99.5%, the degassing process time is 5h.
Comparative example 1：A kind of carboxylic styrene butadiene latex, difference lies in preparation process is with embodiment 1：
Water is mutually expected, oil phase material, backing material, each component in other material at the same mixing and 900rpm speed stir 12h, obtain
.
Comparative example 2：A kind of carboxylic styrene butadiene latex, difference lies in preparation process is with embodiment 1：
It will configure that the water that is formed mutually is expected, oil phase material, backing material are all mutually mixed, stir 4h under the speed of 900rpm, then add
Enter each component in other material, 8h is stirred under the speed of 1000rpm, obtain.
Comparative example 3：A kind of carboxylic styrene butadiene latex, difference lies in lack the first emulsifying agent, the second emulsification with embodiment 1
Agent and neopelex.
Comparative example 4：A kind of carboxylic styrene butadiene latex, difference lies in replace 3- mercaptos using tert-dodecyl mercaptan with embodiment 1
Base ethyl butyrate.
Experiment：Predominantly detect polymerization stability, mechanical stability, chemical stability, conversion ratio, average grain diameter, foam volume
And smell；
Test specimen：Embodiment 1-14 and comparative example 1-4 is chosen as sample；
Test method：According to《The measure of GBT 8301-2008 concentrated natural latex mechanical stabilities》Requirement, using XR-14
Latex stability tester is respectively detected embodiment 1-14 and comparative example 1-4, records data and analyzes.
Result of the test：Embodiment 1-14, the Testing index of comparative example 1-4 are as shown in table 2.
2 embodiment 1-14 of table, the Testing index of comparative example 1-4
As shown in Table 2, the conversion ratio of first, embodiment 1-14 be maintained at 99.6% and more than, average grain diameter 7-8 ×
10-8In the range of m, and the conversion ratio of comparative example 1-3 can only achieve 90.1-90.8%, and average grain diameter is in 29-35 × 10-8M's
In the range of, illustrate the compounding use of either the first emulsifying agent, the second emulsifying agent and neopelex, or water phase
The order by merging of material, oil phase material, backing material etc., can produce the conversion ratio and particle diameter of carboxylic styrene butadiene latex more obvious
Influence；And in comparative example 4, employ tert-dodecyl mercaptan and replace 3- mercaptobutyric acid ethyl esters, other components and order by merging are not
Become, still cause conversion ratio to reduce, illustrate the carboxyl of polymerization and generation of the 3- mercaptobutyric acids ethyl ester to styrene and butadiene
The particle diameter of styrene-butadiene latex produces more active influence.
Second, embodiment 1-14 has more excellent polymerization stability, mechanical stability and chemical stability at the same time, i.e.,
Polymerization stability, mechanical stability and the chemical stability of embodiment 1-14 is corresponded well below comparative example 1-4's
Polymerization stability, mechanical stability and chemical stability, illustrate water mutually expect, the component in oil phase material, backing material etc., and mixing
Order, the polymerization stability of the carboxylic styrene butadiene latex of formation, mechanical stability and chemical stability can be produced significant
Influence, i.e., water formed by the way of in the application and mutually expects, oil phase material, backing material etc. and mixed according to corresponding order,
Help to improve polymerization stability, mechanical stability and the chemical stability for the carboxylic styrene butadiene latex to be formed.
3rd, viscosity possessed by embodiment 1-14 is less than the viscosity in comparative example 1-3, illustrates the first emulsifying agent, second
The order that emulsifying agent and neopelex and three add, the viscosity of the carboxylic styrene butadiene latex that can be formed produce compared with
Big influence.
In 4th, comparative example 1-2, the preparation process of use is different from the preparation process in embodiment 1-14, and add
The order of defoamer is also different, and result in has more foam in comparative example 1-2, can directly affect the product after follow-up use
The quality of (such as paper).
Mixed in 5th, embodiment 1-14 using 3- mercaptobutyric acids ethyl ester with styrene and butadiene progress first time, and
Mixed in comparative example 4 using tert-dodecyl mercaptan with styrene and butadiene progress first time, other components and preparation process
All same, although however, 4 foam of comparative example prepared is less, the taste produced is larger, is unfavorable for health.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention belong to protection scope of the present invention.It should be pointed out that for the art
Those of ordinary skill for, some improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of carboxylic styrene butadiene latex, it is characterised in that be made of the component of following parts by weight：
Water is mutually expected：
First 4060-4155 parts of solvent；
First 55-75 parts of emulsifying agent；
370-388 parts of acrylic acid；
200-230 parts of N hydroxymethyl acrylamide；
125-150 parts of acrylamide；
18-33 parts of pH adjusting agent；
Oil phase material：
6915-6980 parts of styrene；
4005-4100 parts of butadiene；
92-110 parts of 3- mercaptobutyric acid ethyl esters；
Backing material：
210-250 parts of mbs seed latex；
10-16 parts of neopelex；
4000-5200 parts of liquid caustic soda mixture；
Other material：
4th 1400-1600 parts of solvent；
0.3-0.9 parts of disodium ethylene diamine tetraacetate；
1450-1468 parts of initiator mixture；
28-38 parts of aqueous defoamer；
750-880 parts of liquid caustic soda；
Second 39-55 parts of emulsifying agent；
First emulsifying agent chooses anion emulsifier；Second emulsifying agent chooses nonionic emulsifier；Described first is molten
Agent and the 4th solvent are soft water.
