Chemical modification of styrene–butadiene–styrene (SBS) rubber by reactive grafting with maleic anhydride

A procedure to increase the adhesion of block styrene-butadiene-styrene (SBS) rubber consisting of the reactive grafting with maleic anhydride (MA) in the presence of an organic peroxide radical initiator is proposed. The influence of the reactive grafting on the surface properties of SBS has been studied with special emphasis on the improvement of the adhesion to polyurethane adhesive. The grafting of MA onto SBS was carried out in the presence of different concentrations of 2,5-dimethyl-2,5-di(tertbutyl peroxy) hexane (DBPH) as initiator to generate oxygen radicals by thermal decomposition, which induce the grafting reaction. The modification process was performed in the molten state using a Brabender mixer to premix the reactants and a hot press to initiate the functionalizing reaction. ATR-IR and XPS spectroscopies were employed to verify the grafting of MA on SBS. The changes in wettability on the modified SBS rubber were determined by contact angle measurements. Adhesion properties were evaluated from T-peel tests of SBS rubber/polyurethane adhesive joints. Reasonable extents of MA grafting on SBS were obtained (evidenced by the presence of a weak carbonyl vibration at 1700 cm^-1 in the ATR-IR spectra and by the carbon- oxygen band at a binding energy of 287.0 eV in the XPS spectra). The higher the DBPH amount, the higher the MA amount grafted onto the SBS surface. The maximum grafting level was obtained using 2 wt% MA. Grafted species seemed to be mainly concentrated on the surface of the SBS-molded sheets. The wettability of the modified rubber increased with respect to the original polymer, new carbon-oxygen moieties were created and the C/O ratio increased. A noticeable enhancement in peel strength values was observed, which was ascribed to the creation of interfacial interactions between the polyurethane and the SBS rubber surfaces.     

Water-based chlorination treatment of SBS rubber soles to improve their adhesion to waterborne polyurethane adhesives in the footwear industry

Solutions of trichloroisocyanuric acid (TCI) in different organic solvents are commonly employed in the footwear industry to improve the adhesion of SBS (styrene-butadiene-styrene) rubber soles to polyurethane adhesive. To avoid the use of organic solvents in the chlorinating solutions, several water-based chlorinating treatments were investigated in this study: (i) inorganic chlorine compounds (HCl-acidified sodium hypochlorite solution; free active chlorine (FAC) = 47.8 g/l); (ii) organic chlorine donors (aqueous solution of 3 wt% TCI/H₂O, and ethanol solutions of 3 wt% HD (1,3-dichloro-5,5-dimethylhydantoine), or NCS (N-chlorosuccinimide); (iii) organic chlorine donor salts (aqueous solutions containing 3 wt% DCI (sodium dichloro isocyanurate), CB (chloramine B, N-chloro-sodium-phenylsulphenamide), or CT (chloramine T, N-chloro-sodium-p-toluenesulphenamide). The surface modifications produced by treatment of SBS rubber with the aqueous chlorinating agents were compared with those obtained by using the current solvent-based chlorinating treatment (3 wt% TCI/MEK). The FAC concentration and the chlorine stability in the solutions were determined by iodine titration, and the SBS rubber surface pH was determined with a flat pH probe. The surface modifications on the SBS rubber were analyzed by ATR-IR spectroscopy, XPS, contact-angle measurements and SEM. The adhesion properties were evaluated by T-peel strength tests on treated SBS rubber/waterborne polyurethane adhesive/roughened leather joints. The failed surfaces obtained after peel tests were analyzed by ATR-IR spectroscopy to precisely assess the locus of failure of the adhesive joints. The nature of the modifications produced on the SBS rubber surface depended on the chlorinating system used, the SBS rubber surface pH value, and the free active chlorine concentration of the chlorinating solution. The most effective chlorinating agents were TCI/H₂O and HD/EtOH, but they were not stable over time due to quick chlorine evolution. Treatment with NaClO/HCl and DCI/H₂O provided acceptable adhesive strength values although there was fast chlorine evolution in the NaClO/HCl solution; the free active chlorine concentration in the DCI/H₂O solution was stable for at least 4 days after preparation. Finally, the treatment with NCS/EtOH, CB/H₂O and CT/H₂O did not chemically modify the SBS rubber surface, so the adhesion to polyurethane adhesive was not improved.     

