CN103450409A - Environment-friendly styrene-acrylic emulsion with ultra-low VOC (Volatile Organic Compound) content and preparation method thereof - Google Patents
Environment-friendly styrene-acrylic emulsion with ultra-low VOC (Volatile Organic Compound) content and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly styrene-acrylic emulsion with ultra-low VOC (Volatile Organic Compound) content and a preparation method thereof. The preparation method is characterized in that natural olefin matters are added to styrene and butyl acrylate serving as main monomers and acrylic acid serving as a functional monomer and participate in polymerization reaction so as to obtain the environment-friendly styrene-acrylic emulsion with the ultra-low VOC content. The system for preparing the styrene-acrylic emulsion comprises the following components in percentage by mass: 14-22% of styrene, 15-26% of butyl acrylate, 0.85-1% of acrylic acid, 0-4% of natural olefins matters, 0.1-0.6% of triggering agent, 0.5-3.0% of emulsifying agent and the balance of water. The styrene-acrylic emulsion is prepared by adding the natural olefin matters, so that smell can be reduced, the VOC content (lower than 500ppm) is reduced, and the conversion rate of monomers can also be increased. The preparation method is simple in process, low in energy consumption and cost and easy for realizing industrialization. The styrene-acrylic emulsion is environment-friendly and meets the practical production requirements.
Description
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Technical field
The present invention relates to the preparation of benzene emulsion, particularly environment-friendly type benzene emulsion of a kind of ultralow VOC content and preparation method thereof.
Background technology
Along with the more attention of people to environment protection; environmentally friendly product more and more receives general concern, and emulsion adhesive is because having nonflammable explosive, production cost is low, the advantage such as easy to use becomes tackiness agent, coating for internal and external wall, leather treatment, fabric finishing agent gradually development trend.Yet the volatile organic matter of the product emulsion that market produces in recent years (volatile organic compounds, VOC) higher (residual monomer content generally surpasses 0.5% to content, 5/1000ths), the content that reduces VOC (makes residual monomer content reach 500 ppm, below 5/10000ths), making product emulsion almost there is no smell is the target that the present emulsion polymerization technique makes great efforts to reach.The content that how further to reduce Volatile residual monomers in letex polymerization is to be badly in need of the subject matter solved in scientific research in recent years and production to reduce product VOC content.
For head it off, a lot of researchers have been done large quantity research aspect aftertreatment, are mainly the following aspects:
(1) the nitrogen flooding division (Chen Yongliang. eliminate the method [J] of monomer smell in emulsion polymer. print 1994 (8): 20-24.) during chemical industry
Blow people's nitrogen while stirring in polymeric kettle in the polymerization later stage, thereby expeling unreacted monomer, but because some monomer has certain solubleness in water, emulsifying agent also can increase the steady dissolution of monomer in water, so do not reach certain effect in this method practical application of this occasion, but also can cause the pollution of production plant environment, so should not take.
(2) rays method (Chen Yongliang. eliminate the method for monomer smell in emulsion polymer .)
The air that contains ozone with gammairradiation, make the unreacted monomer cracking, thereby eliminate unsaturated C=C key, although this method obtains effect preferably, condition is harsher, is difficult to practical application.
(3) to polymkeric substance take to vacuumize (Chen Yongliang. eliminate the method for monomer smell in emulsion polymer .)
After reaction finishes, in the situation that do not have coolingly, polymeric system is vacuumized, the volatile monomers that will not participate in polymerization is taken away.Although the result of doing like this can reduce the smell of volatile monomers to a certain extent, also reduced monomer conversion simultaneously, make unreacted monomer directly be pumped, rather than participate in reacting generating copolymer, so this method is very undesirable.
(4) later stage insulation add strong reductant (Chen Yongquan. add the smell that hydrazine hydrate is eliminated acrylic ester emulsion polymerization residual monomer. chemistry world, 1994,35 (8): 436-438.)
Add the strong reductant hydrazine hydrate can solve preferably its problem.Although found through experiments the smell aspect, make moderate progress, hydrazine hydrate itself is a kind of poisonous compound, and this product is environment-protective adhesive, and add-on is many, can cause human body poisoning; Add-on has been lacked, and can't remove residual monomer fully, so this method does not continue to continue to use.
(5) microwave treatment reaction (Yang Bo; He Hui; The Judd people. microwave radiation prepares the progress of emulsion particle. insulating material, 2008,41 (2): 49-52.)
