Water-based petroleum resin emulsion with high solid content and preparation method thereof

Abstract

The invention provides a water-based petroleum resin emulsion with high solid content, which is prepared from petroleum resin, a polymer modifier, a dispersing agent and a compound emulsifier in parts by weight as follows: # imgabs0 #, and also provides a preparation method of the water-based petroleum resin emulsion with high solid content. The water-based petroleum resin prepared by the method disclosed by the invention is relatively high in solid content, good in stability, better in tackifying effect and high in production efficiency, and can meet the application requirements of the current market on water-based adhesives.

Description

Technical Field

[0001] The invention belongs to the field of chemical industry and relates to an aqueous petroleum resin emulsion, in particular to an aqueous petroleum resin emulsion with high solid content and a preparation method thereof. Background Art

[0002] Petroleum resin has the advantages of low softening point, good fluidity and good adhesion. It is currently widely used in adhesives, sealants, coatings, inks and other industries. It can effectively improve the wettability of products and interfaces, thereby improving the adhesion between products and interfaces. It is often used as a tackifier in various products.

[0003] As environmental protection requirements become increasingly stringent, the demand for water-based adhesives, water-based sealants, water-based coatings, water-based inks, etc. is increasing, and petroleum resins are widely used in the above products. Therefore, this puts forward new requirements for petroleum resins as tackifiers: preparing solid petroleum resins into water-based emulsions to expand their application in water-based systems.

[0004] Patents for the preparation of water-based petroleum resin emulsions have been disclosed. For example, the patent with application number CN201510239975.4 discloses a petroleum resin emulsion and a preparation method thereof. In terms of weight percentage, the raw materials of the petroleum resin emulsion include the following components: 30-35% petroleum resin; 30-35% water; 30-35% cyclohexane oil; 3-5% emulsifier; and an appropriate amount of stabilizer. The present invention uses water as a dispersion medium, cyclohexane oil as a dissolving agent for petroleum resin, and is emulsified by an emulsifier to prepare the petroleum resin emulsion, which has stable performance, fast drying, non-toxic, odorless, and safe characteristics, and its preparation method is simple and conducive to production and processing. The cyclohexane oil added in the patent is a component with a low molecular weight. In the subsequent use process, the cyclohexane oil has the risk of migration and precipitation, which poses a great risk to the stability and environmental protection of the product. For another example, the patent with application number 202011161888.9 discloses a high-solid content water-based petroleum resin emulsion and a preparation method thereof, which belongs to the technical field of water-based petroleum resin emulsion preparation. The high solid content aqueous petroleum resin emulsion of the present invention comprises petroleum resin, viscosity regulator, dispersant and composite emulsifier, wherein the mass ratio of petroleum resin to viscosity regulator is 4-10:1, and the mass of dispersant and emulsifier is 1-5% and 5-20% of the mass of petroleum resin respectively. The present invention can be carried out on a reactor with ordinary stirring, and the obtained emulsion has a solid content of 50-70%, good stability, and no demulsification occurs after being placed at room temperature for 1 year. The operation is simple and conducive to industrial production. Although the patent adds liquid paraffin or petroleum resin oligomers, the viscosity of petroleum resin when melted is improved, because paraffin itself has almost no bonding effect, it will have a negative impact on the tackifier effect of petroleum resin in the subsequent use process. At the same time, the addition of a large number of small and medium molecular weight components has certain negative risks on the physical properties, heat resistance and weather resistance of the final product.

[0005] At present, when adding small molecular weight components in the preparation process of petroleum resin, the high temperature melting and long mixing time in the reactor may cause the degradation of the resin. At the same time, there is a great risk of migration and precipitation of small molecular weight components, or reduction of viscosity increasing effect, or reduction of physical properties, thus reducing the comprehensive performance of products made of water-based petroleum resin emulsion. Summary of the invention

[0006] In view of the above technical problems in the prior art, the present invention provides a high-solid content aqueous petroleum resin emulsion and a preparation method thereof. The high-solid content aqueous petroleum resin emulsion and the preparation method thereof are intended to solve the technical problems of poor viscosity increasing effect and stability of the aqueous petroleum resin emulsion in the prior art.

