ABA-type block copolymers containing poly(dimethylsiloxane) and ketonic resins

Block copolymer containing segments of poly(dimethylsiloxane) (PDMS) and ketonic resins were synthesized. Dihydroxy-terminated PDMS were reacted with the isophorone diisocyanate (IPDI) to obtain the diisocyanate-terminated PDMSs (urethane). These urethanes were reacted with reactive hydroxyl groups in the cyclohexanone–formaldehyde, acetophenone–formaldehyde, and in situ melamine-modified cyclohexanone–formaldehyde resins. Formation of block copolymers was illustrated by several characterization methods, such as chemical and spectroscopic analysis and gel permeation chromatography. The solubilities of the block copolymers were determined, and their surface properties were investigated by contact angle measurements. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 643–648, 1998     

Influence of semi‐crystalline poly(ε‐caprolactone) and non‐crystalline polylactide blocks on the thermal properties of polydimethylsiloxane‐based block copolymers

Poly(A)‐block‐poly(B), poly(A)‐block‐poly(B)‐block‐poly(A) and B(A)₂ block copolymers were prepared through coordinated anionic ring‐opening polymerization of ε‐caprolactone (CL) and lactic acid (LA) using hydroxy‐terminated polydimethylsiloxane (PDMS) as initiator. A wide range of well‐defined combinations of PDMS‐block‐PCL and PDMS‐block‐PLA diblock copolymers, PCL‐block‐PDMS‐block‐PCL and PLA‐block‐PDMS‐block‐PLA triblock copolymers and star‐PDMS(PCL)₂ copolymers were thus obtained. The number‐average molar masses and the structure of the synthesized block copolymers were identified using various analytical techniques. The thermal properties of these copolymers were established using differential scanning calorimetry. Considering PDMS‐block‐PCL copolymers, the results demonstrate the complex effect of polymer architecture and PCL block length on the ability of the PDMS block to crystallize or not. In the case of diblock copolymers, crystallization of PCL blocks originated from stacking of adjacent chains inducing the extension of the PDMS block that can easily crystallize. In the case of star copolymers, the same tendency as in triblock copolymers is observed, showing a limited crystallization of PDMS when the length of the PCL block increases. In the case of PDMS‐block‐PLA copolymers, melting and crystallization transitions of the PLA block are never observed. Considering the diblock copolymers, PDMS sequences have the ability to crystallize. © 2019 Society of Chemical Industry     

Enhancement of mechanical and optical performance of commercial polystyrenes by blending with siloxane‐based copolymers

Well‐defined poly(styrene‐block ‐dimethylsiloxane) copolymers (PS‐b ‐PDMS) with low polydispersity index (M_w /M_n ) and different compositions were synthesized by sequential anionic polymerization of styrene (S) and hexamethyl(ciclotrisiloxane) (D₃) monomers. Synthesized PS‐b ‐PDMS copolymers were characterized by ¹H‐nuclear magnetic resonance, size exclusion chromatography, Fourier transform infrared spectroscopy, and transmission electron microscopy. The physicochemical characterization determined that block copolymers have molar mass values close to ～135,000 g mol^?1, narrow M_w /M_n < 1.3, and chemical composition ranging from low to intermediate PDMS content. Blends of these copolymers with a commercial polystyrene (PS) were obtained by melt mixing and subsequently injection. Films obtained were flexible, and showed lower transparency than the original PS matrix. On the other hand, a 10 wt % incorporation of PS‐b ‐PDMS copolymers leads to better mechanical performance by enhancing elongation at break (～8.8 times higher) and opacity values (～18 times higher). In addition, UV–Vis barrier capacity of the resulting blends is also increased (up to 400% higher). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45122.     