Select the post-processing step after microwave radiation finishes as experiment, make the residual monomer that has neither part nor lot in reaction be converted into polymkeric substance, reduce the monomer smell in emulsion, this method just started to have received good effect, and smell has disappeared, guaranteed the stability of product emulsion simultaneously, but, through the normal temperature storage of month, find the emulsion through microwave treatment, breakdowns of emulsion all, and solidify fully.Illustrate by microwave treatment and can not guarantee standing storage, so or need further to improve.
Above method effect is unsatisfactory, in actual production, does not promote.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming that overcomes prior art, with not enough, provides a kind of preparation method of environment-friendly type benzene emulsion of ultralow VOC content.
Another object of the present invention is to provide a kind of environment-friendly type benzene emulsion of the ultralow VOC content prepared by aforesaid method.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of environment-friendly type benzene emulsion of ultralow VOC content is that to take vinylbenzene (St), butyl acrylate (BA) be main monomer, and vinylformic acid (AA) is function monomer, adds natural olefines material to participate in polyreaction.Described natural olefines material is preferably rosin, Abietyl modified thing, sunflower seed oil, peanut oil, soya-bean oil or sweet oil; Preferred, described natural olefines material is Abietyl modified thing or sunflower seed oil.
Preferably, the preparation method of the environment-friendly type benzene emulsion of described ultralow VOC content specifically comprises the following steps:
(1) preparatory stage
Emulsifying agent, initiator are dissolved in the water respectively and obtain emulsifier solution and initiator solution;
(2) the pre-emulsification stage
The emulsifier solution of getting 45～55% quality joins natural olefines material and participates in, in the monomer of polymerization, stirring the pre-emulsion that obtains white thickness;
(3) the seed priming stage
By the heating of remaining emulsifier solution, while being warmed up to approximately 76～78 ℃, drip the pre-emulsion of 18～22% quality and the initiator solution of 1/6～1/3 quality, be incubated approximately 30～40 min;
(4) step of reaction
After insulation finishes, continue to drip remaining pre-emulsion, and drip the initiator solution of 1% quality every 10～20 min, after dripping, temperature of reaction is controlled between 76～84 ℃, be incubated approximately 1～1.25 h;
(5) holding stage
Be warming up to 88～91 ℃, continue approximately 1～1.25 h of insulation;
(6) the cooling dress sample stage
After insulation finishes, while being cooled to 40～50 ℃, with sodium hydrogen carbonate solution adjust pH to 6～7, cooling dress sample then, obtain the environment-friendly type benzene emulsion of ultralow VOC content;
In system, the quality percentage composition of each component is respectively: vinylbenzene 14～22%, and butyl acrylate 15～26%, vinylformic acid 0.85～1%, natural olefines material 0～4%, initiator 0.1～0.6%, emulsifying agent 0.5～3.0%, surplus is water.
Emulsifying agent described in step (1) is preferably at least one in sodium lauryl sulphate (SDS), alkylphenol polyoxyethylene (OP-10) and polyoxyethylene nonylphenol ether (NP-10).
Initiator described in step (1) is preferably ammonium persulphate (APS).
When described natural olefines material is Abietyl modified thing, the monomer that participates in polymerization is vinylbenzene (St), butyl acrylate (BA) and vinylformic acid (AA), and emulsifying agent is the compound emulsifying agent that sodium lauryl sulphate (SDS) and alkylphenol polyoxyethylene (OP-10) form; In system, the quality percentage composition of each component is respectively: vinylbenzene 14～22%, butyl acrylate 18～26%, vinylformic acid 1%, Abietyl modified thing 0～4%, initiator 0.1～0.6%, sodium lauryl sulphate 0.5～2.0%, alkylphenol polyoxyethylene 0.5～1.0%, surplus is water; Preferably, described Abietyl modified thing is ester gum, and its quality percentage composition is 2%, and the quality percentage composition of compound emulsifying agent is 3.0%, and the quality percentage composition of initiator is 0.5%; Temperature of reaction in step (4) is controlled at 78～82 ℃.