[0007] The present invention provides a high solid content aqueous petroleum resin emulsion, which is prepared from petroleum resin, polymer modifier, dispersant and composite emulsifier, and the weight parts of each component are as follows:

[0008]

[0009] Furthermore, the polymer modifier is prepared by twin-screw blending of a second petroleum resin and a modified polymer, and the mass ratio of the second petroleum resin to the modified polymer is 1:1; the modified polymer comprises ethylene vinyl acetate copolymer (EVA) or ethylene acrylic acid copolymer (EAA).

[0010] Furthermore, the first petroleum resin and the second petroleum resin are any one of C5 petroleum resin, C9 petroleum resin or modified petroleum resin, and the softening point thereof is 60-120°C.

[0011] Furthermore, the modified petroleum resin is one or a mixture of two or more of phenol-modified resin, terpene-modified resin and acid-modified resin.

[0012] Furthermore, the dispersant is one of sodium lignin sulfonate, calcium lignin sulfonate, sodium dodecyl sulfonate, calcium dodecyl sulfonate, or a mixture of two or more thereof, preferably sodium lignin sulfonate or calcium lignin sulfonate.

[0013] Furthermore, the emulsifier is one or a mixture of two or more of Span 20, Span 80, Tween 80, fatty acid glyceride, OP-10, OP-4, and OP-20.

[0014] The present invention also provides a method for preparing the above-mentioned high-solid content aqueous petroleum resin emulsion, comprising the following steps:

[0015] 1) The second petroleum resin and the modified polymer are put into a twin-screw extruder in an equal mass ratio for mixing, extruding and granulating to obtain a polymer modifier, and the extruder temperature is controlled at 100-120° C.;

[0016] 2) The first petroleum resin, the polymer modifier and the dispersant are put into a twin-screw extruder according to the mass ratio, and the extruder temperature is 90-100° C. After the material comes out of the extruder, the melt directly enters the reactor, and the reactor temperature is 90-100° C., and stirring is started to appropriately cool down;

[0017] The weight proportions of the first petroleum resin, polymer modifier and dispersant are as follows:

[0018] First Petroleum Resin 100;

[0019] Polymer modifier 5-20;

[0020] Dispersant 0.5-3;

[0021] 3) lowering the material temperature to 90-100°C, adding an aqueous solution of an emulsifier at the same temperature to the reactor, wherein the mass percentage concentration of the aqueous solution of the emulsifier is 2-10%, and stirring the reaction vessel; the mass ratio of the emulsifier to the first petroleum resin is 1-5:100;

[0022] 4) After the dropwise addition is completed, continue to add distilled water at the same temperature into the reaction kettle for stirring, wherein the amount of distilled water added is 9 to 50% of the mass of the aqueous solution of the composite emulsifier;

[0023] 5) After cooling and filtering the above emulsion, a petroleum resin emulsion can be obtained.

[0024] Furthermore, in step 2), the stirring rate is 150-200 rpm, and the stirring time is 10-30 min; in step 3), the stirring rate is 500-600 rpm, and the stirring time is 10-30 min; in step 4), the stirring rate is 600-750 rpm, and the stirring time is 10-30 min.

[0025] Furthermore, the solid content of the obtained petroleum resin emulsion is 50-70%.

[0026] The principle of the present invention is:

[0027] 1) When preparing petroleum resin emulsion conventionally, small molecule modifiers are generally added. However, small molecule modification itself has the problem of easy migration and precipitation. Therefore, the present invention adopts polar polymerization (large molecular weight)

[0028] As a modified component, it does not migrate and increases the polarity of the petroleum resin.

