The Role of Polyether-Modified Polysiloxanes in Controlling Coating Leveling and Smooth Tactile Feel: Molecular Structure, Surface Migration, and Interfacial Control Mechanisms

1. Why Leveling and Tactile Feel Are Both Related to Surface State

1.1 Coating Film Formation Includes Wet-Film and Dry-Film Stages

In coating formulations, issues such as poor leveling, cratering, orange peel, edge pullback, waviness, poor slip, and insufficient surface smoothness may appear to be application defects, viscosity-related problems, or resin-selection issues. However, their underlying causes are often closely related to the interfacial state of the coating. After application, a coating typically goes through two key stages:

Stage	Main Manifestations	Key Influencing Factors
Wet-film stage	Wetting, spreading, leveling, cratering, orange peel	Surface tension, surface tension differences, substrate wetting, evaporation process, viscosity change
Dry-film stage	Smoothness, fineness, anti-blocking, low friction, tactile feel	Surface energy, surface-enriched components, coefficient of friction, coating film hardness, microscopic surface state

Leveling is not simply a matter of reducing the viscosity of the system, and tactile feel is not determined solely by the hardness or softness of the resin. Whether a coating film can form a flat, uniform, and fine surface is affected not only by viscosity, rheology, evaporation, film thickness, and application conditions, but is also closely related to surface tension control during the wet-film stage, as well as surface composition and friction characteristics during the dry-film stage.

1.2 Surface Tension Differences Are an Important Cause of Many Surface Defects

If local surface tension differences exist in the wet coating film, they may induce non-uniform flow, leading to defects such as cratering, orange peel, waviness, edge pullback, or uneven gloss. Industrial data show that even small surface tension differences may trigger cratering. For example, when overspray droplets fall onto a wet film that is still in a flowable state, a surface tension difference between the two may cause local spreading and cratering.

One important direction for improving leveling is to regulate the interfacial state, reduce unfavorable surface tension differences, and improve substrate wetting and wet-film spreading, so that the coating film can more easily form a continuous and uniform surface.

2. What Are Polyether-Modified Polysiloxanes?

Polyether-modified polysiloxanes are a class of polysiloxane surface additives organically modified with polyether segments. Conventional polydimethylsiloxane, or PDMS, silicone oils have low surface energy and can provide smoothness and surface tension reduction. However, their compatibility with most coating resins is limited, and improper use may easily lead to cratering, haze, reduced recoatability, and other problems. In modern coatings, organically modified polysiloxanes are widely used, and polyether modification is one important approach. The introduction of polyether segments helps improve the compatibility between polysiloxanes and coating systems, making their surface activity, migration ability, and formulation adaptability easier to adjust.

Polyether-modified polysiloxanes are organically modified siloxanes in which polyether segments are introduced onto the polysiloxane main chain or side chains. Their function arises from the combination of “low-surface-energy siloxane segments” and “compatibilizing polyether segments.” They retain the surface-regulating ability of organosilicones while reducing the application risks associated with the insufficient compatibility of conventional silicone oils.

Structural Component	Main Function
Polysiloxane segment	Provides low surface energy, surface migration, smoothness, and low friction
Polyether segment	Improves compatibility, dispersibility, hydrophilic/hydrophobic balance, and system adaptability

3. How Molecular Structure Determines Performance

3.1 Polysiloxane Segments: Providing the Basis for Low Surface Energy and Smoothness

The polysiloxane main chain consists of Si—O—Si bonds. The chain segments are flexible and have low surface energy. Under suitable conditions of compatibility, molecular weight, dosage, and drying/curing process, polysiloxane segments tend to enrich at the air/coating film interface. The main contributions of polysiloxanes to coating performance include:

① Regulating surface tension: They help reduce the surface tension of the wet coating film and, to a certain extent,

reduce the sensitivity of the wet film to local surface tension disturbances.

② Promoting surface enrichment: Low-surface-energy segments more readily migrate to the air/coating film interface, providing a basis for improved leveling and tactile feel.

③ Reducing the coefficient of friction: When the dry-film surface is rich in siloxane characteristics, surface friction resistance decreases, giving a smoother and finer tactile feel.