When described natural olefines material is sunflower seed oil, the monomer that participates in polymerization is vinylbenzene (St), butyl acrylate (BA) and vinylformic acid (AA), emulsifying agent is the compound emulsifying agent that sodium lauryl sulphate (SDS) and polyoxyethylene nonylphenol ether (NP-10) form, in system, the quality percentage composition of each component is respectively: vinylbenzene 14～22%, butyl acrylate 15～25%, vinylformic acid 0.85%, sunflower seed oil 0～4%, initiator 0.1～0.5%, sodium lauryl sulphate 0.5～2.0%, polyoxyethylene nonylphenol ether 0.4～0.8%, surplus is water.Preferably, the quality percentage composition of sunflower seed oil is 1%, and the quality percentage composition of compound emulsifying agent is 2.5%, and the quality percentage composition of initiator is 0.3%; Temperature of reaction in step (4) is controlled at 78～84 ℃.
A kind of environment-friendly type benzene emulsion of ultralow VOC content, prepare by above-mentioned preparation method.
The present invention has following advantage and effect with respect to prior art:
The present invention is by adding a class to participate in polyreaction with the natural olefines material of two keys, solved that existing method is easily polluted, working conditions harsh, monomer conversion is low, easily introduces toxic substance, the easy problem of breakdown of emulsion.Add natural olefines material to prepare benzene emulsion, not only can reduce smell, reduce VOC content (lower than 500 ppm), but also can improve the transformation efficiency of monomer.The inventive method process is simple and easy to control, and power consumption is few, and cost is low, is easy to realize industrialization, realistic need of production.
The accompanying drawing explanation
Fig. 1 adds affect the as a result figure of the amount of Abietyl modified thing and sunflower seed oil on monomer conversion.
When Fig. 2 is Abietyl modified thing participation monomer copolymerization, affect the as a result figure of emulsifier on monomer conversion and solid content.
When Fig. 3 is sunflower seed oil participation monomer copolymerization, affect the as a result figure of emulsifier on monomer conversion and solid content.
When Fig. 4 is Abietyl modified thing participation monomer copolymerization, affect the as a result figure of emulsifier on monomer conversion and gel fraction.
When Fig. 5 is sunflower seed oil participation monomer copolymerization, affect the as a result figure of emulsifier on monomer conversion and gel fraction.
When Fig. 6 is Abietyl modified thing participation monomer copolymerization, affect the as a result figure of initiator amount on solid content and viscosity.
When Fig. 7 is sunflower seed oil participation monomer copolymerization, affect the as a result figure of initiator amount on solid content and monomer conversion.
Fig. 8 is while adding respectively Abietyl modified thing and sunflower seed oil and monomer copolymerization, the size distribution figure of emulsion, A: Abietyl modified thing, B: sunflower seed oil.
Fig. 9 is the FTIR figure of the benzene emulsion that adds Abietyl modified thing to prepare.
Figure 10 is the FTIR figure of the benzene emulsion that adds sunflower seed oil to prepare.
Figure 11 is the VOC content situation figure as a result that embodiment 8 and 9 adds benzene emulsion before and after natural olefines material.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is done to further detailed description, but embodiments of the present invention are not limited to this.
The preparation of the environment-friendly type benzene emulsion of the ultralow VOC content of embodiment 1
Comprise the following steps:
(1) preparatory stage
1) emulsifying agent of getting certain proportioning is added in tap water, with glass stick, stirs and makes it be dissolved as transparent liquid, obtains the composite emulsifying agent solution, stand-by;
2) get a certain amount of initiator and be dissolved in tap water and obtain initiator solution, stand-by;
3) monomer (vinylbenzene, butyl acrylate, vinylformic acid) and the natural olefines material of the participation of weighing according to a certain percentage polymerization are put into the single port bottle, stand-by;
4) the preparation saturated sodium bicarbonate solution, stand-by.
(2) the pre-emulsification stage
Get half amount of the emulsifier solution that dissolved and put into the single port flask that monomer is housed, stir about 0.5 h under the effect of mechanical stirrer, obtain the pre-emulsion of white thickness, places stand-by on one side.
(3) the seed priming stage
The emulsifier solution that is left half is put into to the four-necked bottle that constant pressure funnel, thermometer, mechanical stirring rod and reflux condensing tube are housed and do end liquid, four-necked bottle is put into oil bath pan, opens the heating unit heating, and stirring rod stirs; When temperature is raised to approximately 76 ℃, get 20 % quality pre-emulsions and be added drop-wise in four-necked bottle, drip the initiator solution of 1/4 quality with dropper simultaneously, can see that emulsion has blue light, and start in four-necked bottle to occur refluxing; After dropwising, be incubated approximately 0.5 h.
