Modified phenolic resin overcome the shortcomings of phenolic resin, such as poor heat resistance and low mechanical strength. They offer excellent mechanical properties, strong heat resistance, strong bonding, and chemical stability. They are widely used in compression molding powders, coatings, glues, fibers, anti-corrosion, and thermal insulation applications.

1. Applications of Modified Phenolic Resins in Compression Molding Powders

Compression molding powders are essential for the production of molded products. They are primarily made from modified phenolic resins. In manufacturing, a common method involves using both roller compaction and twin-screw extrusion. Wood is used as a filler to impregnate the resin, and other reagents are then added and mixed thoroughly. The powder is then pulverized to produce compression molding powder. Materials such as quartz can be added to produce compression molding powders with enhanced insulation and heat resistance. Compression molding powders are a raw material for various plastic products, which can be manufactured industrially through injection molding or compression molding. Figure 2 shows the application of modified phenolic resin in compression molding powders. Compression molding powders are primarily used in electrical components such as switches and plugs for household items.

2. Application of Modified Phenolic Resins in Coatings

For 70 years, coatings have used phenolic resins. Rosin-modified phenolic resins or 4-tert-Butylphenol formaldehyde resin are the main ones in phenolic coatings. These resins make coatings better at resisting acid and heat, so they're common in lots of engineering projects. Still, because they give things a yellow color, you can't use them if you want a light-colored finish. Besides being mixed with tung oil, they can also be blended with other resins. To increase a coating's alkali resistance and air-dried hardness, alkyd resins can be added to improve the coating's alkali resistance and hardness. For coatings requiring acid and alkali resistance and good adhesion, epoxy resins can be added to enhance the coating's performance. Figure 3 illustrates the application of modified phenolic resins in coatings.

3. Application of Modified Phenolic Resins in Phenolic Adhesives

Phenolic adhesives are mainly made from modified thermosetting phenolic resins. If phenolic resin is used to create adhesives, its viscosity can be a problem, restricting it to plywood bonding. But, modifying phenolic resin with polymers can improve its heat resistance and adhesion. Phenolic-nitrile adhesives can even have good mechanical strength and toughness, especially when it comes to impact resistance.

4. Application of Modified Phenolic Resins in Fibers

Phenolic resins also have a wide range of applications in the fiber industry. Phenolic resin is melted and drawn into fibers, which are then treated in polyoxymethylene. After a period of time, the filaments solidify, resulting in a fiber with a solid structure. To further enhance the fiber's strength and modulus, the modified phenolic resin can be mixed with molten low-concentration polyamide and drawn into fibers, as shown in Figure 4. The spun fibers are typically yellow and possess high strength. They will not melt or burn even at temperatures of 8,000°C. It will also self-extinguish in these harsh environments, preventing fires from occurring at the source. At room temperature, polyamide-modified phenolic resin fibers are highly resistant to concentrated hydrochloric and hydrofluoric acids, but less resistant to strong acids and bases such as sulfuric acid and nitric acid. These products are primarily used in factory protective clothing and interior decoration, minimizing employee injuries and fatalities in the event of a fire. They are also commonly used as insulation and thermal insulation materials in engineering projects.

5. Application of Modified Phenolic Resins in Anti-Corrosion Materials

Phenolic resins are used to make anti-corrosion stuff, but the modified versions are more common. You'll often see these as phenolic resin mastics, phenolic-epoxy composite fiberglass, or phenolic-epoxy coatings. A good example is phenolic-epoxy coatings, which mix the acid resistance of phenolic resins with the alkali resistance and stickiness of epoxy resins. This mix makes them great for protecting pipelines and vehicles from corrosion.

6. Application of Modified Phenolic Resin in Thermal Insulating Materials

Because modified phenolic resin offers superior heat resistance compared to pure phenolic resin, modified phenolic resin foams occupy a prominent position in the thermal insulation market, as shown in Figure 5. Modified phenolic resin foams also offer thermal insulation, are lightweight, and are difficult to spontaneously ignite. Furthermore, when exposed to flames, they do not drip, effectively preventing the spread of fire. Consequently, they are widely used in thermal insulation color-coated steel sheets, room insulation, central air conditioning, and pipes requiring low temperatures. Currently, polystyrene foam is the most widely used insulation material on the market, but its performance is far inferior to that of modified phenolic resin foam. Modified phenolic resin foam, due to its low thermal conductivity and excellent thermal insulation, has earned it the title of "King of Insulation" in the insulation industry.

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For outdoor environments, you should choose EPDM. Nitrile suits oil and fuel contact best. For mixed chemical resistance, select neoprene and chloroprene. Evaluate your project’s environmental exposure, chemical compatibility, and temperature requirements. These factors will help you make the right material choice for reliable, long-term performance.

1. Comparison Overview

Key Properties

When you compare Chloroprene Rubber(such as Polychloroprene Rubber CR2440) , EPDM, and Nitrile Rubber, you need to focus on several critical properties. These include oil resistance, weathering, ozone/UV resistance, fire performance, temperature range, and cost. The table below summarizes how each material performs in these areas:

Property

Ozone and Weathering Resistance Table

Fire Resistance Classification Table

2. Pros and Cons

You should weigh the advantages and disadvantages of each material before making your selection.

Chloroprene Rubber

• Pros: Offers balanced resistance to oil, chemicals, and weathering; Performs well in outdoor and marine environments; Less flammable than many other rubbers.
• Cons: Faces supply chain risks due to regulatory restrictions; Ozone resistance is lower than EPDM or Nitrile; Cost can be higher than EPDM.

