Preparation and surface properties of silicone-modified polyester-based polyurethane coats.A series of novel silicone-modified polyesters (SPE SPE - Software Practice and Experience ) were prepared by substituting part of diol diol
an organic compound containing two hydroxy groups, a dihydric alcohol. Called also glycol. with low molecular weight hydroxyl-terminated poly(dimethylsiloxane) (PDMS (Product Data Management System) See PDM. ). Then, isophorone diisocyanate Isophorone diisocyanate (IPDI) is an organic compound in the class known as isocyanates. More specifically, it is an aliphatic diisocyanate. It is produced in relatively small quantities, accounting for (with hexamethylene diisocyanate) only 3. (IPDI IPDI Isophorone Diisocyanate
IPDI Institute for Politics, Democracy and the Internet (George Washington University) ) as hard segments and 1,4-butanediol as chain extender See Media Center Extender, bus extender and DOS extender. were added to SPE to prepare a silicone-modified polyurethane (SPU SPU Seattle Pacific University
SPU Seattle Public Utilities
SPU Strategy and Policy Unit
SPU Sripatum University (Thailand)
SPU Split, Croatia (Airport Code)
SPU Synergistic Processor Unit ). The effects of the type of diol, diacid, and hydroxyl-terminated PDMS, and the amount of hydroxyl-terminated PDMS on the preparation and surface properties of SPU were investigated. It was found that the amount of PDMS incorporated into a polyester chain was relatively higher when 1,6-hexanediol (HDO HDO High Density Overlay (phenolic resin-impregnated plywood used in concrete forms)
HDO Hearing Designation Order (FCC proceedings)
HDO Humanitarian Demining Operation
HDO High Demand Occupation ) and 1,10-decandiol (DDO DDO - Dynamic Drive Overlay ) were used as diol and the PDMS with lower molecular weight was used as organosilicone compound. Consequently, the SPU coats with HDO as diol, adipic acid a·dip·ic acid
A white crystalline dicarboxylic acid, C6H11O4, that is derived from oxidation of various fats, slightly soluble in water and soluble in alcohol and acetone, and used especially in the manufacture of (AA) as diacid, and short chain PDMS as silicone segment had the lowest surface-free energy since it had the highest and most homogeneous distribution of silicone segments at its top layer surfaces.
Keywords: Hydroxyl-terminated poly(dimethylsiloxane), polyesters, polyurethanes, surface-free energy, coats, silicones, ESCA ESCA Electron Spectroscopy for Chemical Analysis
ESCA Escaflowne (anime series)
ESCA European Speech Communication Association
ESCA Escuela Superior de Comercio y Administración (México) , XPS (1) See XML Paper Specification.
(2) A brand name for certain models of Inspiron laptops from Dell. , Auger, SIMS, crosslinking, cure, surface analysis, stain resistance
Thermoplastic A polymer material that turns to liquid when heated and becomes solid when cooled. There are more than 40 types of thermoplastics, including acrylic, polypropylene, polycarbonate and polyethylene. polyurethanes (TPUs) are a versatile group of multicomponent segmented polymers that have excellent mechanical properties, good hardness, and high abrasion and chemical resistance. (1) They are widely used as melt-spandex, synthetic leather, film, adhesive, tube, and wire and cable materials. They find application in the automobile, health care, footwear, and coating industries. When TPUs are used in the coating industry, enhancement of the hydrophobicity of the surfaces of TPU TPU - Text Processing Utility films is of interest as a means of improving the stain resistance of TPU coats or reducing the wettability of TPU coats.
Modification with organosilicone is one of the ideal methods available for improving the hydrophobicity of the surfaces of TPU coats. The most widely used organosilicone is poly(dimethylsiloxane)s (PDMS). For example, Ho et al. (2-6) synthesized poly(dimethylsiloxane)-urea-urethane copolymers by a two-step polymerization polymerization
Any process in which monomers combine chemically to produce a polymer. The monomer molecules—which in the polymer usually number from at least 100 to many thousands—may or may not all be the same. method. Wang et al. (7) prepared PDMS-containing polyurethanes that were derived from a hydroxyl-terminated poly(tetramethylene oxide) (PTMO), secondary aminoalkyd functional PDMS oligomer oligomer /ol·i·go·mer/ (ol´i-go-mer) a polymer formed by the combination of relatively few monomers.
oligomer ( , 4,4'-methylene diphenyl diphenyl /di·phen·yl/ (di-fen´il) a toxic compound comprising two linked benzene rings, used as a fungistat in containers for shipping citrus fruits.