(4) step of reaction
After insulation finishes, continue to drip continuously remaining pre-emulsion, and drip the initiator solution of 1% quality every 10～20 min, about 2 h left and right drip, and temperature of reaction is controlled between 76～84 ℃.
(5) holding stage
After pre-emulsion and initiator solution all drip, about 1 h of insulation, while almost not refluxing in four-necked bottle, regulate heating unit and start to be warming up to 90 ℃, continues approximately 1 h of insulation, and further reaction is complete to make residual monomer.
(6) the cooling dress sample stage
After reaction finishes, close heating unit, whole reaction unit is proposed to oil bath pan, continue to stir, when temperature is down to 40～50 ℃, with saturated sodium bicarbonate solution adjust pH to 6～7, then cooling dress sample, obtain the oyster white environmental-friendly type emulsion with blue phase, obtain the environment-friendly type benzene emulsion of ultralow VOC content.
In system, the quality percentage composition of each component is respectively: vinylbenzene 14～22%, and butyl acrylate 15～26%, vinylformic acid 0.85～1%, natural olefines material 0～4%, initiator 0.1～0.6%, emulsifying agent 0.5～3.0%, surplus is water.
The impact of the add-on of the Abietyl modified thing of embodiment 2 and sunflower seed oil on monomer conversion
Add the quality percentage composition of each component of benzene emulsion system of Abietyl modified thing (ester gum) as follows: butyl acrylate (BA) 20%, vinylbenzene (St) 20%, vinylformic acid (AA) 1%, ester gum 0～4%, alkylphenol polyoxyethylene (OP-10) 1%, sodium lauryl sulphate (SDS) 2%, ammonium persulphate 0.5 %, surplus is water.Method according to embodiment 1 prepares benzene emulsion.
Add the quality percentage composition of each component of benzene emulsion system of sunflower seed oil as follows: butyl acrylate (BA) 17%, vinylbenzene (St) 17.85%, vinylformic acid (AA) 0.85%, sunflower seed oil 0～4%, polyoxyethylene nonylphenol ether (NP-10) 0.8%, sodium lauryl sulphate (SDS) 1.7%, ammonium persulphate 0.3%, surplus is water.Method according to embodiment 1 prepares benzene emulsion.
Result as shown in Figure 1, variation along with Abietyl modified thing consumption or sunflower seed oil consumption, monomer conversion all presents first increases the trend reduced afterwards, this is because a small amount of Abietyl modified thing or a small amount of sunflower seed oil can participate in monomer polymerization after by emulsification, thereby raising monomer conversion, but Abietyl modified thing and oil are all water-fast, produce gel thereby easily separate out when add-on is too much, make transformation efficiency reduce.So the optimum amount of Abietyl modified thing is 2%, and the optimal addn of sunflower seed oil is 1%.
The impact of embodiment 3 emulsifiers on monomer conversion and solid content
When Abietyl modified thing participates in monomer copolymerization, the quality percentage composition of each component of benzene emulsion system is as follows: butyl acrylate (BA) 20%, vinylbenzene (St) 20%, vinylformic acid (AA) 1%, ester gum 2%, alkylphenol polyoxyethylene (OP-10) 0.5～2.5%(0.5%, 1%, 1.5%, 2%, 2.5%), sodium lauryl sulphate (SDS) 1.5～3.5%(1.5%, 2%, 2.5%, 3%, 3.5%), ammonium persulphate 0.5%, surplus is water.Method according to embodiment 1 prepares benzene emulsion.
When sunflower seed oil participates in monomer copolymerization, the quality percentage composition of each component of benzene emulsion system is as follows: butyl acrylate (BA) 17%, vinylbenzene (St) 17.85%, vinylformic acid (AA) 0.85%, sunflower seed oil 1%, polyoxyethylene nonylphenol ether (NP-10) 0.5～1.5%(0.5%, 0.8%, 1%, 1.2%, 1.5%), sodium lauryl sulphate (SDS) 1.75～2.5%(1.25%, 1.7%, 2%, 2.3%, 2.5%), ammonium persulphate 0.3%, surplus is water.Method according to embodiment 1 prepares benzene emulsion.
