Preparation of epoxy resin modified benzoyl propylene emulsion adhesive

Liu Bo (School of Petrochemicals, Shenyang University of Technology, Liaoyang, Liaoning, 111003)
Summary: Epoxy resin modified benzoyl propylene emulsion adhesive is prepared by method of emulsion polymerization. The effects of different trigger addition, compound emulsizer addition, styrene/acrylate butyl quality ratio, epoxy resin addition and other factors on its peeling strength were analyzed by orthographic experimental method, and the optimal polymerization formula was optimized. The composition is indicated by infrared spectroscopy (FF1R), and the results show that the resulting products have good bonding strength and other properties.
key words: epoxy resin; Change; Benzoyl propylene emulsion; Adhesives
in the figure classification number: 0632.6 document identification code: A article number: 1001-9677 (2012) 09-0092-04
benzene-propylene emulsion is one of the water-based adhesives, with many excellent properties, has been successfully used in all walks of life. However, there are still many shortcomings in traditional benzoyl propylene emulsion adhesives and their derivatives, such as poor film-forming performance, high minimum film-forming temperature, low adhesive coating strength, etc. In order to give the phenylpropyl emulsion adhesive better performance, a small number of functional monomers can be introduced into the phenylpropan emulsion through emulsion co-fusion, to achieve the modified phenyl propylene emulsion. The cross-linking of traditional phenylpropane emulsions by epoxy resin can improve the film-forming properties, film hardness and anti-stain resistance of phenyl-propylene emulsion adhesives. In addition, by adding a small number of functional monosomes, select different types and ratios of emulsifying agents, especially for particle design, such as the use of nuclear shell composition design and polymerization, it can have certain properties, and thus be given some different special purposes. Epoxy resins are usually the aerations of ethylene chloropropanebiphenol propane (DPA). Epoxy resin contains hydroxyl, epoxy and other polar radicals. It is easy to produce secondary, hydrogen and primary keys with many surfaces, and therefore has a very strong adhesion. At the same time, epoxy and hydroxyl energy react with other compounds such as ammonia, hydroxyl, and carboxyl to form a network structure, resulting in high mechanical properties. The ether key of the structural towel can be rotated from the south, and there are many hydrocarbon fat bonds between the intersection points, which makes it resilient. Epoxy resins have excellent resistance to chemicals, especially acid-base properties. Epoxy base has good bonding, ether bonds are resistant to corrosion, hydroxyl bonding. In this way, epoxy resin can and benzoyl propylene emulsion adhesive polymer, so that the advantages of epoxy resin into the benzoyl propylene emulsion adhesive, improve the strength of benzoyl propylene emulsion adhesive, adhesion, film-forming properties, film hardness and anti-stain resistance, etc.
1. Experimental materials, instruments, equipment and experimental processes
1.1 Experimental materials, instruments, equipment
butyl acrylates (BA), chemical purity, Shenyang Dongling Fine Chemistry Company; ammonium persulphate (APS), pure analysis, Tianjin Damao chemical reagent supply station; Styrene (St), chemical pure, Shenyang Xinxi reagent plant; sodium sulphate, pure analysis, Tianjin Damao chemical reagent supply station; Sodium sulphate (SDS), chemical purity, Tianjin Ruijint Chemical Co., Ltd.; Emulsifying agent OP110, industrial products, Liaoning Oak Chemical Co., Ltd. Epoxy E144, industrial products, Shenyang Chemical Co., Ltd. Acrylamide (AM) chemical purity, Shenyang Xinxi reagent plant; sodium bicarbonate, pure analysis, Shenyang Xinxi reagent factory Il box warm water bath, CS501 type, Liaoyang test equipment factory; Ten dry box, 668 type, Chongqing experimental equipment factory; Electronic all-in-one material test machine, CMT6104 type, Shenzhen Xini Si test is not ready to limit the company; Infrared Spectrometer, Nicolet I 470, Meimei NICOLET, Rotary Viscosity Meter, NDJ Type 1, Shanghai Balance Instrument Factory, DSC Differential Thermal Analyzer, Mettler-ToledoDSC Type 822, Mettler, Switzerland.
1.2 preparation of epoxy resin modified benzoyl propylene emulsion adhesive
adding quantitative deionized water to 500mL four-mouth bottles, adding quantitative compound emulsions, sodium bicarbonate, epoxy resin (Epoxy resins have been dissolved in 50% styrene monosylene monosomes) and acrylates monoglycers for high-speed emulsification (300rpm), when controlled at about 15arins, as seed emulsions and nuclear emulsions.
in the 500mL four-mouth bottle to add quantitative deionized water, add quantitative compound emulsizer, monosome, high-speed emulsification (300rpm), time control at about 15min, as a shell emulsion backup.