Synthesis of polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane via polysiloxane‐based macroinitiator in supercritical CO2

Polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane (PDMS‐b‐PS‐b‐PDMS) was synthesized by the radical polymerization of styrene using a polydimethylsiloxane‐based macroazoinitiator (PDMS MAI) in supercritical CO₂. PDMS MAI was synthesized by reacting hydroxy‐terminated PDMS and 4,4′‐azobis(4‐cyanopentanoyl chloride) (ACPC) having a thermodegradable azo‐linkage at room temperature. The polymerization of styrene initiated by PDMS MAI was investigated in a batch system using supercritical CO₂ as the reaction medium. PDMS MAI was found to behave as a polyazoinitiator for radical block copolymerization of styrene, but not as a surfactant. The response surface methodology was used to design the experiments. The parameters used were pressure, temperature, PDMS MAI concentration and reaction time. These parameters were investigated at three levels (?1, 0 and 1). The dependent variable was taken as the polymerization yield of styrene. PDMS MAI and PDMS‐b‐PS‐b‐PDMS copolymers obtained were characterized by proton nuclear magnetic resonance and infrared spectroscopy. The number‐ and weight‐average molecular weights of block copolymers were determined by gel permeation chromatography. Copyright © 2004 Society of Chemical Industry     

Synthesis of block copolymers from PDMS macroinitiators

The synthesis of polystyrene‐b‐polydimethylsiloxane‐b‐polystyrene (PSt‐b‐PDMS‐b‐PSt) copolymers is described. Commercially available difunctional PDMS containing vinylsilyl terminal species was reacted with hydrogen bromide resulting in the PDMS macroinitiators. The terminal alkyl bromide groups were then used as initiators for atom transfer radical polymerization (ATRP) to produce block copolymers. Using this technique, triblock copolymers consisting of a PDMS centre block and polystyrene terminal blocks were synthesized. ATRP of St from those macroinitiators showed linear increases in M_n with conversion, demonstrating the effectiveness of ATRP to synthesize a variety of inorganic/organic polymer hybrids. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of advance PA6‐b‐PDMS multiblock copolymers

Advance polyamide‐6‐b‐polydimethylsiloxane (PA6‐b‐PDMS) multiblock copolymers were first synthesized via the polymerization in bulk. Binary carboxyl terminated PA6 was served as the hard segment and PDMS modified with hexamethylene diisocyanate (PDMS‐NCO) was the soft segment. A series of PA6‐b‐PDMS copolymers based on different content and length of soft segments were obtained. Interestingly, Differential scanning calorimetry (DSC) studies revealed no obvious change in melting temperature after introducing PDMS segments to copolymers. The high melting temperatures indicated these copolymers possess potential applications in automotive industry that require high continuous use temperatures. DSC and transmission electron microscopy studies both demonstrated increasing the length and the content of the soft segment contributed to increasing of the degree of microphase separation. However, the improvement of thermal stability resulting from PDMS segments was also observed by thermo gravimetric analysis. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41114.     

Synthesis and characterization of Pst‐b‐PDMS‐b‐PSt copolymers by atom transfer radical polymerization

Polystyrene‐b‐poly(dimethylsiloxane)‐b‐polystyrene (Pst‐b‐PDMS‐b‐PSt) triblock copolymers were synthesized by atom transfer radical polymerization (ATRP). Commercially available difunctional PDMS containing vinylsilyl terminal species was reacted with hydrogen bromide, resulting in the PDMS macroinitiators for the ATRP of styrene (St). The latter procedure was carried out at 130°C in a phenyl ether solution with CuCl and 4, 4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as the catalyzing system. By using this technique, triblock copolymers consisting of a PDMS center block and polystyrene terminal blocks were synthesized. The polymerization was controllable; ATRP of St from those macroinitiators showed linear increases in M_n with conversion. The block copolymers were characterized with IR and ¹H‐NMR. The effects of molecular weight of macroinitiators, macroinitiator concentration, catalyst concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3764–3770, 2004     

Preparation and characterization of block and graft copolymers using macroazoinitiators having siloxane units