Result as shown in Figures 2 and 3, increase along with emulsifier content, solid content first increases rear reduction and raises again, and monomer conversion is first to increase rear reduction, then slightly raise again, this is because when emulsifier is less, can only the cover part emulsion particle, between emulsion particle, easy autohemagglutination produces gel, and the micella that emulsifier forms when less is fewer, thereby make the monomer that can join in micellar aqueous solution fewer, transformation efficiency is relatively just lower, increase along with emulsifier, system tends towards stability, the corresponding rising of solid content, but when adding too much emulsifying agent, micella can be little and many, thereby cause system monomer conversion decline or substantially constant, so only add appropriate emulsifying agent just can obtain more stable emulsion system.When adding Abietyl modified thing to participate in monomer polymerization, the 3%(OP-10 1% that the consumption of emulsifying agent is total add-on, SDS 2%) time, solid content and monomer conversion are the highest, and system is relatively the most stable; And when adding sunflower seed oil to participate in monomer polymerization, the 2.5%(NP-10 0.8% that emulsifier is total add-on, SDS 1.7%) time, solid content and monomer conversion are the highest, and system is also relatively the most stable.
The impact of embodiment 4 emulsifiers on monomer conversion and gel fraction
When Abietyl modified thing participates in monomer copolymerization, the quality percentage composition of each component of benzene emulsion system is as follows: butyl acrylate (BA) 20%, vinylbenzene (St) 20%, vinylformic acid (AA) 1%, ester gum 2%, alkylphenol polyoxyethylene (OP-10) 0.5～2.5%(0.5%, 1%, 1.5%, 2%, 2.5%), sodium lauryl sulphate (SDS) 1.5～3.5%(1.5%, 2%, 2.5%, 3%, 3.5%), ammonium persulphate 0.5%, surplus is water.Method according to embodiment 1 prepares benzene emulsion.
When sunflower seed oil participates in monomer copolymerization, the quality percentage composition of each component of benzene emulsion system is as follows: butyl acrylate (BA) 17%, vinylbenzene (St) 17.85%, vinylformic acid (AA) 0.85%, sunflower seed oil 1%, polyoxyethylene nonylphenol ether (NP-10) 0.5～1.5%(0.5%, 0.8%, 1%, 1.2%, 1.5%), sodium lauryl sulphate (SDS) 1.75～2.5%(1.25%, 1.7%, 2%, 2.3%, 2.5%), ammonium persulphate 0.3%, surplus is water.Method according to embodiment 1 prepares benzene emulsion.
As seen from Figure 4, increase along with emulsifier content, conversion of monomer takes the lead in increasing rear reduction and then slightly raises, and gel takes the lead in reducing rear rising, because when emulsifier content is less, the micella produced is less, only has a small amount of emulsion particle capped, thereby easily has gel to produce, cause that monomer conversion is lower, when emulsifier content reaches a certain amount of, the Micelle of generation is many, forms gel few, monomer conversion increases, but emulsification dosage should not add too much, only have when adding when appropriate, just can obtain more stable system.Further illustrate while adding Abietyl modified thing to participate in monomer polymerization, the optimum amount of emulsifying agent is total add-on 3%.
As seen from Figure 5, along with the increase of emulsifier content, monomer conversion increases, gel fraction reduces, when emulsifier content increases to 2.5%, monomer conversion is the highest, and gel fraction is minimum, afterwards, although monomer conversion first is tending towards steadily, gel fraction reduces gradually, and monomer conversion finally reduces, further illustrate while adding sunflower seed oil to participate in monomer polymerization, the emulsifying agent optimum amount is total add-on 2.5%.
When the Abietyl modified thing of embodiment 5 participates in monomer copolymerization, the impact of initiator amount on solid content and viscosity
The quality percentage composition of each component of benzene emulsion system is as follows: butyl acrylate (BA) 20 %, vinylbenzene (St) 20 %, vinylformic acid (AA) 1%, ester gum 2%, alkylphenol polyoxyethylene (OP-10) 1%, sodium lauryl sulphate (SDS) 2%, ammonium persulphate 0.1～0.6%, surplus is water.Method according to embodiment 1 prepares benzene emulsion.