UV-Ozone Surface Treatment of SBS Rubbers Containing Fillers: Influence of the Filler Nature on the Extent of Surface Modification and Adhesion

SBS rubbers containing different loadings of calcium carbonate and/or silica fillers were surface treated with UV-ozone to improve their adhesion to polyurethane adhesive. The surface modifications produced on the treated filled SBS rubbers have been analyzed by contact angle measurements, ATR-IR spectroscopy, XPS and SEM. The adhesion properties have been evaluated by T-peel strength tests on treated filled SBS rubber/polyurethane adhesive/leather joints. The UV-ozone treatment improved the wettability of all rubber surfaces, and chemical (oxidation) and morphological modifications (roughness, ablation, surface melting) were produced. The increase in the time of UV-ozone treatment to 30 min led to surface cleaning (removal of silicon-based moieties) due to ablation and/or melting of rubber layers and also incorporation of more oxidized moieties was produced. Although chemical modifications were produced earlier in an unfilled rubber for short time of treatment with UV-ozone, they were more noticeable in filled rubbers for extended length of treatment, mainly for S6S and S6T rubbers containing silica filler. The oxidation process seemed to be inhibited for S6C and S6T rubbers (containing calcium carbonate filler). On the other hand, the S6S rubber containing silica filler and the lowest filler loading showed the higher extent of modification as a consequence of the UV-ozone treatment. The UV-ozone increased the joint strength in all joints, more noticeably in the rubbers containing silica filler, in agreement with the greater extents of chemical and morphological modifications produced by the treatment in these rubbers. Finally, the nature and content of fillers determined the extent of surface modification and adhesion of SBS rubber treated with UV-ozone.     

Surface Characterization of Vulcanized Rubber Treated with Sulfuric Acid and its Adhesion to Polyurethane Adhesive

Modifications produced on a vulcanized styrene –butadiene rubber surface by treatment with sulfuric acid were studied and several experimental variables were considered.

The treatment of R1 rubber with sulfuric acid produced a noticeable decrease in contact angle which was mainly ascribed to an increase in surface energy due to the formation of sulfonic acid moieties and C?O bonds, and the removal of zinc stearate. The rubber surface swelled and became brittle as a result of the treatment, and when flexed microcracks were created. A rubber surface layer modification was produced with a consequent decrease in tensile strength and elongation-at-break values. The treatment enhanced the T-peel strength of R1 rubber/polyurethane adhesive joints and the locus of failure was cohesive in the rubber.

The optimum immersion time in H₂SO₄ solution was less than 1 min., and the reaction time in air was not found to be critical; the neutralization with ammonium hydroxide and the high concentration of the sulfuric acid (95 wt%) were essential to produce adequate effectiveness of the treatment.     

Influence of Additives in Adhesion of UV Radiation Surface-Treated SBS Rubber

In this study, the effect of additives (oils, lubricants) included in the formulations of different block styrene-butadiene-styrene (SBS) rubbers on the effectiveness of the ultraviolet (UV) radiation treatment to improve adhesion to polyurethane adhesive was analyzed. The modifications on the UV-treated rubber surfaces for different lengths of treatment have been characterized by contact-angle measurements (ethylene glycol, 25°C), Attenuated Total Reflectance-Infrared (ATR-IR) spectroscopy, X-ray Photoelectron Spectroscopy (XPS), and Scanning Electron Microscopy (SEM). The adhesion properties have been evaluated from T-peel strengths of treated rubber/polyurethane adhesive/leather joints. The UV-radiation treatment on all rubber surfaces produced an increase in wettability, carbon-oxygen polar moieties, and ablation. The oxidation degree produced on the rubber surface treated with UV radiation was less when oils and lubricants were included in the formulation, likely due to competition of the oxidation process with the migration of low-molecular-weight additives to the rubber surface. On the SBS2 rubber surface (rubber containing carbon black and calcium carbonate fillers), the migration of oils and lubricants was also produced during the UV-radiation treatment, but a decrease in adhesion occured likely due to the lower tensile strength and higher extent of oxidation produced by the UV radiation treatment.     