EPDM

• Pros: Excels in outdoor, UV, and ozone-exposed applications; Maintains flexibility at low temperatures; New formulations provide flame resistance and self-healing properties; Cost-effective for large-scale projects.
• Cons: Poor resistance to oils and fuel; Requires additives for optimal fire performance; Not suitable for applications involving petroleum-based fluids.

Nitrile Rubber

• Pros: Outstanding oil and fuel resistance; Enhanced heat resistance in modern compounds; Can be blended for specialized performance, such as static dissipation; Eco-friendly options are emerging.
• Cons: Weathering and ozone resistance are lower than EPDM; Not inherently flame retardant; Flexibility decreases at low temperatures.

3. Choosing the Right Material

Environmental Factors

You need to assess the environment where your rubber material will operate. Outdoor exposure, sunlight, ozone, and weathering can quickly degrade some rubbers. EPDM stands out for its excellent resistance to ozone and sunlight, making it the top choice for outdoor applications. You benefit from EPDM’s ability to withstand harsh weather, UV rays, and temperature swings. This material can last up to 20 years or more in outdoor conditions. If your project involves exposure to oils or solvents, Chloroprene Rubber (such as Neoprene AD-20) offers good oil resistance and performs well in parts exposed to chemicals. EPDM is also more environmentally friendly because it is non-toxic and recyclable, while Neoprene (Chloroprene Rubber) is less sustainable.

Chemical Resistance

You must match the rubber’s chemical resistance profile to your application. Each material reacts differently to oils, fuels, and industrial chemicals. Nitrile Rubber provides high oil resistance but performs poorly against weather and ozone. Chloroprene Rubber offers moderate oil resistance and excellent weather resistance. EPDM does not resist oils but excels in weather and ozone resistance.

You should always check the chemicals your project will encounter. Select Nitrile Rubber for oil and fuel contact. Use Chloroprene Rubber for balanced resistance to chemicals and weather. Choose EPDM for applications with no oil exposure but high weathering demands.

4. Summary

Choosing the right rubber material for your project depends on matching its properties to your application’s demands. You need to consider oil resistance, weathering, ozone and UV exposure, and the specific environment where the rubber will perform. Each rubber type offers unique strengths that make it ideal for certain uses.

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Polyvinyl alcohol (PVA) is a water-soluble synthetic polymer with excellent film-forming properties, surface activity, and strong adhesion to inorganic and cellulosic materials. Global annual PVA production is approximately 1.05 million tons, with Japan producing approximately 300,000 tons. Approximately 14,100 tons of this is used as a paper processing chemical, a surface sizing agent for plain paper, a sizing agent for coated and coated paper, a fluorescent brightener, an inkjet ink absorber, an adhesive for inorganic fillers, and a silicone sealant for release paper.

The paper business faces challenges like using different types of wood pulp and faster, bigger machines for making paper and printing. Because of this, they need better water-soluble polymers with special features. These polymers are important for making fancy specialty papers and papers used in tech. To adapt to these fundamental changes in the papermaking industry, Kuraray Japan has developed and mastered the properties of modified PVA with novel properties. This article will focus on two specialty PVA: the silanol-modified "R-series PVA" and the high-barrier "Exceval PVA" with the introduction of special hydrophobic groups. The two types will be discussed, along with their properties and applications in paper processing additives.

2. PVA Properties and Dissolution Methods

Industrially, PVA is produced by polymerizing and then saponifying polyvinyl acetate. Its fundamental properties depend on its degree of polymerization and saponification. Most commercially available PVAs had a degree of polymerization of 200 to 4000 and a degree of saponification of 30% to 99.9% by mole fraction. The main varieties of PVA produced by Kuraray (Kuraray PVA) are shown in Tables 1 and 2.

3. Specialty Kuraray PVA

To date, Kuraray has produced a variety of Kuraray PVAs with varying degrees of polymerization and saponification, which are used in a wide range of applications. As demand grows for better PVA and more varied uses, just tweaking the polymerization and saponification degrees isn't enough anymore. So, Kuraray PVA now comes with special groups added to give it extra function.

This article will introduce two types of functionalized PVA: the "R-series PVA," modified with silanol groups, and the "Exceval PVA (Exceval HR-3010)," which incorporates special hydrophobic groups for high barrier properties.

3.1 Silanol-Modified R-series PVA

The R-series is a modified PVA with silanol groups. Table 3 lists the quality standards for the R-series products.

3.2 High Barrier Exceval PVA

Exceval PVA is a PVA containing special hydrophobic groups. The introduction of hydrophobic groups enhances the crystallinity of the solid polymer, resolving the dilemma of achieving both high water resistance and stable aqueous solution viscosity, which is difficult to achieve with standard PVA. The use of PVA is increasing annually. PVA is usually used as a stabilizer in adhesives that need to resist water. But, when used in food packaging films, PVA doesn't block oxygen well when it's humid. Exceval PVA is also being developed as an improved material. In coated paper applications, Exceval PVA has also been successfully used when higher water resistance than PVA is required.

This article reports on the results of a new application study for Exceval PVA, specifically its use as an oil-resistant agent in food packaging. The product specifications of the Exceval PVA used in this study are shown in Table 4.