④ Improving anti-blocking and assisting scratch resistance: A low-friction surface can reduce surface damage caused by external friction, but scratch resistance still depends on resin hardness, crosslinking density, wax powders, fillers, and the overall coating film structure.

3.2 Polyether Segments: Improving Compatibility and System Adaptability

Polyether segments are usually composed of ethylene oxide, or EO, and propylene oxide, or PO, units. Their main function is to regulate the compatibility, dispersion state, and hydrophilic/hydrophobic balance of polysiloxanes in coating systems. The functions of polyether segments are mainly reflected in the following aspects:

① Improving system compatibility: They reduce the compatibility gap between polysiloxanes and resins, water, or solvents, thereby lowering the risk of cratering, turbidity, haze, and related issues.

② Adjusting the hydrophilic/hydrophobic balance: EO units are more hydrophilic, while PO units are relatively hydrophobic. The EO/PO ratio affects waterborne-system adaptability, surface activity, and formulation compatibility.

③ Influencing foaming tendency: Increasing EO content usually improves hydrophilicity and compatibility in waterborne systems. However, foaming tendency cannot be determined solely by the EO/PO ratio; it is also related to molecular weight, EO/PO arrangement, dosage, other surfactants in the system, and compatibility with defoamers.

④ Regulating the degree of surface migration: When there are more polyether segments, compatibility is usually better, but surface enrichment may be relatively milder. When the polysiloxane character is stronger, the surface effect may be more pronounced, but the risk of compatibility issues may also increase.

3.3 Relationship Between Key Structural Variables and Performance

Structural Variable	Main Influence on Performance
Length of polysiloxane segment	Affects surface tension regulation, smoothness, and degree of surface enrichment
Number of polyether grafts	Affects compatibility, dispersibility, and cratering risk
EO/PO ratio	Affects hydrophilicity, waterborne-system adaptability, surface activity, and foaming tendency
Molecular weight	Affects migration speed, intensity of surface effect, and durability of tactile feel
End-group structure	Affects recoatability, reactivity, migration resistance, and post-processing adaptability

4. How Polyether-Modified Polysiloxanes Improve Leveling

4.1 Leveling Problems First Occur During the Wet-Film Stage

After application, a coating forms a wet film. Before the wet film dries or cures, the surface of the coating film remains in a flowable state. At this stage, if local surface tension differences exist on the coating surface, they may drive uneven flow and cause defects such as orange peel, cratering, waviness, and edge pullback. These surface tension differences may arise from substrate surface contamination, spray-back or overspray droplets, uneven evaporation of water or solvent, local distribution differences of resin, additives, pigments, and fillers, as well as airflow and wet-film thickness variations during application.

One key to improving leveling is to reduce unfavorable surface tension gradients in the wet film, allowing the coating film to maintain a more stable spreading and flow state before drying or curing.

4.2 Regulating Surface Tension Differences Through Interfacial Migration

Polyether-modified polysiloxanes have surface activity. After being added to a coating, under suitable compatibility and migration conditions, their molecules migrate toward the air/coating film interface and form an oriented arrangement at the interface:

① The polysiloxane segments tend to distribute at the low-surface-energy interface.

② The polyether segments maintain certain interactions with the resin, water, or solvent.

This structural feature allows polyether-modified polysiloxanes with appropriate structures and dosages to reduce coating surface tension and, to a certain extent, weaken local surface tension differences. Rather than simply pursuing the idea that “the lower the surface tension, the better,” the more important point is to make the surface tension distribution of the wet film more uniform while ensuring wetting, compatibility, and an appropriate application window, thereby reducing defects caused by local surface tension differences.

4.3 Improving Substrate Wetting and Wet-Film Spreading

Wetting is the prerequisite for leveling. Only when the coating liquid first spreads sufficiently on the substrate surface can subsequent leveling occur effectively. If the coating does not adequately wet the substrate, problems such as edge pullback, exposed substrate, poor spreading, and unstable adhesion may occur. Polyether-modified polysiloxanes with suitable structures and dosages usually help reduce the contact angle of the coating on the substrate and improve wet-film spreading. This effect is especially important for waterborne coatings and low-surface-energy substrates. Because water has high surface tension, wetting plastic, old coating films, composite materials, and similar substrates is often more challenging in waterborne systems, requiring suitable surface additives to improve spreading and leveling.