[0029] 2) Since the polymer itself has a high viscosity, it is difficult to mix it with the petroleum resin quickly and evenly at a low temperature. The present invention adopts a twin-screw blending extrusion method and utilizes the strong shearing ability of the twin-screw to quickly and fully mix the petroleum resin and the modified polymer.

[0030] 3) Conventional petroleum resin is generally prepared into emulsion by melting in a reactor, which has the problem of slow heat transfer. When the amount is large, the material is heated in the reactor for a long time, which is prone to negative conditions such as oxidative degradation. The molten material of the present invention adopts a twin-screw method. The material is almost in a sealed environment and quickly turns into a melt state under the action of heat and screw shear force, reducing the negative effects of thermal oxidative aging on the material.

[0031] Compared with the prior art, the technical effect of the present invention is positive and obvious.

[0032] 1) The invention does not add small and medium molecular weight components, which reduces the negative effects of small molecule migration, reduced viscosity increasing effect, and reduced material properties that may exist in the subsequent use of the water-based petroleum resin emulsion;

[0033] 2) The twin-screw extruder is introduced into the mixing process of the present invention, which improves the mixing efficiency and mixing effect, makes the polymer modified components and other additives dispersed better, and improves the emulsification effect. At the same time, the introduction of the twin-screw extruder reduces the thermal oxidation aging that may occur in the high-temperature melting process of the material, and improves the comprehensive physical properties of the petroleum resin;

[0034] 3) Due to the addition of polar polymers, the overall hydrophilicity of the present invention is improved, which can effectively improve the emulsification effect and the production efficiency of emulsion preparation, and the prepared aqueous petroleum resin emulsion has a better viscosity-increasing effect.

[0035] 4) The present invention utilizes polymer modification components to mix high polar polymers such as EVA and EAA with petroleum resin by twin screw extrusion blending to obtain a polymer modifier. Twin screw extrusion blending has the advantages of fast speed, good mixing effect, less contact with air and less oxidative degradation of materials.

[0036] 5) The water-based petroleum resin prepared by the technical solution of the present invention has a high solid content, good stability, better viscosity-increasing effect, and high production efficiency, and can meet the current market demand for water-based adhesives. DETAILED DESCRIPTION

[0037] Example 1

[0038] 2.5 kg of EVA and 2.5 kg of C5 petroleum resin were extruded and granulated by a twin-screw extruder to obtain 5 kg of polymerization modifier, and the extruder temperature was controlled at 100-120°C;

[0039] 100kg C5 petroleum resin, 5kg polymer modifier and 3kg sodium dodecyl sulfate are put into a twin-screw extruder, and the temperature of the extruder is set at 90-100°C. After the material comes out of the extruder, the melt directly enters a reactor, and the temperature of the reactor is 90-100°C. Stirring is turned on to appropriately cool down the temperature, and the stirring speed is 150rpm. When the material temperature drops to 90°C, 50kg of a 2wt.% emulsifier aqueous solution (a mixed aqueous solution of Span 20 and fatty acid glyceride) is added dropwise, and the stirring speed is increased to 500rpm, and stirring is carried out for 30min; 60kg of distilled water at the same temperature is continued to be added dropwise for dilution, and stirring is carried out at 600rpm for 30min. The petroleum resin emulsion is cooled and filtered to obtain a solid content of 50% of the emulsion, and no demulsification occurs after being placed for 1 year.