Table 5 shows that coating with Exceval PVA RS-2117 achieves air resistance roughly equivalent to that achieved with partially saponified PVA-217, while significantly reducing water absorption. Paper coated with partially saponified PVA exhibits higher air resistance. This is because the highly hydrophobic, partially saponified PVA has a lower surface tension in aqueous solution, inhibiting penetration into the paper. However, partially saponified PVA suffers from a significant reduction in water resistance. While Exceval PVA, modified with a special hydrophobic group, is fully saponified, it still exhibits the same permeability as partially saponified PVA, offering both improved water resistance and air impermeability.

R-series PVA contains highly reactive silanol groups, which improve adhesion to various inorganic materials. Using the R-series in inkjet media reduces the amount of polyvinyl alcohol used as a binder for silica particles, improving print quality. Even without a crosslinker, the R-series provides high water resistance. Exceval PVA is a modified, hydrophobic polyvinyl alcohol that offers excellent water resistance and gas barrier properties under high humidity conditions. The lower air permeability of coated paper provides a higher barrier to oils and greases than fully water-soluble polyvinyl alcohol, a property further enhanced when used with flake minerals. Exceval is now FDA-registered as safe for contact with food, opening doors for its use in food packaging paper.

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Carbon foam, a functional carbonaceous material with a honeycomb structure, not only boasts excellent properties such as low density, high strength, oxidation resistance, and adjustable thermal conductivity, but also boasts excellent processability. Therefore, it can be used as a thermal conductor, insulator, catalyst carrier, biosolidifier, and absorber. It holds broad application prospects in military applications, energy-saving building insulation, chemical catalysis, biological wastewater treatment, and energy. Carbon foam can be sorted into two kinds—one that lets heat pass through easily (thermally conductive) and another that stops heat from passing through (thermally insulating). The difference lies in how much the original carbon material has been turned into graphite. Mesophase pitch and phenolic resin are two typical carbonaceous precursors for producing high- and low-thermal-conductivity carbon foams, respectively. Currently, both thermosetting and thermoplastic phenolic resins are high-quality carbonaceous precursors for producing low-thermal-conductivity carbon foam. Using phenolic resin as the raw material, a phenolic resin foam can be produced by adding a blowing agent and a curing agent and foaming at normal pressure. Carbon foam is then produced by high-temperature carbonization. The compressive strength of this carbon foam is below 0.5 MPa, which restricts how it can be used.

When Phenolic Resin 2402 is used as the raw material, the pores of the carbon foam produced at different foaming pressures are all nearly spherical (Figure 6). Since no foaming agent is added, the foaming process follows a self-foaming mechanism, whereby the matrix material undergoes a cracking reaction at a certain temperature, generating corresponding small molecular gases. As gases form, they gather and grow into pores. The viscosity, structure, volume, shape, and gas production rate of the base material change as cracking gas is produced. This means the structure of pores in carbon foam depends on the base material's viscosity, gas production rate, volume, how quickly its viscosity changes, and outside pressure within the foaming temperature range.

At foaming temperatures between 300 and 425°C, 2402 phenolic resin makes lots of cracking gas (Figure 3(a)) and has low viscosity (<2×104Pa·s, Figure 4(d)). Because of this, surface tension causes the pores to be round. When the foaming pressure is 1.0 MPa, the low outside pressure causes bubbles to merge and grow, leading to larger pore sizes (500-800 μm). Also, the larger pores mean the carbon foam has thinner connections and many pores are close to becoming open cells (Figure 6(a)).

When the foaming pressure goes up to 3.5 MPa, the pore size of the carbon foam goes down (300-500 μm), the connections get thicker, and the pore structure is more consistent (Figure 6(b)). If the foaming pressure keeps increasing to 5.0 MPa, the pore size keeps going down, but the consistency of the pore structure starts to get worse (Figure 6(c)). At a foaming pressure of 6.5 MPa, the pore structure of the carbon foam keeps getting worse, but the pore density goes up (Figure 6(d)).

When the foaming temperature goes above 425°C, the viscosity of the 2402 phenolic resin quickly goes up. The foaming pressure clearly has an important impact on how consistent the pore structure is and how dense the carbon foam is. If the foaming pressure is less than the pressure inside the bubble, the cracking gas produced later can still overcome the base material's viscosity and keep gathering and growing in the already formed bubble. This results in a fairly consistent pore structure in the bubble, but no new bubbles will form. But, if the foaming pressure is high enough, the cracking gas produced later can only form new, smaller bubbles at the connections of the already formed bubbles or in the base material, which makes the pore structure of the foamed carbon worse and increases the pore density.

Conclusion

(1) The way thermoplastic phenolic resin (resin for refractory) foams is based on its own reaction. How well it foams depends on the conditions (pressure, temperature, and time). It's also influenced by how the molecules interact, considering their size, distribution, how they lose weight when heated, and how their viscosity changes with temperature. Viscosity and temperature are key.

(2) When heated to 300-420°C, 2402 Phenoic formaldehyde resin breaks down fast, making a lot of gas. If the material's viscosity is below 2×104 Pa·s at this point, the resulting foamed carbon has good bubbles that are round and evenly spaced.

(3) Lower pressures when foaming help make foamed carbon with consistent pores. Higher pressures stop the gas from clumping together and getting bigger, which causes more bubbles to form. This makes the pore structure uneven and increases how many bubbles there are.

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In today's industry, new materials are boosting how well products work. Polyvinyl Alcohol (PVA) is one of these. It's a special kind of synthetic polymer that's becoming very important for making glues, coatings, and films. PVA is great at forming films, sticking things together, dissolving in water, and blocking stuff from getting through. All these things make products better and more competitive.