The essence of how polyether-modified polysiloxanes improve leveling can be summarized as follows: during the wet-film stage, they regulate the interfacial state, reduce unfavorable surface tension differences, and improve substrate wetting and wet-film spreading, making it easier for the coating film to form a flat and continuous surface.

5. How Polyether-Modified Polysiloxanes Improve Tactile Feel

5.1 Tactile Feel Comes from Dry-Film Surface Properties

The tactile feel of a coating film is not a single property. Instead, it is the combined perception of friction, smoothness, dryness, fineness, tackiness, and microscopic surface flatness when the hand contacts the coating surface. Factors affecting tactile feel include the coefficient of friction, or COF; surface energy; coating film hardness and elasticity; microscopic surface roughness; surface-migrating components; waxes, matting agents, fillers, and resin systems; and the degree of drying or curing.

Polyether-modified polysiloxanes mainly improve low-friction-related tactile properties such as smoothness and fineness by changing the dry-film surface composition and reducing surface friction, rather than by changing the overall hardness or softness of the main resin.

5.2 Low-Surface-Energy Segments Promote Surface Enrichment

During drying or curing of the coating film, polysiloxane segments, because of their lower surface energy, tend to enrich at the air/coating film interface under suitable conditions. After a low-friction surface with siloxane characteristics forms on the dry film, the surface usually feels smoother and finer to the touch. However, tactile properties such as dryness, softness, and wax-like feel must still be evaluated together with the resin, wax powders, matting agents, fillers, and curing state. Industrial surface control additives generally provide two types of effects: one is interfacial tension control during the wet-film stage, such as leveling, wetting, and anti-cratering; the other is dry-film surface effects, such as smoothness, anti-blocking, scratch resistance, and tactile feel improvement.

5.3 Smoothness and Scratch Resistance Need to Be Distinguished

By reducing surface friction, polyether-modified polysiloxanes can reduce frictional resistance on the coating film surface under external force, thereby helping improve smoothness, anti-blocking, and light scratch performance. However, smoothness is not the same as scratch resistance. Scratch resistance also depends on the hardness of the main resin, crosslinking density, coating film thickness, wax powders or wear-resistant additives, filler type, curing degree, and surface microstructure. Polyether-modified polysiloxanes can improve smoothness, reduce friction, and, under certain conditions, assist in improving scratch resistance, but they cannot replace the overall design of the resin, wax, and wear-resistant additive system.

6. Technical Key: Balancing Compatibility and Migration

6.1 If Compatibility Is Too High, Surface Effects May Be Insufficient

If a polyether-modified polysiloxane is too compatible with the resin system, more of it will remain inside the coating film, and the proportion that migrates to the air/coating film interface will be insufficient. In this case, issues may arise such as insignificant leveling improvement, insufficient surface smoothness, limited tactile improvement, and weak effects at low dosage. This indicates that although the additive is stably present in the system, it has not sufficiently reached the interfacial position where it needs to function.

6.2 If Compatibility Is Insufficient, Surface Defects Are More Likely

If the compatibility between the polyether-modified polysiloxane and the system is insufficient, excessive migration, local enrichment, or precipitation may occur, causing cratering, haze in clearcoats, gloss reduction, surface oil spots, reduced recoatability, and poorer intercoat adhesion.

Therefore, stronger migration is not always better for polyether-modified polysiloxanes. They need to achieve an appropriate balance between compatibility with the system and surface migration ability. Additives require controlled compatibility: they must have a moderate surface migration ability to reach the interface and perform their function, while also maintaining sufficient compatibility to avoid clearcoat turbidity, haze, cratering, precipitation, or reduced recoatability.

6.3 Compatibility and Migration Explain Performance Differences Among Products

Although different products may all be called polyether-modified polysiloxanes, they may have different functional focuses. The application performance of polyether-modified polysiloxanes is jointly determined by their surface migration ability, system compatibility, and the film-forming process of the coating.