Result as shown in Figure 6, increase along with initiator amount, solid content and viscosity all are the trend increased progressively, but when initiator amount is too much, solid content tends towards stability, and viscosity is on a declining curve, and this is because initial decomposition of initiator produces a small amount of free radical, make reactive polymeric become macromolecular substance, impel the increase of solid content and viscosity.When initiator amount reach total add-on 0.6% the time, the monomer primitive reaction is complete, solid content tends towards stability, too large variation no longer occurs, and the polyradical excessively that at this moment initiator produces impels trigger rate to accelerate, polymericular weight is less, causes emulsion viscosity to reduce.So, when the add-on of initiator is the total input amount 0.5% of material, corresponding solid content is the highest, viscosity is optimum also.
When embodiment 6 sunflower seed oils participate in monomer copolymerization, the impact of initiator amount on solid content and monomer conversion
The quality percentage composition of each component of benzene emulsion system is as follows: butyl acrylate (BA) 17%, vinylbenzene (St) 17.85%, vinylformic acid (AA) 0.85%, sunflower seed oil, polyoxyethylene nonylphenol ether (NP-10) 0.8%, sodium lauryl sulphate (SDS) 1.7%, ammonium persulphate 0.1～0.5%%, surplus is water.Method according to embodiment 1 prepares benzene emulsion.
Result as shown in Figure 7, increase along with initiator concentration, the free radical generating rate increases, so the speed of trigger monomer is also accelerated in micella, thereby monomer conversion and solid content raise, after initiator concentration surpasses certain value, polyreaction stops speed and increases, and the mean lifetime that enters free radical in micella reduces, and makes the amount of initiator of actual trigger monomer reaction reduce, thereby make monomer conversion reduce, solid content is also on a declining curve.So, when the add-on of initiator is the total input amount 0.3% of material, corresponding monomer conversion and solid content are the highest.
Embodiment 7
The optimum amount that draws each component according to above-described embodiment prepares benzene emulsion, measures its particle diameter and uses FTIR(Fu Shi conversion infrared spectrum analysis instrument) to be analyzed, result is as shown in Fig. 8,9 and 10.
When Abietyl modified thing participates in monomer copolymerization, the quality percentage composition of each component of benzene emulsion system is as follows: butyl acrylate (BA) 20%, vinylbenzene (St) 20%, vinylformic acid (AA) 1%, ester gum 2%, alkylphenol polyoxyethylene (OP-10) 1%, sodium lauryl sulphate (SDS) 2%, ammonium persulphate 0.5%, surplus is water.Method according to embodiment 1 prepares benzene emulsion.
When sunflower seed oil participates in monomer copolymerization, the quality percentage composition of each component of benzene emulsion system is as follows: butyl acrylate (BA) 17%, vinylbenzene (St) 17.85%, vinylformic acid (AA) 0.85%, sunflower seed oil 1%, polyoxyethylene nonylphenol ether (NP-10) 0.8%, sodium lauryl sulphate (SDS) 1.7%, ammonium persulphate 0.3%, surplus is water.Method according to embodiment 1 prepares benzene emulsion.
As seen from Figure 8, adopt the size distribution of ZetaPALS type laser particle analyzer test emulsion, emulsion particle diameter is all less, and distribution uniform is better dispersed; The median size that A schemes Abietyl modified thing participation monomer copolymerization gained emulsion is about 1.858 nm, and its particle size distribution index (particle dispersion index, PDI) is 0.236; The median size that B figure sunflower seed oil participates in monomer copolymerization gained emulsion is about 59.58 nm, and its particle size distribution index (particle dispersion index, PDI) is 0.180; Show that the gained multipolymer is nanometer particle.
Fig. 9 result: at 3083-2958 cm
-1the stretching vibration absorption peak that C-H on phenyl ring is arranged in scope; 2958 cm wherein
-1be-CH
3the stretching vibration absorption peak; At 1732 cm
-1it is the stretching vibration absorption peak of C=O; At 1494 cm
-1it is the skeletal vibration absorption peak of phenyl ring; At 1453 cm
-1that the vibration of the COO-in vinylformic acid can be judged in structure and has monosubstituted phenyl ring to exist; 701 cm
-1it is the characteristic peak of the C-H out-of-plane bending in phenyl ring; Charateristic avsorption band 1695 cm of Abietyl modified thing
-1with 1782 cm
-1do not occur in spectrogram, illustrate that AA, BA, St and four kinds of monomers of Abietyl modified thing (ester gum) have all participated in copolymerization.