[0040] Example 2

[0041] 10 kg of EVA and 10 kg of C9 petroleum resin were extruded and granulated by a twin-screw extruder to obtain 20 kg of polymerization modifier, and the extruder temperature was controlled at 100-120°C;

[0042] 100kg C9 petroleum resin, 20kg polymer modifier and 0.5kg sodium lignin sulfonate are put into a twin-screw extruder, and the temperature of the extruder is set at 90-100°C. After the materials come out of the extruder, the melt directly enters a reactor, and the temperature of the reactor is 90-100°C. Stirring is started to appropriately cool down, and the stirring speed is 200rpm. When the material temperature drops to 100°C, 50kg of a 10wt.% emulsifier aqueous solution (a mixed aqueous solution of Tween 80 and OP-10) is added dropwise, and the stirring speed is increased to 600rpm, and stirring is carried out for 10min; 8.8kg of distilled water at the same temperature is continuously added dropwise for dilution, and stirring is carried out at 750rpm for 10min. The petroleum resin emulsion is cooled and filtered to obtain a solid content of 70% of the emulsion, and no demulsification occurs after being placed for 1 year.

[0043] Example 3

[0044] 5 kg of EAA and 5 kg of C5 petroleum resin were extruded and granulated by a twin-screw extruder to obtain 10 kg of polymerization modifier, and the extruder temperature was controlled at 100-120°C;

[0045] 100kgC9 petroleum resin, 10kg polymer modifier and 1kg calcium lignin sulfonate are put into a twin-screw extruder, and the temperature of the extruder is set at 90-100°C. After the materials come out of the extruder, the melt directly enters a reactor, and the temperature of the reactor is 90-100°C. The stirring is turned on to appropriately cool down the temperature, and the stirring speed is 180rpm. When the material temperature drops to 95°C, 50kg of a 4wt.% emulsifier aqueous solution (a mixed aqueous solution of fatty acid glyceride and OP-20) is added dropwise, and the stirring speed is increased to 550rpm, and the mixture is stirred for 15min; 27.3kg of distilled water at the same temperature is continuously added dropwise for dilution, and the mixture is stirred at 700rpm for 15min. The mixture is cooled and filtered to obtain a petroleum resin emulsion, which has a solid content of 60% and is placed for 1 year without demulsification.

[0046] Example 4

[0047] 8 kg of EAA and 8 kg of C5 petroleum resin were extruded and granulated by a twin-screw extruder to obtain 16 kg of polymerization modifier, and the extruder temperature was controlled at 100-120°C;

[0048] 100 kg of modified petroleum resin, 16 kg of polymer modifier, 2 kg of calcium dodecyl sulfonate and 1 kg of sodium lignin sulfonate are put into a twin-screw extruder, and the temperature of the extruder is set at 90-100° C. After the materials come out of the extruder, the melt directly enters a reactor, and the temperature of the reactor is 90-100° C., and stirring is turned on to appropriately cool down, and the stirring speed is 160 rpm. When the material temperature drops to 92° C., 50 kg of a 6 wt. % emulsifier aqueous solution (OP-20 aqueous solution) is added dropwise, and the stirring speed is increased to 580 rpm, and stirred for 20 min; 18.2 kg of distilled water at the same temperature is continued to be added dropwise for dilution, and stirred at 650 rpm for 20 min. The petroleum resin emulsion is cooled and filtered to obtain a solid content of 65% of the emulsion, and no demulsification occurs after being placed for 1 year.

[0049] Example 5

[0050] 8 kg of EVA and 8 kg of modified petroleum resin were extruded and granulated by a twin-screw extruder to obtain 16 kg of polymerization modifier, and the extruder temperature was controlled at 100-120° C.;

[0051] 100kgC9 petroleum resin, 16kg polymer modifier, and 3kg calcium dodecyl sulfonate are put into a twin-screw extruder, and the temperature of the extruder is set at 90-100°C. After the material comes out of the extruder, the melt directly enters the reactor, and the temperature of the reactor is 90-100°C. The stirring is turned on to appropriately cool down the temperature, and the stirring speed is 160rpm. When the material temperature drops to 92°C, 50kg of 6wt.% emulsifier aqueous solution (a mixed aqueous solution of fatty acid glyceride and Span 80) is added dropwise, and the stirring rate is increased to 580rpm, and stirred for 20min; 14kg of distilled water at the same temperature is continued to be added dropwise for dilution, and stirred at 650rpm for 20min. The petroleum resin emulsion is cooled and filtered to obtain a solid content of 66.7% of the emulsion, and no demulsification occurs after being placed for 1 year.