Product Structural Tendency	Possible Performance Characteristics	Issues to Consider
Stronger polysiloxane character	More obvious smoothness, low friction, and surface tension regulation	Compatibility, recoatability, haze risk
Higher polyether proportion	Better compatibility and stronger waterborne-system adaptability	Surface effect may be relatively mild
Higher EO content	Increased hydrophilicity; suitable for some waterborne systems	Foaming tendency must be verified in the specific system
Higher PO content	Increased hydrophobicity; may reduce foam-stabilizing tendency	Water dispersibility and compatibility need to be evaluated
Reactive end groups	Help improve migration resistance and durability of surface effects	Must match the curing system
Highly compatible structure	More suitable for clearcoats and high-gloss systems	Smoothness and migration effects may be weaker

7. How the Synthesis Process Supports Structural Design

One common preparation route for polyether-modified polysiloxanes is hydrosilylation between hydrogen-containing polysiloxanes and allyl polyethers, through which polyether segments are incorporated into the siloxane backbone. In the literature, polyether-modified polysiloxanes can be prepared from hydrogen-containing silicone oils and allyl polyethers under a platinum-catalyzed system.

For coating applications, the significance of the synthesis process lies in the fact that it determines the molecular structure. The main structural design factors affecting final performance include:

① Structure of hydrogen-containing polysiloxane: Determines available grafting sites, the length of the siloxane segment, and the contribution of low surface energy.

② Structure of allyl polyether: Determines the EO/PO ratio, polyether molecular weight, hydrophilic/hydrophobic balance, and system compatibility.

③ Grafting density: Affects the number of polyether segments, thereby influencing compatibility, migration, and surface activity.

④ End-group design: Affects whether the molecule has reactivity, migration resistance, and post-processing adaptability.

⑤ Molecular weight control: Affects surface migration speed, durability of tactile feel, clearcoat transparency, and formulation stability.

8. Basic Considerations in Formulation Applications

In practical formulations, the use of polyether-modified polysiloxanes should take into account leveling, tactile feel, compatibility, foam, recoatability, and post-processing performance at the same time. The following considerations can serve as basic guidelines for small-scale screening:

Application Objective	Key Properties to Focus On	Suggested Evaluation Methods
Improve leveling	Wet-film spreading, surface tension difference control, orange peel improvement	Leveling test panel, spray appearance, cratering observation
Improve substrate wetting	Contact angle reduction, spreading ability, edge pullback improvement	Contact angle, substrate spreading, edge pullback observation
Improve tactile feel	Smoothness, fineness, low friction, anti-blocking	Manual tactile evaluation, coefficient of friction, anti-blocking test
Use in waterborne systems	Water dispersibility, low foaming, risk of pinholes and cratering	Foaming test, defoaming speed, pinhole observation
Use in clearcoat systems	Compatibility, transparency, gloss retention	Haze, gloss, storage stability
Use in multi-layer coating systems	Recoatability, intercoat adhesion, influence of low-energy surface layer	Recoat appearance, tape test, intercoat adhesion

Where conditions allow, additional tests may include dynamic surface tension, contact angle change over time, COF, haze/gloss, and cross-cut adhesion or pull-off adhesion after recoating. Dosage gradients should also be set during use. Too low a dosage may be insufficient; an appropriate dosage can improve leveling and tactile feel; excessive dosage may lead to cratering, haze, excessive slipperiness, increased foam, or reduced recoatability.

9. Future Development Directions

9.1 Low-Foam Polyether-Modified Polysiloxanes

Waterborne coatings need to balance wetting, leveling, and foam control. Future products will place greater emphasis on reducing foam stabilization and pinhole risk while improving wetting and leveling.

9.2 Highly Compatible Polyether-Modified Polysiloxanes

Clearcoats, high-gloss coatings, UV coatings, and high-solids systems have high requirements for transparency, gloss, and appearance. Highly compatible products help reduce the risk of haze, cratering, and gloss loss.