Influence of Additives in Adhesion of UV Radiation Surface-Treated SBS Rubber

In this study, the effect of additives (oils, lubricants) included in the formulations of different block styrene–butadiene–styrene (SBS) rubbers on the effectiveness of the ultraviolet (UV) radiation treatment to improve adhesion to polyurethane adhesive was analyzed. The modifications on the UV-treated rubber surfaces for different lengths of treatment have been characterized by contact-angle measurements (ethylene glycol, 25°C), Attenuated Total Reflectance-Infrared (ATR-IR) spectroscopy, X-ray Photoelectron Spectroscopy (XPS), and Scanning Electron Microscopy (SEM). The adhesion properties have been evaluated from T-peel strengths of treated rubber/polyurethane adhesive/leather joints. The UV-radiation treatment on all rubber surfaces produced an increase in wettability, carbon–oxygen polar moieties, and ablation. The oxidation degree produced on the rubber surface treated with UV radiation was less when oils and lubricants were included in the formulation, likely due to competition of the oxidation process with the migration of low-molecular-weight additives to the rubber surface. On the SBS2 rubber surface (rubber containing carbon black and calcium carbonate fillers), the migration of oils and lubricants was also produced during the UV-radiation treatment, but a decrease in adhesion occured likely due to the lower tensile strength and higher extent of oxidation produced by the UV radiation treatment.     

Polyester Polyol-Based Polyurethane Adhesive; Effect of Treatment on Rubber Surface

Polyester polyols were synthesized using vegetable oil fatty acids having different characteristics (mainly in terms of hydroxyl functionality) and epoxy resin, using triethylamine as a catalyst. Polyols were characterized by the FTIR spectroscopy. Polyurethane adhesives were synthesized from it and used in bonding rubber. Treatment of sulphuric acid on the non-polar styrene butadiene rubber (SBR) surface was studied for the bond strength improvement via an increase in wettability of the rubber surface. Wettability was found by measuring the contact angle using Goniometer. Bond strength was evaluated by a 180° T-peel test. The surface modification and mode of bond failure were studied by Scanning Electron Microscopy (SEM). The synthesized polyurethane adhesives were compared with the commercial adhesive.     

Treatment with Ar–O2 low-pressure plasma of vulcanized rubber sole containing noticeable amount of processing oils for improving adhesion to upper in shoe industry

Vulcanized rubber (L3 rubber) containing intentionally noticeable excess of processing oils in its formulation was treated with Argon–Oxygen (Ar–O₂) (2:1, vol/vol) low-pressure (LP) plasma for achieving a satisfactory level of adhesion to waterborne polyurethane adhesive. The effectiveness of the Ar–O₂ LP plasma treatment of L3 rubber depended on both the configuration of the plasma chamber shelves and the treatment time. Surface modifications were assessed by attenuated total reflectance-IR and X-ray photoelectron spectroscopy, contact angle measurements, and scanning electron microscopy. Ar–O₂ LP plasma treatment in direct configuration provided the most effective surface modification of the L3 rubber, and the increase in the treatment time improved the extent of the surface modifications. However, even important surface modifications were produced by Ar–O₂ LP plasma treatment, adhesion of treated L3 rubber was not improved due to the creation of weak boundary layer at the polyurethane–rubber interface after joint formation. Heating at 80 °C for 12 h of the as-received L3 rubber prior to Ar–O₂ LP plasma treatment enhanced the extent of the surface modifications, and improved adhesion was obtained for Ar–O₂ LP plasma treatment times higher than 600 s.     

Influence of calcium carbonate added to the SBS rubber formulation on the surface modifications produced by halogenation

To improve the adhesion properties of styrene–butadiene–styrene (SBS) rubber sole to polyurethane adhesive, surface treatments are required, of which halogenation with trichloroisocyanuric acid (TCI) solutions in organic solvents is the most commonly used treatment in the footwear industry. Calcium carbonate filler is commonly added to improve the mechanical properties and to reduce shining of SBS rubber formulations. The influence of the filler on the effectiveness of surface chlorination of SBS rubber had not been considered in the existing literature. Therefore, 10 wt% calcium carbonate filler was added to the SBS rubber formulation and the surface modifications and adhesion properties produced by treatment with TCI solutions were investigated. The resulting surface modifications and adhesion were compared to those obtained in unfilled SBS rubber. It is shown that the treatment with TCI solutions was less effective in the calcium-carbonate-filled SBS rubber and a lower peel strength to polyurethane adhesive was obtained; however, a cohesive failure in the rubber was always obtained.     