1. PVA in Adhesives: The Cornerstone of Strong Adhesion

PVA stands out because it sticks things together very well. Its molecular structure contains numerous hydroxyl (-OH) groups, which form strong hydrogen bonds with a variety of substrates, resulting in a secure bond.

How PVA Works in Adhesives:

• Excellent Adhesive Properties: PVA's hydroxyl groups allow it to wet and stick to things like paper, wood, cloth, leather, and certain plastics, creating a strong bond.
• Excellent Film-Forming Properties: When PVA solution dries, it makes a continuous, smooth, and very flexible film. This film helps the glue stick better. It also spreads stress evenly on the surface, which lowers stress points and makes the bond stronger and last longer.
• Excellent Cohesive Strength: Hydrogen bonding between PVA molecular chains also imparts high cohesive strength to the adhesive layer, making the bond less susceptible to breakage when subjected to external forces.
• Modified Polymer Adhesives: PVA is often used as a modifier for polymer adhesives such as polyvinyl acetate (PVAc) emulsions. The addition of PVA significantly increases the viscosity, cohesive strength, wet adhesion, and initial tack of PVAc-based adhesives, while also improving their film-forming properties.

Typical Product Applications:

• Paper and Packaging: PVA is a key adhesive component in the production of products such as paperboard, corrugated boxes, envelopes, and tapes. Its rapid cure and high bond strength meet the demands of high-speed production lines.
• Wood and Furniture: In the woodworking industry, PVA-based adhesives are favored for their excellent adhesion to wood and relatively low cost. Textiles: PVA can be used as a textile adhesive for non-woven fabric production and garment lamination.

2. PVA in Coatings: Improving Performance and Aesthetics

PVA is also widely used in coatings. It not only serves as a film-forming agent but also as an additive, significantly improving the coating's application performance and final film finish.

Mechanisms of PVA in Coatings:

• Enhancing Adhesion: Similar to its role in adhesives, PVA helps the coating adhere better to the substrate surface, reducing flaking and blistering, and improving coating durability.
• Improving Leveling and Uniformity: PVA's film-forming properties help create a smooth, uniform coating. In paper coatings, PVA acts as a carrier, helping evenly distribute pigments and optical brighteners, enhancing the paper's gloss and printability.
• Thickening and Stabilization: In water-based coatings, PVA acts as a thickener, adjusting the viscosity and making it easier to apply. It also acts as a protective colloid, stabilizing pigment dispersions and preventing settling.
• Optical Enhancement: In paper or textile coatings, PVA is an excellent carrier for optical brighteners. It helps the agents distribute more evenly and anchor them to the surface, effectively absorbing UV light and reflecting bluish-white light, significantly improving the product's whiteness and brightness.

Typical Product Applications:

• Paper Coating: CCP Polyvinyl Alcohol BP-05 (CCP BP 05), a partially hydrolyzed form of PVA, exhibits both hydrophilic and hydrophobic properties, making it ideal as a component in paper coatings. It improves paper's smoothness, printability, ink bleed resistance, and surface strength. BP-05 is recommended for paper coating, indicating its specialized application in this area.
• Architectural Coatings: In building materials such as cement mortar and gypsum board, PVA can be used as an additive to improve flexibility, bonding strength, and crack resistance.
• Specialty Coatings: PVA can also be used to create high-performance coatings, such as packaging coatings with excellent barrier properties, or as a surface treatment for leather, making it smoother and easier to print.

3. PVA in Films: A Model of Versatility

PVA film is very useful because of its special mix of features. It can be used in many areas, especially for packaging and things that are thrown away after use.

Properties of PVA Film:

• High Barrier: PVA film keeps oxygen and smells out well. This makes it a good option for keeping safe things that are easily changed or have strong smells.
• Water Solubility and Biodegradability: One of the best things about PVA film is that it can dissolve in water. Also, it can break down under certain conditions, which is good for the environment. This helps meet the rising needs for eco-friendly products. This gives it unique advantages in disposable and water-soluble film applications.
• Controllable Water Solubility: By controlling the degree of polymerization and hydrolysis of PVA, its dissolution rate and temperature in water can be precisely tailored to meet the needs of various applications.
• Chemical Stability: PVA exhibits excellent resistance to oils, greases, and most organic solvents.

Typical Product Applications:

• Soluble Packaging: Selvol Polyvinyl Alcohol 205 (Celvol 205), a partially hydrolyzed PVA with low viscosity, sees main application across adhesives, papermaking, and textile sectors. Its low viscosity can make it more useful in some film and coating processes. A common use involves creating packaging films for things like laundry detergent and dishwashing tabs. People can just put the whole package in water, and it will dissolve. This makes things easier and cuts down on plastic waste.
• Agricultural Film: Controlled-release PVA films can be used to encapsulate pesticides or fertilizers, slowly releasing them under specific conditions to reduce environmental pollution.
• Medical Applications: PVA's biocompatibility and controllable properties also offer potential applications in the medical field, such as drug delivery vehicles and contact lenses.

4. The Future of PVA

Polyvinyl alcohol (PVA), with its unique chemical structure and physical properties, plays a vital role in three major areas: adhesives, coatings, and films. From providing strong adhesion, enhancing the decorative and protective properties of coatings, to creating environmentally friendly and convenient packaging solutions, PVA's applications are continuously deepening and expanding.