Figure 10 result: at 3028-2959cm
-1the stretching vibration absorption peak that C-H on phenyl ring is arranged in scope; 2959 cm wherein
-1with 2873 cm
-1be-CH
3with-CH
2-C-H stretching vibration absorption peak; At 1731 cm
-1it is the stretching vibration absorption peak of the C=O in the butyl acrylate base; At 1732 cm
-1it is the stretching vibration absorption peak of C=O; At 1494 cm
-1it is the skeletal vibration absorption peak of phenyl ring; At 1453 cm
-1it is the vibration absorption peak of the COO-in vinylformic acid; 1384cm
-1be-CH
3c-H flexural vibration absorption peak; At 1166-1029cm
-1it in scope, is phenyl ring C-H in-plane bending vibration absorption peak; And 762 cm
-1can in description architecture, there is monosubstituted phenyl ring to exist; 700 cm
-1it is the characteristic peak of the C-H out-of-plane bending in phenyl ring; 1620-1680cm in spectrogram
-1the charateristic avsorption band that sunflower seed oil do not occur, illustrate that AA, BA, St and sunflower seed oil have all participated in copolymerization.
Add each component percentage composition of environment-friendly type benzene emulsion system of ultralow VOC content of Abietyl modified thing as follows: butyl acrylate (BA) 20%, vinylbenzene (St) 20%, vinylformic acid (AA) 1%, ester gum 2%, alkylphenol polyoxyethylene (OP-10) 1%, sodium lauryl sulphate (SDS) 2%, ammonium persulphate 0.5%, surplus is water, prepare benzene emulsion according to the method for embodiment 1, measure the VOC content of benzene emulsion, result as shown in figure 11, with do not add Abietyl modified phase ratio, VOC content is down to 271.8ppm by 2212ppm.
Adopt the VOC content of gas chromatograph for determination benzene emulsion, specific as follows:
1) configuration of standardized solution, take in chromatogram sterling to the 100 mL volumetric flask of the monomers to be measured such as a certain amount of vinylbenzene, butyl acrylate, then with DMF, is diluted to scale to shake up;
2) mensuration of standardized solution, the certain density standardized solution that accurately absorption has prepared adds in the head space bottle, after sealing, puts into head space-chromatographic instrument and is measured by operational condition, records peak area;
3) sample analysis, accurately drawing a certain amount of sample solution enters in the head space automatic sampler, under the working conditions of above-mentioned head space-chromatogram, measure, record peak area, can calculate the concentration of residual monomer in emulsion according to the concentration of the peak area of measuring in experiment and standardized solution, i.e. VOC content.
Embodiment 9
Add each component percentage composition of environment-friendly type benzene emulsion system of ultralow VOC content of sunflower seed oil as follows: butyl acrylate (BA) 17%, vinylbenzene (St) 17.85%, vinylformic acid (AA) 0.85%, sunflower seed oil 0.85%, polyoxyethylene nonylphenol ether (NP-10) 0.8%, sodium lauryl sulphate (SDS) 1.7%, ammonium persulphate 0.3%, and water 54.7%, prepare benzene emulsion according to the method for embodiment 1, measure the VOC content of benzene emulsion, result as shown in figure 11, with with sunflower seed oil, compare, VOC content is down to 269.7ppm by 2997ppm.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. the preparation method of the environment-friendly type benzene emulsion of a ultralow VOC content is characterized in that: take vinylbenzene, butyl acrylate is main monomer, and vinylformic acid is function monomer, adds natural olefines material to participate in polyreaction.
2. the preparation method of the environment-friendly type benzene emulsion of ultralow VOC content according to claim 1, it is characterized in that: described natural olefines material is rosin, Abietyl modified thing, sunflower seed oil, peanut oil, soya-bean oil or sweet oil.
3. the preparation method of the environment-friendly type benzene emulsion of ultralow VOC content according to claim 2, it is characterized in that: described natural olefines material is Abietyl modified thing or sunflower seed oil.