[0052] Example 6

[0053] 6 kg of EAA and 6 kg of C9 petroleum resin were extruded and granulated by a twin-screw extruder to obtain 12 kg of polymerization modifier, and the extruder temperature was controlled at 100-120°C;

[0054] 100kg C5 petroleum resin, 12kg polymer modifier, and 2kg calcium dodecyl sulfonate are put into a twin-screw extruder, and the temperature of the extruder is set at 90-100°C. After the material comes out of the extruder, the melt directly enters the reactor, and the temperature of the reactor is 90-100°C. The stirring is turned on to appropriately cool down the temperature, and the stirring speed is 200rpm. When the material temperature drops to 91°C, 50kg of a 4wt.% emulsifier aqueous solution (a mixed aqueous solution of fatty acid glyceride and OP-20) is added dropwise, and the stirring speed is increased to 600rpm, and stirred for 25min; 18.4kg of distilled water at the same temperature is continued to be added dropwise for dilution, and stirred at 700rpm for 25min. The petroleum resin emulsion is cooled and filtered to obtain a solid content of 63.6% of the emulsion, and no demulsification occurs after being placed for 1 year.

[0055] Comparative Example 1

[0056] 10kg of liquid paraffin and 90kg of C5 petroleum resin were added to a reactor at 160°C, and slowly stirred until melted and mixed evenly for about 120 minutes. After about 30 minutes, the temperature was lowered to 120°C, 2kg of sodium dodecyl sulfonate was added, and the mixture was stirred evenly at 200rpm; the temperature was lowered to 95°C, and 50kg of 18wt.% composite emulsifier aqueous solution (mixed aqueous solution of Span20 and fatty acid glyceride) was added dropwise, the stirring rate was increased to 500rpm, and the mixture was stirred for 30min; 30kg of distilled water at the same temperature was added dropwise to dilute, and the mixture was stirred at 600rpm for 30min, and the mixture was cooled and filtered to obtain a petroleum resin emulsion, which had a solid content of 61% and was not demulsified after being placed for 1 year.

[0057] Comparative Example 2

[0058] 10kg of liquid cyclohexane oil and 90kg of C5 petroleum resin were added to a reactor at 160°C, and slowly stirred until melted and mixed evenly for about 120 minutes. After about 30 minutes, the temperature was lowered to 120°C, 2kg of sodium dodecyl sulfonate was added, and stirred and mixed evenly at 200rpm; the temperature was lowered to 95°C, and 50kg of 18wt.% composite emulsifier aqueous solution (mixed aqueous solution of Span20 and fatty acid glyceride) was added dropwise, the stirring rate was increased to 500rpm, and stirred for 30min; 30kg of distilled water at the same temperature was continued to be added dropwise for dilution, stirred at 600rpm for 30min, cooled and filtered to obtain a petroleum resin emulsion, the solid content of which was 61%, and no demulsification occurred after being placed for 1 year.

[0059] The physical properties are compared with the petroleum resin emulsion of Example 3, and the main resin adopts the same water-based acrylic emulsion.

[0060] Sample preparation for comparison of precipitation resistance: Mix water-based petroleum resin emulsion and water-based acrylic emulsion in equal proportions, apply them on a glass plate, and dry them under the same conditions until a dry film is formed. Layer oil-absorbing paper on the dry film on the glass plate, press a 50g weight on the oil-absorbing paper, and place it in a 150℃ oven for 2 hours to compare the oil-absorbing paper.

[0061] Comparison of adhesion effect Sample preparation: Mix water-based petroleum resin emulsion and water-based acrylic emulsion in equal proportions, apply them on galvanized metal plates, dry them under the same conditions, and wait until the film is dry. Use the cross-grid test method to test and compare the adhesion.