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Polyvinyl alcohol (PVA) is a widely used synthetic material. PVA ability to dissolve in water and break down naturally makes it a good choice for packaging films. The main production methods for PVA film are aqueous solution coating and melt blow molding. PVA is hard to shape with heat because it melts at a higher temperature than it decomposes. This is due to the strong links between its molecules and its crystal structure. Therefore, the most important factor in the processing of PVA film is the selection of appropriate additives.

1. Effect of Plasticizer Amount on Tensile Strength, Tear Strength, and Elongation at Break of Polyvinyl Alcohol Film

As shown in Figure 1, film ability to resist breaking lessens as more plasticizer is added. This suggests that plasticizers reduce how strong the film is. The plasticizer gel theory explains that when the plasticizer mixes with the resin, it loosens the points where the resin molecules connect. These connections have different strengths. The plasticizer pulls them apart and hides the forces that hold the polymer together. This reduces the secondary forces between the polymer macromolecules, increases the flexibility of the macromolecular chains, and accelerates the relaxation process. Tensile strength goes down as you add more plasticizer.

As the amount of plasticizer is increased, the film becomes more flexible and stretches further before breaking. This suggests that plasticizers make the film more pliable. Plasticizers achieve this by weakening the attraction between the large molecules in the polymer. This increased flexibility and longer relaxation period lead to the film ability to stretch further.

The data indicates that as more plasticizer is added, the film becomes easier to tear. This likely happens as the plasticizer reduces the film's surface energy and lessens the energy needed for both plastic flow and lasting deformation. These factors, in turn, contribute to the film's reduced resistance to tearing.

2. Effect of Crosslinker Amount on the Tensile Strength, Elongation at Break, and Tear Strength of PVA Film

As shown in Figure 3, the film's tensile strength goes up gradually as the amount of crosslinker is increased, during which the elongation at break goes down gradually. When a certain point is reached, the film's tensile strength goes down gradually, while the elongation at break goes up gradually. At first, as more crosslinker is added, the number of working polymer chains goes up, intermolecular forces get stronger, and the polymer chains become less flexible. The ability of the large molecular chains to change shape and rearrange decreases while the chain relaxation is difficult. So, the tensile strength goes up, while the elongation at break goes down. Continuing the use of crosslinkers causes degradation and branching to increase gradually, which decreases the number of working polymer chains, and increases the flexibility of the polymer chains. The ability of the large molecular chains to change shape and rearrange increases, while the chain relaxation becomes easier. As a result, the tensile strength starts to go down again, while the elongation at break goes back up.

As shown in Figure 4, the tear strength of the film changes with the amount of crosslinker. At first, it goes up, but then it starts to go down. This happens because when crosslinking starts, more crosslinker helps the polymer network form. This makes the film's surface energy go up gradually. It then needs more energy to spread plastic flow and irreversible viscoelastic processes. Because of this, the film's tear strength gets better as crosslinking happens. But, if there is too much crosslinker with too much polymer broken down, and there are more branching reactions, the tear strength gets worse.

3. Conclusions

• When you add more plasticizer, PVA film becomes less strong but stretches and tears more easily.
• When you add more crosslinker, film strength and resistance to tearing improve at first, but then weaken, while its ability to stretch keeps getting better.

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Polyvinyl alcohol (PVA) is a fundamental raw material for vinylon production and is also used in the production of adhesives, emulsifiers, and other products. In the PVA production process, solution polymerization is used to ensure a narrow degree of polymerization distribution, low branching, and good crystallinity. The VAM polymerization rate is strictly controlled at approximately 60%. Due to the control of the polymerization rate during the VAM polymerization process, approximately 40% of the Vinyl Acetate Monomer (VAM) remains unpolymerized and requires separation, recovery, and reuse. Therefore, research on VAM recovery process is a crucial component of the PVA production process. There is a polymer-monomer relationship between Ethylene Vinyl Acetate (EVA) and vinyl acetate monomer (VAM). Vinyl acetate monomer is one of the basic raw materials for making ethylene vinyl acetate polymer.

This paper uses the chemical simulation software Aspen Plus to simulate and optimize the VAM recovery process. We studied how process settings in the first, second, and third polymerization towers affect the production unit. We found the best settings to save water used for extraction and lower energy consumption. These parameters provide an important theoretical basis for the design and operation of VAM recovery.

1 Vinyl Acetate Monomer Recovery Process

1.1 Simulation Process

This process includes the first, second, and third polymerization towers in the vinyl acetate monomer recovery process. The detailed flow diagram is shown in Figure 1.

1.2 Thermodynamic Model and Module Selection

The vinyl acetate monomer recovery unit of the polyvinyl alcohol plant primarily processes a polar system consisting of vinyl acetate, methanol, water, methyl acetate, acetone, and acetaldehyde, with liquid-liquid separation between vinyl acetate and water. The main equipment in the vinyl acetate monomer recovery unit of the polyvinyl alcohol plant was simulated using Aspen Plus software. The RadFrac module was employed for the distillation tower, and the Decanter module for the phase separator.

2 Simulation Results

We ran a process simulation on the vinyl acetate monomer recovery unit in the polyvinyl alcohol plant. Table 3 shows a comparison of the simulation results and actual values for the main logistics. As shown in Table 3, the simulation results are in good agreement with the actual values, so this model can be used to further optimize the process parameters and process flow.