α,ω-Amine terminated organofunctional polydimethylsiloxane (PDMS) was condensed with 4,4′-azobis-4-cyanopentanoyl chloride (ACPC) to prepare macroazoinitiators containing siloxane units. Interfacial polycondensation reaction at room temperature was applied: ACPC was slightly dissolved in carbon tetrachloride and it was poured on aqueous NaOH solution of PDMS. Block copolymers containing PDMS as a block segment combined with polystyrene (PS) have been derived by the polymerization of styrene monomer initiated by these macroazoinitiators. PS-b-PDMS block copolymers were characterized by using nuclear magnetic resonance and infrared spectroscopy. Thermal and mechanical properties of the block copolymers were studied by using thermogravimetric analysis, differential scanning calorimetry, and a Tensilon stress-strain instrument. The morphology of block copolymers was investigated by scanning electron microscopy. PDMS-g-polybutadiene (PBd) graft copolymers were also prepared by reaction of PBd with the above macroazo-initiator. Increase in the amount of macroazoinitiator in the mixture of PBd (52% w/w) leads to the formation of crosslinked graft copolymers. Molecular weights of soluble graft copolymer samples were between 450 and 600 K with a polydispersity of 2.0–2.3. © 1996 John Wiley & Sons, Inc.     

Poly(dimethylsiloxane)urethane‐co‐poly(methyl methacrylate) with 2,4‐toluene diisocyanate and m‐xylene diisocyanate. I. Compatibility and impact strength of copolymers

In this study, slightly crosslinked poly(dimethylsiloxane)urethane‐co‐poly(methyl methacrylate) (PDMS urethane‐co‐PMMA) graft copolymers based on two diisocyanates, 2,4‐toluene diisocyanate (2,4‐TDI) and m‐xylene diisocyanate (m‐XDI), were successfully synthesized. Glass‐transition behaviors of the copolymers were investigated. Results confirm that PDMS–urethane and PMMA are miscible in the 2,4‐TDI system, but are only partially miscible in the m‐XDI system. The methylene groups adjoining the isocyanate in the m‐XDI system show increased phase‐separation behavior over the 2,4‐TDI system, in which the benzene ring adjoins the isocyanate. The functional group of PDMS–urethane improves the impact strength of the copolymers. The toughness depends on the compatibility of PDMS–urethane and PMMA segments in the copolymers. In the m‐XDI system, the impact strength of the copolymer containing 3.75 phr macromonomer achieves a maximum value (from 13.02 to 22.21 J/m). The fracture behavior and impact strength of the copolymers in the 2,4‐TDI system are similar to that of PMMA homopolymer, although they are independent of the macromonomer content in the copolymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1875–1885, 2002     

Block copolymers derived from azobiscyanopentanoic acid. XI. Properties of silicone–PMMA block copolymers prepared via polysiloxane(azobiscyanopentanamide)s

Mechanical, thermal, and surface properties of poly(dimethylsiloxane)–poly(methyl methacrylate) block copolymers (PDMS-b-PMMA) prepared by the use of polysiloxane(azobiscyanopentanamide)s were intensively investigated. The mechanical strength of block copolymers was found to decrease with an increase of siloxane contents. Dynamic mechanical analysis (DMA) of block copolymers having long siloxane chain length (SCL) and high siloxane content revealed the existence of two glass transitions attributable to microphase separation of two segments. Differential scanning calorimetry (DSC) also gave some evidence of microphase separation supporting the DMA results. It was observed that the incorporation of PDMS segments in block copolymers improved thermal stability of PMMA, as confirmed by thermogravimetric analysis. Surface analysis of the block copolymers films cast from several solutions indicated surface accumulation of PDMS segments, as revealed by water contact angle and ESCA measurements.     