9.3 Low-Migration or Reactive Polyether-Modified Polysiloxanes

To improve wipe resistance, recoatability, post-processing adaptability, and long-term tactile stability, low-migration or curing-reactive structures will receive increasing attention.

9.4 Tactile-Feel-Customized Polyether-Modified Polysiloxanes

The tactile feel of a coating film is not only smoothness; it also includes dryness, softness, fineness, anti-blocking, wear resistance, and other comprehensive sensory properties. Future products will pay more attention to differentiated tactile design for different application scenarios.

9.5 Multifunctional Surface Control Additives

Polyether-modified polysiloxanes will continue to evolve from single-function leveling or single-function smoothness additives toward comprehensive surface control additives that combine wetting, leveling, smoothness, anti-blocking, and application stability.

10. Reagents and Reference Materials Related to Structural Research, Synthesis, and Formulation Screening of Polyether-Modified Polysiloxanes

Note: The following products are mainly intended for structural research, synthesis route development, mechanism verification, and formulation comparison related to polyether-modified polysiloxanes. They are not coating leveling or tactile-feel additives that can be directly added to formulations. Practical application should be evaluated in combination with SDS information, regulatory status, system compatibility, and small-scale formulation testing.

Table 1. Siloxane Backbones, Silicone Oil References, and Hydrogen-Containing Siloxane Intermediates

Category	CAS No.	Aladdin Item No.	Name	Specification or Purity	Product Features and Applications
Vinyl-terminated siloxane polymer	68083-19-2	P433303	Poly(dimethylsiloxane), vinyl terminated	Viscosity 850–1150 cSt at 25°C	Used for reactive organosilicone systems, hydrosilylation model systems, and research on low-surface-energy siloxane segments; can be used to investigate the influence of vinyl-terminated structures on surface enrichment, smoothness, and low-friction performance of coating films
Non-reactive silicone oil reference	63148-62-9	S433164	Silicone oil	Viscosity 5 cSt at 25°C	Low-viscosity silicone oil reference; used to compare conventional silicone oil with polyether-modified polysiloxanes in terms of leveling, smoothness, compatibility, and cratering risk
Hydroxy-terminated siloxane polymer	70131-67-8	P433356	Poly(dimethylsiloxane), hydroxy terminated (PDMS)	Viscosity 3500 cSt	Used for hydroxy-terminated siloxane modification, reactive surface additives, and research on coating surface tactile feel; can be used to evaluate the influence of siloxane segments on dry-film smoothness, anti-blocking, and tactile properties
Hydrogen-containing siloxane intermediate	63148-57-2	P477954	Poly(methylhydrosiloxane), trimethylsilyl terminated	Viscosity: ~3 cSt	A commonly used hydrogen-containing siloxane intermediate for polyether-modified polysiloxanes; can undergo hydrosilylation with allyl polyethers to construct organosilicone surface additives containing polyether side chains
Non-reactive high-molecular-weight siloxane reference	9016-00-6	P195721	Polydimethylsiloxane, trimethylsiloxy terminated	Average M.W. 115,000	High-molecular-weight silicone oil reference; used to study the influence of siloxane chain length on surface enrichment, smooth tactile feel, migration behavior, and compatibility risk
Siloxane chain-control raw material	107-46-0	H105443	Hexamethyldisiloxane (HMDSO)	≥99%	Can be used as a siloxane chain-control material and low-molecular-weight siloxane reference; used to study the influence of low-surface-energy siloxane structures on wetting, spreading, and surface smoothness
Hydrogen-containing trisiloxane intermediate	1873-88-7	H138408	1,1,1,3,5,5,5-Heptamethyltrisiloxane	≥98% (GC)	A trisiloxane intermediate containing Si–H bonds; can be used to prepare trisiloxane-type polyether-modified surfactants and is commonly used in studies of wetting, spreading, and low surface tension
Cyclic siloxane monomer	556-67-2	O160041	Octamethylcyclotetrasiloxane (D4)	≥98% (GC)	A basic monomer for siloxane polymer synthesis; used to prepare siloxane backbones with different chain lengths and to study the influence of siloxane segment length on leveling, smoothness, and compatibility
Hydrogen-containing disiloxane intermediate	3277-26-7	T110097	1,1,3,3-Tetramethyldisiloxane	≥98%	A small-molecule intermediate containing Si–H bonds; can be used in hydrosilylation model studies to help evaluate the reactivity of Si–H structures with allyl polyethers and the construction of functionalized siloxanes