3 Process Parameter Optimization

3.1 Determination of the Amount of Stripping Methanol

Polymerization Tower 1 takes out vinyl acetate monomer (VAM) from the stream that remains after polymerization. It uses methanol vapor at the bottom for heat. The right amount of methanol is important for how well the tower works. This study looks at how different amounts of methanol affect the mass fraction of PVA at the tower's bottom and the mass fraction of VAM at the top, assuming the feed stays the same and the tower's design is constant.

As shown in Figure 2, when the heat capacity needed for separation in Polymerization Tower 1 is satisfied, raising the stripping methanol amount lowers the PVA mass fraction at the bottom and the VAM mass fraction at the top. The stripping methanol amount has a linear relationship with the PVA mass fraction at the bottom and the VAM mass fraction at the top.

3.2 Optimization of the Feed Position in Polymerization Tower 2

In Polymerization Tower 2, an extractive distillation tower, the locations where the solvent and feed enter greatly affect how well the separation works. This column uses extractive distillation. Based on the physical properties of the extractant and the mixed feed, the extractant should be added from the top of the column. Figure 3 shows how the mixture feed position affects the methanol mass fraction at the top and the reboiler load at the bottom, keeping other simulation settings the same.

3.3 Optimizing the Extraction Water Amount in Polymerization Column 2

In Polymerization Column 2, extractive distillation is used to separate vinyl acetate and methanol azeotrope. By adding water to the top of the column, the azeotrope is disrupted, allowing for the separation of the two substances. The extract water flow rate has a big impact on how well Polymerization Column 2 separates these materials. With consistent simulation settings, I looked at how the amount of extract water affected the methanol mass fraction at the top and the reboiler load at the bottom of the column. The results are shown in Figure 4.

3.4 Optimizing the Reflux Ratio in Polymerization Column 3

In Polymerization Column 3, the reflux ratio is important for separating vinyl acetate from lighter substances like methyl acetate and trace water. This boosts the quality of vinyl acetate obtained from the side stream. We kept the simulation settings constant and studied how the reflux ratio affects both the mass fraction of vinyl acetate from the side stream and the reboiler load. The calculation results are shown in Figure 6. Maintaining the polymerization tower's reflux ratio around 4 helps ensure the vinyl acetate from the side line meets quality standards and keeps the reboiler load low.

4. Conclusion

(1) Using AspenPlus software, a suitable thermodynamic model is selected to simulate the entire process of vinyl acetate monomer recovery of the polyvinyl alcohol plant. The simulation results are in good agreement with the actual values and can be used to guide the process design and production optimization of the plant.

(2) Based on the establishment of a correct process simulation, the influence of the process parameters of the polymerization tower 1, polymerization tower 2, and polymerization tower 3 on the plant is investigated, and the optimal process parameters are determined. When vinyl acetate meets the needed separation standards, we can save on extraction water and lower energy use.

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VAE emulsion are water-based and good for the environment. They're used a lot as binders in strong glues. As the tech gets better and the emulsion market grows, people want more VAE emulsions, mainly those with a lot of ethylene. These high-ethylene VAE emulsions are great at resisting water and alkali, so they're becoming more popular.

How much ethylene is in VAE emulsions depends on things like pressure, temperature, time, how much initiator is used, the type and amount of emulsifier, and how the VAE is added. Lately, the market wants VAE emulsions that bind water really well. This paper looks at how the amount of ethylene in VAE emulsions affects them. We used different molecular weights of polyvinyl alcohols (PVA Polyvinyl Alcohol 088-20 and PVA Polyvinyl Alcohol 0588) as protective colloids, and a special PVA was used as part of the protective colloid to see how these colloids change the VAE emulsion properties.

1.Effect of Emulsifier Content on Emulsion Properties

In emulsion polymerization systems, the type and concentration of the emulsifier, as well as various factors that may influence the emulsification effect of the emulsifier, directly affect the stability of the polymerization reaction and, ultimately, the properties of the emulsion. As seen in Table 3 and Figure 2, a rise in emulsifier content leads to a higher conversion rate but a lower gel fraction. If the emulsifier surpasses 4%, the conversion rate drops, suggesting the substance is not chemically stable. Therefore, the optimal emulsifier content for this experiment is 4%.

2. Effect of Initiator Content on Molecular Weight and Emulsion Viscosity

The initiator is the most important component in the entire VAE emulsion formulation. It decomposes and releases free radicals, which are the basis for emulsion polymerization. Figure 3 shows that with increasing initiator content, both molecular weight and viscosity show an upward trend, with the optimal initiator dosage being 2.5%.

3. Effect of Reaction Temperature on Emulsion Reaction

Table 4 shows that with increasing reaction temperature, the reaction rate accelerates, the residual monomer content decreases, and the amount of aggregates increases. Raising the reaction temperature speeds up how fast the initiator breaks down, making more free radicals and boosting the number of spots where reactions can happen. At the same time, a higher temperature makes latex particles move around more randomly, which means they bump into each other and join together more often. Because of these things, the emulsion becomes less stable and might even turn into a gel or separate. Therefore, the initial reaction temperature is determined to be 65°C, and the later reaction temperature is 70°C to 85°C.

4. Effect of Polymerization Reaction Pressure on Ethylene Content, Solids Content, and Viscosity

Figure 4 shows that increasing the reaction pressure within a certain range gradually increases the ethylene content of the VAE emulsion and decreases the glass transition temperature of the product. At a reaction pressure of 7.5 MPa, the ethylene content reaches 21%, and the glass transition temperature lowers to -4°C. As shown in Figure 5, under the best reaction conditions, the solid content goes up as the polymerization pressure increases, but the change is small, staying within (56 ± 0.5)%. The emulsion viscosity first goes up and then down as the polymerization pressure increases, peaking at 3200 mP·s at a polymerization pressure of 6 MPa before going down. This indicates that a certain pressure can facilitate polymerization and increase the emulsion viscosity.