Synthesis, formulation, and characterization of siloxane–polyurethane coatings for underwater marine applications using combinatorial high-throughput experimentation

Crosslinked siloxane–polyurethane coatings were designed, synthesized, formulated, applied, and characterized using combinatorial high-throughput experimentation and eight coatings were selected as candidates for further characterization. First, 72 novel hydroxyalkyl carbamate and dihydroxyalkyl carbamate-terminated poly(dimethylsiloxane) (PDMS) oligomers and their carbamate-linked block copolymers with poly(ε-caprolactone) (PCL) were synthesized using a high-throughput synthesis system. These PDMS oligomers and block copolymers were characterized for their molecular weight using high-throughput Gel Permeation Chromatography (Rapid-GPC). The 72 oligomers were then incorporated into siloxane–polyurethane formulations at four different levels resulting in 288 coatings. After initial screening of these 288 coatings, eight coatings were selected for further characterization. Differential scanning calorimetry, dynamic mechanical analysis, X-ray photoelectron spectroscopy and surface energy analysis demonstrate the presence of PDMS on the surface with a polyurethane underlayer. Pseudo-barnacle adhesion and the attachment strength of reattached live barnacles (Balanus amphitrite) were in good agreement. Out of the eight coatings that were down-selected, two coatings performed well in algal (Ulva), bacterial (Cytophaga lytica, Halomonas pacifica), and barnacle (Balanus amphitrite) laboratory screening assays and are potential candidates for ocean testing. This paper was awarded Second Place in the 2006 Roon Awards competition, held as part of the FutureCoat! conference, sponsored by the Federation of Societies for Coatings Technology, in New Orleans, LA, on November 1-3, 2006.     

Contribution of soft segment entanglement on the tensile properties of silicone–urea copolymers with low hard segment contents

Novel, segmented thermoplastic silicone–urea (TPSU) copolymers based on rather high molecular weight aminopropyl terminated polydimethylsiloxane (PDMS) soft segments (<M_n> 10,800 and 31,500 g/mol), a cycloaliphatic diisocyanate (HMDI) and various diamine chain extenders were synthesized. Copolymers with very low urea hard segment contents of 1.43–14.4% by weight were prepared. In spite of very low hard segment contents, solution cast films showed very good microphase separation and displayed reasonable mechanical properties. Tensile strengths of TPSU copolymers showed a linear dependence on their urea hard segment contents, regardless of the structure of the diamine chain extender used. The modulus of silicone–urea copolymers is dependent on the urea concentration, but not on the extender type or PDMS molecular weight. When silicone–urea copolymers with identical urea hard segment contents were compared, copolymers based on PDMS-31,500 showed higher elongation at break values and ultimate tensile strengths than those based on PDMS-10,800. Since the critical entanglement molecular weight (M_e) of PDMS is about 24,500 g/mol, these results suggest there is a significant contribution from soft segment chain entanglement effects in the PDMS-31,500 system regarding the tensile properties and failure mechanisms of the silicone–urea copolymers.     

Synthesis and characterization of poly(dimethyl siloxane) containing poly(vinyl pyrrolidinone) block copolymers

ABA‐type block copolymers containing segments of poly(dimethyl siloxane) and poly(vinyl pyrrolidinone) were synthesized. Dihydroxyl‐terminated poly(dimethyl siloxane) was reacted with isophorone diisocyanate and then with t‐butyl hydroperoxide to obtain macroinitiators having siloxane units. The peroxidic diradical macroinitiators were used to polymerize vinyl pyrrolidinone monomer to synthesize ABA‐type block copolymers. By use of physicochemical methods, the structure was confirmed, and its characterization was accomplished. Mechanical and thermal characterizations of copolymers were made by stress–strain tests and differential scanning calorimetric measurements. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1915–1922, 1999     

Microstructural organization of polydimethylsiloxane soft segment polyurethanes derived from a single macrodiol