2. a kind of carboxylic styrene butadiene latex according to claim 1, it is characterised in that the carboxylic styrene butadiene latex by weighing as follows
Measure the component composition of number：
Water is mutually expected：
First 4060-4120 parts of solvent；
First 55-70 parts of emulsifying agent；
370-380 parts of acrylic acid；
211-230 parts of N hydroxymethyl acrylamide；
125-140 parts of acrylamide；
22-33 parts of pH adjusting agent；
Oil phase material：
6915-6950 parts of styrene；
4050-4100 parts of butadiene；
92-105 parts of 3- mercaptobutyric acid ethyl esters；
Backing material：
210-240 parts of mbs seed latex；
10-15 parts of neopelex；
4000-4800 parts of liquid caustic soda mixture；
Other material：
4th 1500-1600 parts of solvent；
0.3-0.5 parts of disodium ethylene diamine tetraacetate；
1450-1462 parts of initiator mixture；
28-35 parts of aqueous defoamer；
800-880 parts of liquid caustic soda；
Second 45-55 parts of emulsifying agent.
3. a kind of carboxylic styrene butadiene latex according to claim 1 or 2, it is characterised in that in other described material, initiator mixes
Compound includes initiator and the 3rd solvent, and the ratio of weight and number of the initiator and the 3rd solvent is 0.08-0.12:1, described
Three solvents are soft water.
A kind of 4. carboxylic styrene butadiene latex according to claim 3, it is characterised in that the initiator include ammonium persulfate,
At least one of sodium peroxydisulfate.
A kind of 5. carboxylic styrene butadiene latex according to claim 1 or 2, it is characterised in that in the backing material, liquid caustic soda mixing
Thing includes liquid caustic soda and the second solvent, and the ratio of weight and number of the liquid caustic soda and the second solvent is 1-1.5:1, second solvent is soft
Water.
A kind of 6. carboxylic styrene butadiene latex according to claim 1 or 2, it is characterised in that during the water is mutually expected, pH adjusting agent
Including NaHCO3、Na3PO4、Na2CO3, at least one of NaOH.
A kind of 7. preparation process of carboxylic styrene butadiene latex as described in any one in claim 1 or 2, it is characterised in that bag
Include following steps：
S1, under vacuum, the first solvent of corresponding weight fraction, the first emulsifying agent, acrylic acid, N- hydroxyl first during water is mutually expected
Base acrylamide, acrylamide, pH adjusting agent are uniformly mixed, and are formed water and are mutually expected；
S2, under vacuum, the styrene of corresponding weight fraction, butadiene, 3- mercaptobutyric acids ethyl ester in oil phase material are mixed
Uniformly, oil phase material is formed；
S3, mbs seed latex mix the mbs seed latex of corresponding weight fraction, neopelex, liquid caustic soda in backing material
Compound is uniformly mixed, and forms backing material；
S4, under vacuum, takes the 4th solvent in other material, the water obtained in step S1 mutually to expect 260 parts, obtains in step S2
555 parts of oil phase material, 150 parts of the initiator mixture obtained is mixed, and is carried out polymerisation and is simultaneously formed the first mixture, is warming up to
At 83-85 DEG C, stop heating, obtain the second mixture；
S5, oil phase material, the remaining initiator water obtained in remaining step S1 is mutually expected, obtained in remaining step S2 mix
Compound and the second mixture obtained in step S4It is sufficiently mixed, controlled at 93-95 DEG C, pressure 0.3-0.4MPa, protect
Temperature；
S6, when conversion ratio reaches more than 99.5%, is de-gassed processing, while add water-based to the material obtained in step S5
Defoamer, is uniformly mixed；Add the liquid caustic soda in other material of corresponding parts by weight, disodium ethylene diamine tetraacetate, the second emulsification
Agent, is sufficiently mixed, and eliminates residual benzene, and the degassing process time is 4-5h；
S7, blowing, filtering, obtains carboxylic styrene butadiene latex.
A kind of 8. preparation process of carboxylic styrene butadiene latex according to claim 7, it is characterised in that in the step S4,
After stopping heating, polymerisation elevated temperature, by adjusting cooling water flow, control temperature reacts 10- at 93-95 DEG C
15min。
A kind of 9. preparation process of carboxylic styrene butadiene latex according to claim 7, it is characterised in that in the step S5,
Oil phase material, the remaining initiator mixture that the water obtained in remaining step S1 mutually expects, is obtained in remaining step S2 are adopted
Added with the mode dropped evenly, water mutually expects that with oil phase material while the time of dropwise addition and dropwise addition be 4-4.5h；Initiator mixture
Time for adding be 4.5-5h.
A kind of 10. preparation process of carboxylic styrene butadiene latex according to claim 7, it is characterised in that in the step S5,
The time of the insulation is 1.5-2h.
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| CN108794705A (en) * | 2018-06-30 | 2018-11-13 | 江南大学 | A kind of preparation method and application of modified carboxyl styrene-butadiene latex |
| CN110407983A (en) * | 2018-04-26 | 2019-11-05 | 中国石油化工股份有限公司 | Carboxylic styrene butadiene latex and its preparation method and application |
| CN111154020A (en) * | 2020-01-19 | 2020-05-15 | 杭州龙驹合成材料有限公司 | Regenerated carboxylic styrene-butadiene latex for leather and preparation method thereof |
| CN117551234A (en) * | 2023-12-30 | 2024-02-13 | 珠海金鸡化工有限公司 | Low-odor carboxyl styrene-butadiene latex and preparation method thereof |
| CN118108885A (en) * | 2024-03-01 | 2024-05-31 | 绿能纤材(重庆)科技有限公司 | Preparation method and application of carboxylated styrene-butadiene latex |
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| CN117551234A (en) * | 2023-12-30 | 2024-02-13 | 珠海金鸡化工有限公司 | Low-odor carboxyl styrene-butadiene latex and preparation method thereof |
| CN118108885A (en) * | 2024-03-01 | 2024-05-31 | 绿能纤材(重庆)科技有限公司 | Preparation method and application of carboxylated styrene-butadiene latex |
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