In a four-mouth bottle equipped with agitator, reflow condensing tube, drip funnel, thermometer, seed emulsion (20% monolith total), heat up to 75 degrees C while stirring, add a certain amount of trigger, so that emulsion generates seed emulsion, seed polymerization The time is about 15 to 30min, and then the temperature is set to (75±1) degrees C, began to drop human nuclear emulsion, while intermittently adding a certain amount of trigger, control drop acceleration 1.5 to 2h drop finished, when the nuclear emulsion drop; Continue to drip into the shell emulsion, while intermittently adding a certain amount of trigger, control the drop acceleration of 1.5 to 2h drop, after the shell emulsion, insulation 1h at 80 degrees C. Then cool down to 50 degrees C, add sodium bicarbonate saturation solution 3mL, adjust pH 7 to 9, filter the immediate product, while measuring yield and gel volume. Test the product: solid content, viscosity, etc.
1.3 Test sample preparation and test method
1.3.1 solid content determination
using weighing method (GM) measurement. Accurate weighing of 1 to 2g emulsion sample placed in the weighing bottle, in the oven at 100 oC drying to constant weight of 2h or more, solid content S press calculation:
solid content (S%): S (wl/w2) ×100%
In the form of: w1 - after drying sample constant weight, g
w2 - sample weight, g
1.3.2 viscosity determination
using NDJ 179 rotary viscosity meter, test temperature (25±0.5) degrees C.
of 1.3.3 pH is
by precision pH test paper.
1.3.4 After the determination of the infrared absorption spectrum
filmed the emulsion, the sample was scanned 16 times using the infrared scanner of Nieolet Corporation of the United States to scan the sample with an infrared scanner of magnificence 111750 Fourier transformation.
test method for measuring the shear strength of
1.3.5 peeling strength was carried out according to HG/T2727-95. The sample is 100mm × 20mm × 2mm synthetic leather. The lifting area is 20×15mm2.
1.3.6 differential scanning amount heat method (DSC) determination
after the emulsion into a film, using ThettlerToledoDSC type 822e type differential thermal analyzer to test the glass transition temperature of the polymer, sample weight 4 to 10 mg, atmosphere N2, air flow of 100mL/min, The test range is one 30 to 150 degrees C, the heating rate is 10 degrees C/min
2. Experimental results and discussion
2.1 orthopaedic experiments and results analysis
B A compound emulsifying agent added amount/; C-ST/BA mass ratio; D epoxy resin addition/, effect on epoxy resin modified benzoyl propylene emulsion adhesive peeling strength, the experimental results are seen in Table 1.
Table 1 Orthosopaedic Experimental Table
By the data in Table 1 through a variance analysis, it can be known that the effects of various factors on the technical properties of benzene monopropylene emulsion adhesive are D>A>C>B, the optimization condition is A3B3C2D2, that is, when synthetic phenyl propylene emulsion adhesive, the dosage of the trigger agent is 0.6% of the monolithic content, compound emulsion (composite emulsion) OP110 and sodium tranium sulfonate) dosage is 6% of the mass of the monogam, ST/BA mass ratio is 50/50, epoxy resin addition is 5% of the mass of the monogam, according to A3B3C2D2 sample is the best, the best sample gel volume is 1.30g, solid content is 30%, viscosity 14×10-3Pa. S, pH is 7.3 and peeling strength is 0.90MPa.
2.2 Effects of various factors on the peeling strength of epoxy resin modified benzene emulsion adhesive
2.2.1 Effects of agent addition on the peeling strength of epoxy resin modified benzene emulsion adhesive
Figure 1 Effect of the addition of the trigger on the peeling strength of epoxy resin modified benzene-propylene emulsion
as can be seen from Figure 1, the peeling strength of benzoyl propylene emulsion adhesive increases slightly after reaching its lowest point with the amount of the trigger but remains at a high level. Trigger dosage JJ, the concentration of free fundamentals in the U system is low, the impurities of the system consume a certain amount of free fundamentals, so that the chance of collision between monosomy and free fundamentals is reduced, so the conversion rate is low, so that the adhesive peeling strength is also small; The concentration of free fundamentals in the system is high, which increases the chance of collision between monomers and free fundamentals, results in a large molecular weight of polymers, and a large peeling strength of latex adhesive. To sum up, the amount of the trigger was 0.6% of the monosome content when the peeling strength was higher.