See biphenyl. diisocyanate (MDI (1) (Multiple Document Interface) A Windows function that allows an application to display and lets the user work with more than one document at the same time. ), and 1,4-butanediol via solution polymerization Solution polymerization is a method of industrial polymerization. In this procedure, a monomer is dissolved in a non-reactive solvent that contains a catalyst. The heat released by the reaction is absorbed by the solvent, and so the reaction rate is reduced. in terahy-drofuran (THF THF tetrahydrofolic acid.
tetrahydrofolic acid. )/dimethylacetamide (DMAC DMAC Direct Memory Access Controller
DMAC Data Management and Communications
DMAC Downtown Media Arts Center (Orlando, Florida)
DMAC Direct Memory Access Control
DMAC Direct Machining and Control ). Rochery et al. (8) also incorporated PDMS into PTMO-based polyurethanes by using both hydroxyl-terminated PDMS and IPDI. Mequanint et al. (9) prepared phosphate- and siloxane-containing polyurethane dispersions by a conventional method from hydroxyl-terminated phosphated and siloxane siloxane /si·lox·ane/ (si-lok´san) any of various compounds based on a substituted backbone of alternating silica and oxygen molecules; in polymeric form they are polysiloxanes, and when the side chain substituents are organic radicals, macroglycols. Yen et al. (10) synthesized polyethylene glycol/PDMS mixing soft-segment waterborne polyurethane by a procedure of PU blending or soft-segment copolymerization copolymerization (kōpäl´imrizā´sh . All of the above prepared silicone-containing polyurethanes showed a reduction in surface-free energy. The methods of preparation of PDMS-modified TPU were mainly based on mixing polyether/polyester and PDMS.
The objective of this study was to prepare silicone-modified TPU coats based on hydroxyl-terminated PDMS-modified polyester and IPDI, which has been seldom reported. A series of novel silicone-modified polyesters (SPE) were first prepared by substituting part of diol with low molecular weight hydroxyl-terminated PDMS using a method for synthesis of conventional polyester. Then, isophorone diisocyanate (IPDI) as hard segments and 1,4-butanediol (BDO BDO Big Day Out (Australian music festival)
BDO Banco de Oro (Philippines)
BDO British Darts Organisation
BDO Block Development Officer
BDO Big Dumb Object ) as chain extender were added to prepare a silicone-modified polyurethane (SPU). The structure and the surface properties of SPU coats were characterized by [.sup.1.H]NMR NMR: see magnetic resonance. , optical contact angle system (OCA OCA oculocutaneous albinism. ), X-ray photoelectron pho·to·e·lec·tron
An electron released or ejected from a substance by photoelectric effect.
photoelectron spectrometer (XPS), and scanning electron microscope scan·ning electron microscope
n. Abbr. SEM
An electron microscope that forms a three-dimensional image on a cathode-ray tube by moving a beam of focused electrons across an object and reading both the electrons scattered by the object and (SEM) with EDX EDX Energy Dispersive X-Ray (Spectroscopy)
EDX Electronic Data Exchange
EDX Extended Data Register
EDX Event-Driven Executive (IBM Series/1 OS)
EDX Event-Based Data Exchange (UPNet) . Effects of the type of diol and diacid and the type and quantity of hydroxyl-terminated PDMS, etc. on the surface properties of the obtained polyurethane coats were investigated in detail.
Two kinds of hydroxyl-terminated PDMS, namely PDMS550 (chemical purity chemical purity,
n the degree to which a substance is undiluted or unmixed with extraneous material, typically expressed as a percentage (%). grade, average molecular weight: 550 g/mol) and PDMS1000 (chemical purity grade, average molecular weight: 1000 g/mol), were obtained from Aldrich and were used without further purification. Diacid: adipic acid (AA, chemical purity grade) and phthalic anhydride phthalic anhydride
A white crystalline compound prepared by oxidizing naphthalene and used in the manufacture of phthaleins and other dyes. (PA, chemical purity grade), diol: 1,4-butandiol (BDO, chemical purity grade), 1,6-hexandiol (HDO, chemical purity grade), and 1,10-decandiol (DDO, chemical purity grade) were provided by Sinopharm Group Chemical Reagent Co., Ltd., and neopentylene glycol glycol (glī`kōl), dihydric alcohol in which the two hydroxyl groups are bonded to different carbon atoms; the general formula for a glycol is (CH2)n(OH)2. (NPG NPG Nature Publishing Group (Macmillan Publishers, Ltd)
NPG National Portrait Gallery (UK)
NPG NIOSH Pocket Guide to Chemical Hazards
NPG New Power Generation (Prince) , 99.65%) by Mitsubishi Chemical Company of Japan. Isocyanate i·so·cy·a·nate
Any of a family of nitrogenous chemicals that are used in industry and can cause respiratory disorders, especially asthma, if inhaled. : isophorone diisocyanate (IPDI, Desmodur N-3300) was purchased from Bayer. Catalyst: dibutyltin dilaurate dibutyltin dilaurate
a coccidiostat used in commercial poultry.