Segmented polyurethane (PU) block copolymers were synthesized using 4,4′-methylenediphenyl diisocyanate and 1,4-butanediol as hard segments and oligomeric ethoxypropyl polydimethylsiloxane (PDMS) as the soft segments, with hard segment contents ranging from 26 to 52 wt%. The microphase separated morphology, phase transitions, and degrees of phase separation of these novel copolymers were investigated using a variety of experimental methods. Like similar copolymers with mixed ethoxypropyl PDMS/poly(hexamethylene oxide) soft segments, PU copolymers containing only ethoxypropyl PDMS soft segments were found to consist of three microphases: a PDMS matrix phase, hard domains, and a mixed phase containing ethoxypropyl end group segments and dissolved short hard segments. Analysis of unlike segment demixing using small-angle X-ray scattering demonstrates that degrees of phase separation increase significantly as copolymer hard segment content increases, in keeping with findings from Fourier transform infrared spectroscopy measurements.     

A novel method for preparing silver/poly(siloxane‐b‐methyl methacrylate) nanocomposites with multiple properties in the DMF‐toluene mixture solvent

A novel method for preparing silver/poly(siloxane‐b‐methyl methacrylate) (Ag/(PDMS‐b‐PMMA)) hybrid nanocomposites was proposed by using the siloxane‐containing block copolymers as stabilizer. The reduction of silver nitrate (AgNO₃) was performed in the mixture solvent of dimethyl formamide (DMF) and toluene, which was used to dissolve double‐hydrophobic copolymer, as well as served as the powerful reductant. The presence of the PMMA block in the copolymer indeed exerted as capping ligands for nanoparticles. The resultant nanocomposites exhibited super hydrophobicity with water contact angle of 123.3^° and the thermogravimetry analysis (TGA) revealed that the resultant nanocomposites with more PDMS were more heat‐resisting. Besides, the antimicrobial efficiency of the most desirable nanocomposite (Ag/PDMS₆₅‐b‐PMMA₃₀ loaded with 7.3% silver nanoparticle) could reach up to 99.4% when contacting with escherichia coli within 120 min. As a whole, the resultant nanocomposites by the integration of excellent properties of silver nanoparticles as well as siloxane‐block copolymers can be a promising for the development of materials with hydrophobic, heat‐resisting and outstanding antibacterial properties from the chemical product engineering viewpoint. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4780–4793, 2013     

Surface and mechanical properties of microporous membranes of poly(ethylene glycol)-polydimethylsiloxane copolymer/chitosan

Poly(ethylene glycol)-polydimethylsiloxane (PEG-PDMS) block copolymers were prepared via a condensation reaction between PEG diacid and PDMS diol. PEG diacid was synthesized from the reaction between hydroxy-terminated PEG and succinic anhydride. PDMS diol was prepared from the ring-opening polymerization of octamethylcyclotetrasiloxane (D₄) followed by hydrosilylation with allyl alcohol. The copolymers were incorporated into chitosan in order that good water swellability and wettability of chitosan were retained due to hydrophilic PEG blocks, whereas PDMS block in the copolymers functioned as a toughening modifier. Percent crosslinking of 66-84 was observed once 5-10 wt% of the copolymers was incorporated. As compared to the unmodified sample, the copolymer-containing chitosan exhibited the decreases in both water contact angles and the rate of water vapor permeability. The studies on tensile properties indicated that incorporation of copolymers into chitosan improved the flexibility of the films.     

Surface properties of block and graft polystyrene–polydimethylsiloxane copolymers

The surface compositions of a series of polystyrene‐b‐polydimethylsiloxane (PS‐b‐PDMS) and polystyrene‐g‐polydimethylsiloxane (PS‐g‐PDMS) copolymers were investigated using ATR‐FTIR and XPS technique. The results showed that enrichment of PDMS soft segments occurred on the surface of the block copolymers as well as on that of graft copolymers. And the magnitude order of the enrichment was as follows: PS‐b‐PDMS > PS‐g‐PDMS, which was attributed to the facilitating of the movement of the PDMS segments in PS‐b‐PDMS copolymer. Meanwhile, the solvent type and the contact medium had influence on the accumulation of PDMS on the surfaces. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Poly(hydroxyether of bisphenol A) ‐alt‐polydimethylsiloxane: a novel thermally crosslinkable alternating block copolymer