5. Effect of Modified PVA as a Protective Colloid on VAE Emulsion Properties

To increase how well VAE emulsions resist water, a PVA, changed to include water-repelling groups, was used to take the place of some of the PVA1788 protective colloid. Table 5 shows how varying amounts of the modified PVA (from 10% to 50% of the total protective colloid) change the VAE emulsions' stability, thickness, and water resistance. The data in Table 5 shows that as the amount of modified PVA goes up, the emulsion stays stable without separating, suggesting the modified PVA doesn't really impact the system's stability. Based on Figure 6, the emulsion gets thicker as the modified PVA content rises, peaking at 4000 mPa·s when the modified PVA makes up 5% of the mixture.

6. VAE Emulsions with Different Ethylene Contents and Properties

We made different VAE emulsions by testing how different reaction conditions change the emulsion's properties. These emulsions had different amounts of ethylene, glass transition temperatures, and leftover VAc.

We found that starting the reaction at 65°C works best. The temperature can then be adjusted to between 70°C and 85°C. A 4% emulsifier content and a 2.5% initiator dosage also produce the best results. By controlling the reaction pressure, we were able to create VAE emulsions with ethylene contents from 9% to 23%. By replacing part of the protective colloid with hydrophobic-modified PVA, the water resistance of the emulsions was significantly improved.

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1. Introduction to Phenolic Resins

Phenoic formaldehyde resin are primarily formed by the polycondensation of phenol and formaldehyde. Phenolic resins were first accidentally created by the German scientist Bayer in the 1780s. He mixed phenol and formaldehyde and processed them to produce a fluid product. However, Bayer did not further research or discuss this product. It was not until the 19th century that Bloomer, building on the work of the German chemist Bayer, successfully produced phenolic resin using tartaric acid as a catalyst. However, due to complex operation and high costs, industrialization was not achieved. It was not until the 1820s that the American scientist Buckland ushered in the era of phenolic resins. He noticed this chemical product and, through systematic research and discussion, ultimately proposed the "pressure and heat" curing method for phenolic resins. This laid the foundation for the future development of phenolic resins, and the subsequent rapid development of this type of resin.

2. Research on Modified Phenolic Resins

However, with technological advancements, scientists have discovered that traditional phenolic resins are increasingly unable to meet the needs of emerging industries. Therefore, the concept of modified phenolic resins has been proposed. This involves using phenolic resin as a matrix and adding a reinforcing phase to enhance the performance of the phenolic resin through the properties of the reinforcing phase. While traditional phenolic resins possess remarkable heat resistance and oxidation resistance due to the introduction of rigid groups such as benzene rings into the matrix, they also have numerous drawbacks. During preparation, phenolic hydroxyl groups are easily oxidized and do not participate in the reaction, resulting in a high concentration of phenolic hydroxyl groups in the finished product, leading to impurities. Furthermore, phenolic hydroxyl groups are highly polar and readily attract water, which can lead to low strength and poor electrical conductivity in phenolic resin products. Prolonged exposure to sunlight can also severely alter the phenolic resin, causing discoloration and increased brittleness. These drawbacks significantly limit the application of phenolic resins, making modification of phenolic resins essential to address these shortcomings. Currently, the main types of modified phenolic resins include polyvinyl acetal resin, epoxy-modified phenolic resin, and silicone-modified phenolic resin.

2.1 Polyvinyl Acetal Resin

Polyvinyl acetal resin is currently modified by introducing other components. The principle is to condense polyvinyl alcohol (PVA) and aldehyde under acidic conditions to form polyvinyl acetal. This is primarily because polyvinyl alcohol is water-soluble and the aldehyde condensation prevents it from dissolving in water. This aldehyde is then mixed with a phenolic resin under certain conditions, allowing the hydroxyl groups in the phenolic resin to combine with those in the polyvinyl acetal, undergoing polycondensation and removing a molecule of water to form a graft copolymer. Due to the introduction of flexible groups, the added polyvinyl acetal enhances the toughness of the phenolic resin and reduces its setting speed, thereby reducing the molding pressure of polyvinyl acetal products. However, the only drawback is that the heat resistance of the polyvinyl acetal products is reduced. Therefore, this modified phenolic resin is often used in applications such as injection molding.

2.2 Epoxy-modified phenolic resin

Epoxy-modified phenolic resin is typically prepared using bisphenol A epoxy resin as the reinforcing phase and phenolic resin as the matrix. This reaction primarily involves an etherification reaction between the phenolic hydroxyl groups in the phenolic resin and the hydroxyl groups in the bisphenol A epoxy resin, resulting in the bonding of the hydroxyl groups in the phenolic resin and the hydroxyl groups in the bisphenol A epoxy resin, removing a molecule of water and forming an ether bond. Subsequently, the hydroxymethyl groups in the phenolic resin and the terminal epoxy groups in the bisphenol A epoxy resin undergo a ring-opening reaction, forming a three-dimensional structure. In other words, the curing action of the bisphenol A epoxy resin is stimulated by the phenolic resin, leading to further structural changes. Due to its complex structure, this modified resin exhibits excellent adhesion and toughness. Furthermore, the modified product also possesses the heat resistance of bisphenol A epoxy resin, meaning the two materials can be considered to complement and improve each other. Therefore, this material is primarily used in molding, adhesives, coatings, and other fields.