Table 2. Polyether Segments, Alkylene Oxides, and Allyl-Functionalized Raw Materials

Category	CAS No.	Aladdin Item No.	Name	Specification or Purity	Product Features and Applications
Basic material for polyether segments	25322-68-3	P615493	Polyethylene oxide	Viscosity 65–115 cps	Hydrophilic polyether segment model material; used to study the influence of polyether segments on waterborne compatibility, substrate wetting, leveling, and foaming tendency
Basic material for polyether segments	25322-69-4	P103212	Polypropylene glycol (PPG)	Average molecular weight 4000	A relatively more hydrophobic polyether segment model material; used to study the influence of polyether composition on compatibility, migration, surface activity, and low-foam performance
Allyl polyether intermediate	27274-31-3	A303301	Allyloxy polyoxyethylene ether	Molecular weight 2400	A key intermediate for the synthesis of polyether-modified polysiloxanes; can undergo hydrosilylation with hydrogen-containing siloxanes to introduce polyether segments, thereby regulating compatibility, wetting, and leveling performance
Alkylene oxide monomer	75-56-9	P109311	Propylene oxide	≥99.5% (GC)	Raw material for preparing polypropylene glycol and propylene oxide-type polyether segments; used in polyether structural design studies involving hydrophobicity, low-foam tendency, and compatibility adjustment
Alkylene oxide monomer	75-21-8	E105779	Ethylene oxide	≥99.5%	Raw material for preparing polyethylene oxide and hydrophilic polyether segments; used in polyether structural design studies involving hydrophilicity, waterborne-system adaptability, and substrate wetting
Allyl-functionalized monomer	106-92-3	A106314	Allyl glycidyl ether (AGE)	≥99%	A functionalized monomer containing both allyl and epoxy groups; used to prepare functionalized siloxane intermediates and to study end-group reactivity, adhesion, crosslinking, and durability of surface effects

Table 3. Hydrosilylation Catalysts

Category	CAS No.	Aladdin Item No.	Name	Specification or Purity	Product Features and Applications
Platinum catalyst	16941-12-1	H135562	Chloroplatinic acid hydrate	PrimorTrace™, ≥99.995% metals basis	Catalyst for hydrosilylation reactions; used in studies of reactions between hydrogen-containing siloxanes and allyl polyethers, supporting the construction of polyether-modified polysiloxane structures
Platinum catalyst	18497-13-7	C110574	Chloroplatinic acid hexahydrate	AR, Pt ≥37.5%	Commonly used hydrosilylation catalyst; used in synthesis experiments of polyether-modified polysiloxanes, reaction activity studies, and screening of structural modification conditions
Platinum complex catalyst	68478-92-2	K131672	Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex	0.05 M in poly(dimethylsiloxane), vinyl terminated	Platinum complex catalyst for hydrosilylation reactions; used in addition reactions between hydrogen-containing siloxanes and allyl polyethers, suitable for research on functionalized polysiloxanes and reactive surface additives

Note: The above are representative Aladdin products. More product specifications can be searched on the Aladdin official website by “product name/CAS/item number.”

References

[1] BYK. How to Prevent Cratering.

[2] BYK. The Chemical Structure of Polysiloxanes.

[3] PCI Magazine. No More Ups and Downs: Mastering Leveling of Waterborne Coatings.

[4] Evonik. Surface Control Additives for Industrial and Transportation Coatings.

[5] NOF America. Allylpolyethers for Polyether-Modified Silicones.

[6] Chen, et al. Study on Synthesis of Polyether-Modified Polysiloxane. Advanced Materials Research, 1004–1005, 277–280.

[7] Fu K., Xu M., Zhong R., Yang Z., Zhou A. Preparation, Characterization and Application of Polyether and Long-Chain Alkyl Co-Modified Polydimethylsiloxane. Journal of Polymer Research, 2019.

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