2.2.2 Effect of compound emulsifying agent addition on the peeling strength of epoxy resin modified benzene emulsion
Figure 2 Effect of compound emulsion addition on the peeling strength of epoxy resin modified benzene emulsion adhesive
Composite emulsifying agent plays an important role in polymerization reaction, compound emulsifying agent dosage is too low, did not reach the critical beam concentration, the reaction system can not form the glue beam, basically does not play the role of emulsification, monosome and water are insoluble; When the critical beam concentration is exceeded, with the increase of emulsifying agent dosage, emulsification ability is enhanced, the number of latex particles formed increases, the particle size decreases, the reaction is more complete, the polymerization rate increases, the fluid is stable, so that the gap between latex particles is reduced and the adhesion is enhanced. Therefore, the determination of emulsion dosage should take into account the performance and stability of emulsion. Combined with the above factors, compound emulsifying agent addition is appropriate at 6%.
2.2.3 ST/BA addition on the strength of epoxy resin modified benzene monocrysamine adhesive peeling
Figure 3 BA addition effect on epoxy modified phenyl propylene emulsion peeling strength
This is due to styrene with styrene ring, with rigidity, is a hard monosome, is conducive to increasing the hardness of the ADH adhesive coating, and improve its gloss, but the styrene content is too much, the anti-aging performance of the adhesive coating will be reduced, brittle. Acrylate butyl in the monolith component is a soft monolith, can improve the viscosity of the emulsion, enhance the toughness of the membrane, is good for the increase of peeling strength, but the content of acrylates is too much, will lead to soft adhesive coating, affecting the peeling strength. In summary, the experiment found that when the quality ratio of styrene to acrylates was 50/50, the peeling strength was higher.
2.2.4 Effect of epoxy resin addition on the peeling strength of epoxy resin modified benzene emulsion
Figure 4 effect of epoxy resin addition on epoxy resin modified benzene emulsion peeling strength
With the increase of epoxy resin content, the absorption rate of coating film decreased, cross-linking degree increased, and water resistance increased; However, the amount of epoxy resin continues to increase, not all epoxy resin can enter the latex particles into the nucleus, most will be attached to the surface of the latex particles, so that the gel rate increases, at this time the epoxy resin in the emulsion adhesive film, not only does not enhance the role, but acts as an impurity, so that the overall performance of the adhesive coating decreased. Experiments show that the optimal dosing of epoxy resin is 5%.
2.3 Infrared spectral analysis of epoxy resin modified benzene-propylene emulsion adhesive
Figure 5 epoxy resin modified benzene-propylene emulsion infrared spectral analysis
760cm-1 is the asymmetric telescopic vibration absorption peak of epoxy ring; 1160cm-1 is the characteristic absorption peak of epoxy base; 1730cm-1 is the skeleton vibration absorption peak of the epoxy ring; 769cm-1 and 699cm-1 are the characteristic peaks of single substitute benzene; 1154cm-1 is a characteristic absorption peak of C-O-C one produced when the adipose family and benzene ring monogluents converg together; 1730cm-1 is the absorption peak of the niobium base; 1236, 1023, 1171cm-1 is the telescopic vibration absorption peak of C-O-C in BA; At 965cm-1 is the telescopic vibration absorption peak of C-O in BA; In addition, there is no telescopic vibration absorption peak of C-C at 1637cm-1, indicating that the polymerization reaction has been completed. In summary, all kinds of functional monomers participated in polymerization reaction, and the FT-IR characteristic peak of the corresponding group was obvious, indicating that the expected structure of epoxy resin modified phenyl propylene copolymer emulsion was successfully synthesized.
2.4 Epoxy resin modified benzene-propylene emulsion differential scanning thermal analysis (DSC)
Figure 6 epoxy resin modified benzene-propylene emulsion differential scanning thermal analysis (DSC)
glassing temperature The high and low is one of the important factors affecting the minimum film temperature and bonding performance of emulsion adhesive, as shown in Figure 6, the two glassed temperature tgs of benzene-propylene emulsion adhesive modified by epoxy resin are 41.83 degrees C and 94.33 degrees C, respectively. The glassing temperature Tg is 41.83 degrees C. 94.33 degrees C is the nuclear layer. It can be shown that epoxy resin modified benzene-propylene emulsion adhesive is a nuclear shell structure.
3.Conclusion
After ortho orthodectant experiments, the optimal ratio of epoxy resin modified benzene-propylene emulsion adhesive was 0.6% (as opposed to monosomal mass, the same between 2), the composite emulsizer addition was 6%, the ST/BA mass ratio was 50/50, and the epoxy resin addition was 5%. According to the infrared spectra, various functional monoliths participated in the polymerization reaction, and the FT-IR characteristic peak of the corresponding group was obvious, and the epoxy resin modified benzoyl propylene emulsion adhesive was synthesized. Epoxy resin modified benzoyl propylene emulsion adhesive is an excellent performance
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