2.3 Silicone-Modified Phenolic Resin

Silicone-modified phenolic resin uses silicone as a reinforcing phase. Due to the presence of silicon-oxygen bonds in silicone, silicone possesses excellent heat resistance, significantly higher than that of typical polymer materials. However, silicone has relatively poor adhesion. Therefore, silicone can be introduced to enhance the heat resistance of phenolic resin. The principle is that silicone monomers react with the phenolic hydroxyl groups in the phenolic resin to form a cross-linked structure. This unique cross-linked structure results in a modified composite material with excellent heat resistance and toughness. Tests show this material holds up well under high heat for a long time. That's why it's often used in rockets and missiles that need to withstand extreme temperatures.

Phenolic resins are usually modified using the methods above. You can make modified resins like epoxy-modified, silicone-modified, and polyvinyl acetal resins by starting with phenolic resin. Another way is to turn aldehydes or phenols into other stuff, and then react that with phenols or aldehydes to make modified resins like phenolic novolac resin and xylene-modified phenolic resin. Alternatively, reactions without phenol can produce a first-stage phenolic resin, which then reacts to produce a second-stage phenolic resin, such as diphenyl ether formaldehyde resin.

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Polyvinyl acetate emulsion (PVAc), commonly known as white latex, are widely used as a key polymer adhesive due to their ability to be directly modified with a variety of additives, excellent mechanical strength, and resistance to adhesive defects. Furthermore, their environmental friendliness as a water-based adhesive makes them particularly attractive. However, due to different synthesis processes, white latexes also have some drawbacks, such as limited water and heat resistance, generally high viscosity, and high solids content, which increase their cost.

1. Effect of Polyvinyl Alcohol on Emulsion Viscosity

Experiments were conducted using fully alcoholyzed PVA1799 and partially alcoholyzed PVA1788. The viscosity of the emulsion prepared with PVA1788 was 3.8 Pa·s, while that of the emulsion prepared with PVA1799 was 3.0 Pa·s. This is primarily due to the grafting effect of the tertiary hydrogen atoms -CH(OCOCH3)- in PVA1788. In addition, different polyvinyl alcohol production methods result in different distributions of residual acetate groups within the molecule, resulting in different viscosities in the resulting polyvinyl acetate emulsions. PVA1788 was selected for this experiment.

2. Effect of Initiator on Emulsion Viscosity and Solids Content

Generally, at a specific temperature for polymerization, if you start with very little initiator, both viscosity and solids increase as you add more initiator. The viscosity peaks at 4.2 Pa·s when the initiator is 0.6% of the total monomer, resulting in a 36% solids content. If you keep adding initiator past that point, the emulsion gets less viscous, but the solids stay about the same. During emulsion polymerization, the pH of the medium directly affects the decomposition rate of the initiator. The pH of the emulsion polymerization system is required to be around 6. Due to the presence of a small amount of Acetic Acid Vinyl Ester Monomer and the sulfate groups generated during initiator decomposition, the pH of the system drops to 4-5. Therefore, an appropriate amount of sodium bicarbonate is used to adjust the pH.

3. Effect of Emulsifier Amount on Emulsion Viscosity

With other conditions unchanged, the emulsifier dosage was varied. The results are shown in Figure 1. Too little emulsifier results in poor emulsion stability and easy demulsification. Emulsion viscosity increases with increasing emulsifier dosage, reaching its maximum viscosity at 0.15% of the total monomer content. When the emulsifier dosage exceeds the optimal value, the emulsion particles increase in number, their size decreases, and the viscosity decreases.

4. Effect of Reaction Temperature on Emulsion Viscosity and Solids Content

Experiments show that when you keep the reactant ratios, addition method, and stirring the same, changing the reaction temperature really does change how thick the polyvinyl acetate emulsion is and how much solid stuff is in it. The results are shown in Table 2. This is because polymerization is endothermic, so higher reaction temperatures favor the reaction. However, when the reaction temperature reaches 80°C, exceeding the boiling point of vinyl acetate monomer (72°C), it increases reflux and consumes energy. Low temperatures also slow the reaction, leading to incomplete reaction and low emulsion viscosity.

5. Effect of Monomer Purity on Emulsion Viscosity and Solids Content

Due to storage and transportation requirements, polymerization inhibitors are often added to vinyl acetate before shipment to maintain its stability. To facilitate polymerization, the vinyl acetate was distilled before the experiment. The results are shown in Table 3. Table 3 shows that the properties of vinyl acetate directly affect the emulsion viscosity and solids content. Distillation of the monomer significantly increases the viscosity of the polyvinyl acetate.

6. Conclusions

• The traits of Vinyl Acetate Monomer (VAM) and polyvinyl alcohol change how thick the emulsion is and how much solid stuff is in it.
• The viscosity and solid content of an emulsion are affected by the reaction temperature, the amount of reactants, and how you add monomers, emulsifiers, and initiators during the emulsification procedure.
• We got a milky white polyvinyl acetate emulsion with some great qualities. It has a viscosity of 5.8 Pa•s, a solid content of 42%, a pH between 6 and 8, and a blue tint. The best part is, we achieved this by keeping the reaction temperature at 75 ℃ and carefully adding the emulsifier (0.15%) and initiator (0.6%) drop by drop in batches, based on the total monomer amount.

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