Ultrasonic cleaning of SBR rubber to improve the performance of subsequent plasma torch treatment

Paraffin wax and other moieties in sulfur vulcanized styrene-butadiene rubber formulations may migrate to the surface, reducing the adhesive strength in joints produced with polyurethane adhesive. In this study, with the aim to remove paraffin wax and other anti-adhesion moieties on the rubber surface to improve adhesion, prior to plasma torch treatment, a methyl ethyl ketone (MEK) cleaning in an ultrasonic bath has been carried out. The surface modifications produced on the rubber surface have been analyzed by contact angle measurements, ATR-IR spectroscopy, XPS and SEM. The adhesion properties have been evaluated by T-peel strength of treated rubber/polyurethane adhesive joints. Ultrasonic cleaning in MEK resulted in partial removal of paraffin wax on the rubber surface and, thus, lower contact angle values, decreased relative intensity of the infrared bands due to hydrocarbon moieties and lower percentage of carbon assessed from XPS spectroscopy were obtained. The ultrasonic cleaning in MEK of the rubber increased the effectiveness of the atmospheric pressure plasma torch treatment, and surface oxidation was produced. However, the oxidation degree decreased with time after plasma torch treatment, likely due to ageing of the surface treated rubber.     

UV treatment of synthetic styrene-butadiene-styrene rubber

The effectiveness of the treatment with ultraviolet light (UV) on several polymeric surfaces has previously been established. In this study, a low pressure mercury vapour lamp was used as a source of UV radiation for the surface treatment of a difficult-to-bond block styrenebutadiene-styrene rubber (S6), the treatment time ranging from 10 s to 30 min. The UV-treated S6 rubber surfaces were characterized by contact angle measurements (ethylene glycol, 25°C), ATR-IR spectroscopy, XPS, Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM). T-peel tests on UV-treated S6 rubber/polyurethane (PU) adhesive/ leather joints (before and after ageing) were carried out to quantify adhesion strengths. The UV treatment of S6 rubber produced improved wettability, the formation of C—O, C=O and COO^- moieties, and ablation (removal of a thin rubber layer from the surface). The extent of these modifications increased with increasing treatment time. The extended UV treatment produced greater surface modifications, as well as the incorporation of nitrogen moieties at the surface. Furthermore, noticeable ablation of S6 rubber surface occurred. Peel strength values increased with increased treatment time of UV treatment of S6 rubber. Also, with increasing treatment time, the adhesive joints showed different loci of failure: adhesional failure for the as-received and 2 min-UV treated S6 rubber/polyurethane adhesive/leather joints changed to mixed failure (cohesive in the treated S6 rubber + adhesional failure) for the 30 min-UV treated S6 rubber/polyurethane adhesive/leather joint.     

Improved adhesion of poly(tetrafluoroethylene) by NH3-plasma treatment

—Surface modification of poly(tetrafluor oethylene) (PTFE) by NH₃-plasma treatment was investigated by means of contact angle measurement, XPS, and ATR FT/IR spectroscopy. The modified surfaces were adhesively bonded to nitril rubber. The NH₃-plasma irradiation made PTFE surfaces hydrophilic. The contact angle of water on the modified PTFE surface was 16 deg, and the surface energy was 62-63 mJ/m². The NH₃-plasma irradiation improved adhesion between PTFE and nitril rubber using a phenol-type adhesive. The peel strength of the joints reached 8.1 × 10³ N/m. Carbonyl and amido groups were created on PTFE surfaces by the NH₃-plasma irradiation. The mechanism of the improvement of adhesion by the NH₃-plasma irradiation is discussed.     

Chlorination of SBS rubbers with different styrene contents using trichloro-isocyanuric acid

In order to improve their adhesion to polyurethane adhesives, three unvulcanized block styrene-butadiene-styrene (SBS) rubbers with styrene contents between 33% and 55% were surface-treated with solutions of 2 wt% trichloro-isocyanuric acid (TCI) in ethyl acetate. The joint strength was estimated using T-peel tests and the failed surfaces were analyzed to assess the locus of failure. The failed surfaces were analyzed using ATR-IR spectroscopy, contact angle measurements, XPS, and SEM. An unexpected trend in the joint strength was obtained because the locus of failure depended on both the styrene content and the mechanical properties of each SBS rubber. A mixed mode of failure was obtained in joints produced with S 1 rubber (33 wt% styrene content), whereas failure in the chlorinated layer was observed with S3 rubber (55 wt% styrene content); cohesive failure in the adhesive was found for the joints produced with S2 rubber (44 wt% styrene content).     