[0062] The results of the physical property comparison test are as follows:

[0063]

[0064] After physical property comparison tests, the present invention provides a high solid content water-based petroleum resin emulsion and a preparation method thereof, the preparation process is highly efficient, and the prepared water-based petroleum resin emulsion has obvious advantages in precipitation resistance and viscosity increasing properties.

Claims

1. A high solid content aqueous petroleum resin emulsion, characterized in that: It is prepared from petroleum resin, polymer modifier, dispersant and composite emulsifier. The weight proportions of each component are as follows:

2. A high solid content aqueous petroleum resin emulsion according to claim 1, characterized in that: The polymer modifier is prepared by twin-screw blending of a second petroleum resin and a modified polymer, wherein the mass ratio of the second petroleum resin to the modified polymer is 1:1; and the modified polymer is an ethylene vinyl acetate copolymer or an ethylene acrylic acid copolymer.

3. A high solid content aqueous petroleum resin emulsion according to claim 1 or 2, characterized in that: The first petroleum resin and the second petroleum resin are any one of C5 petroleum resin, C9 petroleum resin or modified petroleum resin, and the softening point thereof is 60-120°C.

4. The high solid content aqueous petroleum resin emulsion according to claim 3, characterized in that: The modified petroleum resin is one or a mixture of two or more of phenol modified resin, terpene modified resin and acid modified resin.

5. The high solid content aqueous petroleum resin emulsion according to claim 1, characterized in that: The dispersant is one of sodium lignin sulfonate, calcium lignin sulfonate, sodium dodecyl sulfonate and calcium dodecyl sulfonate, or a mixture of two or more thereof.

6. The high solid content aqueous petroleum resin emulsion according to claim 1, characterized in that: The emulsifier is one of Span 20, Span 80, Tween 80, fatty acid glyceride, OP-10, OP-4, OP-20, or a mixture of two or more thereof.

7. The method for preparing a high solid content aqueous petroleum resin emulsion according to claim 1, characterized in that: The following steps are involved: 1) The second petroleum resin and the modified polymer are put into a twin-screw extruder in equal weight ratio for mixing. Extrusion granulation to obtain the polymer modifier, the extruder temperature is controlled at 100-120°C; 2) The first petroleum resin, the polymer modifier and the dispersant are put into a twin-screw extruder according to the mass ratio, and the extruder temperature is 90-100° C. After the material comes out of the extruder, the melt directly enters the reactor, and the reactor temperature is 90-100° C., and stirring is started to appropriately cool down; The weight proportions of the first petroleum resin, polymer modifier and dispersant are as follows: First Petroleum Resin 100; Polymer modifier 5-20; Dispersant 0.5-3; 3) lowering the material temperature to 90-100°C, adding an aqueous solution of an emulsifier at the same temperature to the reactor, wherein the mass percentage concentration of the aqueous solution of the emulsifier is 2-10%, and stirring the reaction vessel; the mass ratio of the emulsifier to the first petroleum resin is 1-5:100; 4) After the addition is completed, continue to add distilled water at the same temperature into the reactor and stir. The added amount is 9 to 50% of the mass of the aqueous solution of the composite emulsifier; 5) After the above emulsion is cooled and filtered, a high solid content aqueous petroleum resin emulsion can be obtained.

8. The method for preparing a high solid content aqueous petroleum resin emulsion according to claim 7, characterized in that: The stirring rate in step 2) is 150-200 rpm, and the stirring time is 10-30 min. The stirring rate in step 3) is 500-600 rpm, and the stirring time is 10-30 min. The stirring rate in step 4) is 600-750 rpm, and the stirring time is 10-30 min.

9. The method for preparing a high solid content aqueous petroleum resin emulsion according to claim 7, characterized in that: The solid content of the obtained petroleum resin emulsion is 50-70%.

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