4. the preparation method of the environment-friendly type benzene emulsion of ultralow VOC content according to claim 1 is characterized in that comprising the following steps:
(1) preparatory stage
Emulsifying agent, initiator are dissolved in the water respectively and obtain emulsifier solution and initiator solution;
(2) the pre-emulsification stage
The emulsifier solution of getting 45～55% quality joins natural olefines material and participates in, in the monomer of polymerization, stirring the pre-emulsion that obtains white thickness;
(3) the seed priming stage
By remaining emulsifier solution heating, while being warmed up to 76～78 ℃, drip the pre-emulsion of 18～22% quality and the initiator solution of 1/6～1/3 quality, be incubated 30～40 min;
(4) step of reaction
After insulation finishes, continue to drip remaining pre-emulsion, and drip the initiator solution of 1% quality every 10～20 min, after dripping, temperature of reaction is controlled between 76～84 ℃, be incubated 1～1.25 h;
(5) holding stage
Be warming up to 88～91 ℃, continue insulation 1～1.25 h;
(6) the cooling dress sample stage
After insulation finishes, while being cooled to 40～50 ℃, with sodium hydrogen carbonate solution adjust pH to 6～7, cooling dress sample then, obtain the environment-friendly type benzene emulsion of ultralow VOC content;
In system, the quality percentage composition of each component is respectively: vinylbenzene 14～22%, and butyl acrylate 15～26%, vinylformic acid 0.85～1%, natural olefines material 0～4%, initiator 0.1～0.6%, emulsifying agent 0.5～3.0%, surplus is water.
5. the preparation method of the environment-friendly type benzene emulsion of ultralow VOC content according to claim 4, it is characterized in that: the emulsifying agent described in step (1) is at least one in sodium lauryl sulphate, alkylphenol polyoxyethylene and polyoxyethylene nonylphenol ether; Described initiator is ammonium persulphate.
6. the preparation method of the environment-friendly type benzene emulsion of ultralow VOC content according to claim 4, it is characterized in that: when described natural olefines material is Abietyl modified thing, the monomer that participates in polymerization is vinylbenzene, butyl acrylate and vinylformic acid, and emulsifying agent is the compound emulsifying agent that sodium lauryl sulphate and alkylphenol polyoxyethylene form; In system, the percentage composition of each component is as follows: vinylbenzene 14～22%, butyl acrylate 18～26%, vinylformic acid 1%, Abietyl modified thing 0～4%, initiator 0.1～0.6%, sodium lauryl sulphate 0.5～2.0%, alkylphenol polyoxyethylene 0.5～1.0%, surplus is water.
7. the preparation method of the environment-friendly type benzene emulsion of ultralow VOC content according to claim 6, it is characterized in that: described Abietyl modified thing is ester gum, its quality percentage composition is 2%, and the quality percentage composition of compound emulsifying agent is 3.0%, and the quality percentage composition of initiator is 0.5%; Temperature of reaction in step (4) is controlled at 78～82 ℃.
8. the preparation method of the environment-friendly type benzene emulsion of ultralow VOC content according to claim 4, it is characterized in that: when the natural olefines material described in step (1) is sunflower seed oil, the monomer that participates in polymerization is vinylbenzene, butyl acrylate and vinylformic acid, emulsifying agent is the compound emulsifying agent that sodium lauryl sulphate and polyoxyethylene nonylphenol ether form, in system, the percentage composition of each component is as follows: vinylbenzene 14～22%, butyl acrylate 15～25%, vinylformic acid 0.85%, sunflower seed oil 0～4%, initiator 0.1～0.5%, sodium lauryl sulphate 0.5～2.0%, polyoxyethylene nonylphenol ether 0.4～0.75%, surplus is water.
9. the preparation method of the environment-friendly type benzene emulsion of ultralow VOC content according to claim 8, it is characterized in that: the quality percentage composition of described sunflower seed oil is 1%, the quality percentage composition of compound emulsifying agent is 2.5%, and the quality percentage composition of initiator is 0.3%; Temperature of reaction in step (4) is controlled at 78～84 ℃.
10. the environment-friendly type benzene emulsion of a ultralow VOC content, it is characterized in that: by claim 1-9 any one, described preparation method prepares.
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| CN105349065A (en) * | 2015-12-04 | 2016-02-24 | 重庆江北工农化工有限责任公司 | Emulsion adhesive |
| CN107141394A (en) * | 2017-05-19 | 2017-09-08 | 佛山市顺德区巴德富实业有限公司 | A kind of styrene-acrylic emulsion of zero VOC content and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105349066A (en) * | 2015-12-04 | 2016-02-24 | 重庆江北工农化工有限责任公司 | Reparation method of emulsion adhesive |
| CN105349065A (en) * | 2015-12-04 | 2016-02-24 | 重庆江北工农化工有限责任公司 | Emulsion adhesive |
| WO2018018444A1 (en) | 2016-07-27 | 2018-02-01 | Dow Global Technologies Llc | Crosslinkable surfactants |
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