Weak boundary layers on vulcanized styrene–butadiene rubber treated with sulfuric acid

A synthetic vulcanized styrene-butadiene rubber (R2) was used in this study. The presence of paraffin wax and zinc stearate in the rubber composition prevented the adhesion of R2 rubber to solvent-based polyester-urethane adhesive. To increase the adhesion properties of R2 rubber, a surface treatment with sulfuric acid (cyclization) was applied, and the length of the immersion in sulfuric acid and the time between the immersion time and the neutralization were varied. The treated R2 rubber surfaces were characterized using ATR-IR spectroscopy, contact angle measurements (water, ethanediol), and scanning electron microscopy (SEM). The mechanical properties of the treated rubber were obtained from stress-strain experiments. The joint strength was obtained from the T-peel test on treated R2 rubber/polyurethane adhesive joints. Due to the penetration of the sulfuric acid into the R2 rubber bulk, the mechanical properties decreased. The treatment with sulfuric acid produced several chemical modifications on the rubber surface: sulfonation of the butadiene and the creation of C C and C O bonds. Furthermore, the surface treatment of the R2 rubber with sulfuric acid removes paraffin wax from the rubber surface, which had a beneficial effect on adhesion to the polyurethane adhesive. To remove the wax layer, the surface was wiped with petroleum ether solvent after treating the R2 rubber with sulfuric acid. However, in some experiments a progressive migration of wax from the R2 rubber bulk to the surface with time happened. The migration of wax was prevented by increasing the immersion time in H₂SO₄ by more than 5 min.     

Synthesis and application of dual-curable PVB based adhesive formulations for cord/rubber applications

In this research, formaldehyde-free dual-curable adhesive formulations containing polyvinyl butyral (PVB) were prepared with the reaction of 2,4-toluene diisocyanate (TDI) and 2-hydroxyethyl methacrylate (HEMA) and then applied on cord fabrics upon adhere onto the rubber surfaces. The effects of PVB ratio on peel strength value between the cord and rubber were studied. The structure of the oligomer was characterized by FTIR and ¹H NMR spectroscopy. Thermal properties of coated and UV-cured fabrics were investigated by TGA and DSC. Surface wettability properties of the fabrics after coating were observed with contact angle measurement. The peel strength between cord/rubber surfaces was determined by T-peel test after thermal curing stage under heat and pressure. Results showed that peel strength value increases with increasing PVB amount in the formulation. The highest peel strength of 94.7 N/cm was observed when 5% PVB was included in the formulation. This study leads to a new type of promising adhesives with superior peel strength for cord/rubber applications as it is being a totally formaldehyde-free process.     

Chlorination of vulcanized styrene-butadiene rubber using solutions of trichloroisocyanuric acid in different solvents

The chlorination of vulcanized styrene-butadiene rubbers (SBRs) with trichloroisocyanuric acid (TCI) has been studied. The solvent used to apply the TCI chlorinating solutions on the rubber plays an important role in the effectiveness of the treatment since the solvent determined the degree of penetration of TCI into the rubber and also different chlorinating species were produced depending on the nature of the solvent. Surface modifications produced on a synthetic sulfur-vulcanized SBR using TCI solutions in ethyl acetate (EA), methyl ethyl ketone (MEK), and EA + MEK mixtures have been compared. Furthermore, the effects of a solvent wipe with EA or MEK prior to the chlorination process were also considered. Surface modifications produced by the treatments were analyzed using ATR-IR spectroscopy, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Adhesion was obtained from the T-peel strength of treated rubber/polyurethane adhesive joints. TCI/MEK solutions produced a higher degree of surface modification than TCI/EA solutions, but TCI/EA solutions were more effective in removing zinc stearate from the rubber surface. When high TCI percentages (5-7 wt%) in EA solutions were used, a weak boundary layer (WBL) was created on the rubber surface as a consequence of the deposition of an excess of chlorinating agent on the rubber surface and of by-products (cyanuric and/or isocyanuric acid). The formation of the WBL led to a lack of adhesion in the rubber towards the polyurethane adhesive. When MEK was used as a solvent for TCI, this WBL was not produced on the rubber surface, and thus adhesion was considerably higher even when high concentrations of TCI/MEK were used. Similar effects were produced using EA + MEK mixtures as the solvent for TCI. The wiping of the rubber surface with MEK prior to the chlorination treatment led to good adhesion, irrespective of the percentage of TCI and the solvent used in the chlorinating solution.     