BACKGROUND: An important strategy for making polymer materials with combined properties is to prepare block copolymers consisting of well‐defined blocks via facile approaches. RESULTS: Poly(hydroxyether of bisphenol A)‐block‐polydimethylsiloxane alternating block copolymers (PH‐alt‐PDMS) were synthesized via Mannich polycondensation involving phenolic hydroxyl‐terminated poly(hydroxyether of bisphenol A), diaminopropyl‐terminated polydimethylsiloxane and formaldehyde. The polymerization was carried out via the formation of benzoxazine ring linkages between poly(hydroxyether of bisphenol A) and polydimethylsiloxane blocks. Differential scanning calorimetry and small‐angle X‐ray scattering show that the alternating block copolymers are microphase‐separated. Compared to poly(hydroxyether of bisphenol A), the copolymers displayed enhanced surface hydrophobicity (dewettability). In addition, subsequent crosslinking can occur upon heating the copolymers to elevated temperatures owing to the existence of benzoxazine linkages in the microdomains of hard segments. CONCLUSION: PH‐alt‐PDMS alternating block copolymers were successfully obtained. The subsequent self‐crosslinking of the PH‐alt‐PDMS alternating block copolymers could lead to these polymer materials having potential applications. Copyright © 2008 Society of Chemical Industry     

Silicone Macroinitiator in Atom Transfer Radical Polymerization of Styrene and Vinyl Acetate: Synthesis and Characterization of Pentablock Copolymers

Poly(dimethylsiloxane) (PDMS) based pentablock copolymers has been synthesized via atom transfer radical polymerization (ATRP) of styrene (St) and vinyl acetate (VAc) telomer at 60 °C in the presence of CuCl/PMDETA as a catalyst system. Vinyl acetate telomer was prepared from controlled radical telomerization with Co(acac)₂/DMF with PDI ≈ 1.3. Poly(vinyl acetate-b-styrene-b- dimethylsiloxane- b- styrene-b-vinyl acetate) (PVAc-b-PSt-b-PDMS-b-PSt-b-PVAc) pentablock copolymers provided a method to design block copolymer with PDMS segment, allowing us for the adjustments in the flexibility by PDMS with a large effect from its softening point (T_g), or rigidity of styrene monomer and a higher melting temperature (T_m). Penta-block copolymers were characterized by FTIR, ¹HNMR, DSC, and GPC techniques. Meanwhile, the number-average molecular weights calculated from ¹HNMR spectra were in very good agreement with the theoretically calculated value. It could be concluded from the ¹HNMR and DSC spectrum that the pentablock copolymers of PVAc-b-PSt-b-PDMS-b-PSt-b-PVAc consisting of a PDMS center block and PSt and PVAc terminal blocks were synthesized.     

Relationship between the composition of polycarbonate copolymers and the refractive index

With a polycarbonate (PC)–poly(methyl methacrylate) (PMMA) graft copolymer and a PC–poly(dimethyl siloxane) (PDMS) block copolymer, the relationship between the composition of PC copolymers and the refractive index (n_D) was investigated. According to the results, with a PMMA content of 38 wt %, the n_D value of the PC–PMMA graft copolymer was nearly the same as that of electrical (E) glass (n_D = 1.545), and with a PMMA content of 6 wt %, it was nearly the same as that of electrical corrosion resistance (ECR) glass (n_D = 1.579). However, with a PDMS content of 19 wt %, the n_D value of the PC–PDMS block copolymer was nearly the same as that of E glass, and with a PDMS content of 2 wt %, it was nearly the same as that of ECR glass. The combination of the PC–PDMS block copolymer and the glass fibers (GFs) of ECR glass led to haze values of 8 and 16% with GF contents of 10 and 20%, respectively. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 514–521, 2002; DOI 10.1002/app.2355