Adhesion of polyurethane to surface-modified steel

A number of procedures for cleaning the surface of steel have been tested. By washing with different solvents, ultrasonic solvent cleaning, sand-blasting or grinding, and desorption of organic contamination in an oxygen plasma, the degree of cleaning increased successively, as detected by XPS. The adhesion of polyurethane to steel measured in terms of the tensile shear strength could even approach the critical shear strength of the polyurethane itself. The highest adhesion strengths were obtained by using a combination of cleaning methods, including oxygen plasma treatment. A composite of optimally pretreated steel, a phenolic resin primer, and a polyurethane showed fracture far from the interface to steel in the boundary layer comprised of polyurethane and primer. Strong interactions between the phenolic resin and steel were indicated by the shift of the Fe 2P_3/2 peak to a binding energy of 712.7 eV. The strong adhesion-promoting effect of the hydrogen plasma pretreatment was produced by another effect. With the carbon incorporated in the steel, a thin adhesion-promoting plasma polymer layer was formed. Tests with model primers, instead of the phenolic resin and chemical modification of the phenolic resin, showed that the interaction between the phenolic resin primer and the polyurethane involved the phenolic hydroxyl groups.     

A study of the environmentally friendly polycarbonate surface etching system containing H2SO4–MnO2 colloid

In this paper, an environmentally friendly etching system containing H₂SO₄–MnO₂ colloid was used to investigate surface etching for polycarbonate (PC). The effects of swelling condition, H₂SO₄ concentrations and etching times on surface topography and surface roughness were studied. With the etching treatment, the surface average roughness (R _a) of PC substrates increased from 3 to 76?nm and the adhesion strength between the electroless copper and PC substrate reached 1.08 KN/m. Surface chemistry of PC substrates was investigated by the contact angle measurement and X-ray photoelectron spectroscopy spectra (XPS). After the etching treatment, PC surface became hydrophilic and the contact angle decreased from 95.2 to 39.6^o. XPS analyses indicate that hydroxyl and carboxyl groups are formed on the PC surface as a result of the etching treatment, which improve the adhesion strength between PC substrate and electroless copper film.     

Effect of rubber compounding agent on adhesion strength between rubber and heat-assisted plasma-treated polytetrafluoroethylene (PTFE)

Although heat-assisted plasma treatment enables drastic improvement of the adhesion property of polytetrafluoroethylene (PTFE), plasma-treated PTFE does not strongly adhere to any adherend. To clarify which rubber compounding agents positively affect the adhesion strength of a plasma-treated PTFE/rubber assembly, six types of unvulcanised rubbers were prepared and thermally compressed to a plasma-treated PTFE sheet. Thus, it was found that SiO₂ addition to rubber drastically increased the adhesion strength of a plasma-treated PTFE/rubber assembly and cohesion failure of rubber occurred with large fractions of SiO₂ although no adhesives were used. To confirm the reaction between plasma-treated PTFE and SiO₂ powder, X-ray photoelectron spectroscopy (XPS) measurements were performed for the thermally compressed SiO₂/PTFE assembly after repeated washing. The XPS results indicated that hydrophilic SiO₂ powder strongly adhered to the plasma-treated PTFE, whereas hydrophobic SiO₂ powder did not adhere to the PTFE. In this paper, a model was proposed for a possible mechanism of strong adhesion of a PTFE/rubber assembly through both hydrogen and covalent bonds between silanol groups of the SiO₂ powder surface in the rubber and hydroxyl or carboxyl groups on the plasma-treated PTFE.     

A novel alkoxysilane‐modified high solids hydroxyl acrylic polyurethane: Preparation and surface properties

Alkoxysilane‐modified high solids hydroxyl acrylic polyurethane was prepared by solution polymerization. Its structure, surface, and thermal properties were investigated by ¹H NMR, device of contact angle, thermo gravimetric analysis (TGA), atomic force microscopy (AFM), and X‐ray photoelectron spectroscopy (XPS). Research showed that alkoxysilane modified high solids hydroxyl acrylic polyurethane has superior properties that can be used for automotive paints. The contents of silicone in the alkoxysilane‐modified high solids hydroxyl acrylic polyurethane were 1.25, 1.5, 2, and 2.5 wt %. In this study, γ‐methacryloxypropyltrimethoxysilane (MPTS) was chosen as the modifier. Results showed that the contact angles of water and surface roughness on the film of MPTS modified high solids hydroxyl acrylic polyurethane increased, and thermal stability of the film at high temperatures improved with the increasing of the silicone content in the resins. MPTS modified high solids hydroxyl acrylic polyurethane with 2.5 wt % silicone content had better water resistance, better acid resistance, higher hardness, and excellent weatherability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1866–1871, 2006