dibutyltin dilaurate poisoning
feeding to calves in error causes diarrhea and polyuria. (T-12, chemical purity grade) was obtained from Shanghai No. 1 Reagent Factory of China. Solvents: toluene toluene (tōl`yēn') or methylbenzene (mĕth'əlbĕn`zēn), C7H8 (analytical purity grade), 3-pentanone (analytical purity grade), cyclohexane cyclohexane (sī'kləhĕk`sān), C6H12, colorless liquid hydrocarbon. It is a cyclic alkane that melts at 6°C; and boils at 81°C;. It is nearly insoluble in water. (analytical purity grade), and ethylene glycol ethylene glycol: see glycol.
Simplest member of the glycol family, also called 1,2-ethanediol (HOCH2CH2OH). It is a colourless, oily liquid with a mild odour and sweet taste. (EG, analytical purity grade) were also obtained from Sinopharm Group Chemical Reagent Co., Ltd.
Preparation of Silicone-Modified Polyesters and Related Thermoplastic Polyurethanes
Diacid, diol, and hydroxyl-terminated PDMS with 1 wt% T-12 based on the total mass of monomers as the catalyst were charged into a 100 ml three-necked flask, equipped with a mechanical stirrer, a nitrogen inlet, a reflux condenser Noun 1. reflux condenser - condenser such that vapor over a boiling liquid is condensed and flows back into the vessel to prevent its contents from boiling dry
condenser - an apparatus that converts vapor into liquid , and a receiver pipe. The flask was first heated to 140[degrees]C, then slowly to 180[degrees]C within four hours, and kept at that temperature until the acid number of the system was less than 3 mgKOH/g. The total reaction time was about 12-16 hr. The codes and molar feeding ratios of the obtained SPEs are given in Table 1. To remove unreacted PDMS, all of the resulting polyesters were purified by extracting with cyclohexane at least three times, and dried under vacuum conditions at 105[degrees]C for 48 hr. Since most of the prepared SPEs were solid at room temperature, all of the purification work was carried out in an oven at 60[degrees]C.
The corresponding polyurethanes (namely SPU polymers) were prepared via solution polymerization described as follows: The mixture of SPE/IPDI/BDO (molar ratio: 1/2/1) was dissolved in the mixture of toluene and 3-pentanone (volume ratio: 2/1) at 20 wt% solid, and added to a two-necked flask equipped with a nitrogen inlet, magnetic stirrer A magnetic stirrer is a type of laboratory equipment consisting of a rotating magnet or stationary electomagnets creating a rotating magnetic field. The stirrer is used to cause a stir bar, immersed in a liquid to be stirred, to spin very quickly, stirring it. , and a reflux condenser, and was reacted at 80[degrees]C for one hour, and then poured into a mold. The mold was put into a vacuum oven at 105[degrees]C for 24 hr to finish the reaction and evaporate the solvent. The final product, named SPU-a as corresponding to the polyester of SPE-a (where "a" is the sample number), was dissolved in toluene/3-pentanone (volume ratio: 2/1) again at a concentration of 2 wt%. Polymer coats were prepared by casting the above solution on glass panels using a drawdown Drawdown
The peak to trough decline during a specific record period of an investment or fund. It is usually quoted as the percentage between the peak to the trough.
Notes: rod and dried at 70[degrees]C for one hour. The thickness of the resulted coats was about 1-2 [micro]m.
[.sup.1.H]-NMR SPECTRA: The [.sup.1.H]-NMR spectra of liquid state polymers were determined by AVANCE DMX See DMX512. 500 (Bruker Biospin Gmbh, Germany) at 500 MHz (MegaHertZ) One million cycles per second. It is used to measure the transmission speed of electronic devices, including channels, buses and the computer's internal clock. A one-megahertz clock (1 MHz) means some number of bits (16, 32, 64, etc. . Deuterated chloroform (CD[Cl.sub.3]) was used as the solvent.
CONTACT ANGLES: The contact angles of liquid on SPU coats were measured by OCA15 (DataPhysics Instruments Company, Germany). The connected software for measurement and calculation were SCA (Single Connector Attachment) An 80-pin plug and socket used to connect peripherals. With a SCSI drive, it rolls three cables (power, data channel and ID configuration) into one connector for fast installation and removal. 20 and SCA21, respectively. The complete profile of the sessile sessile /ses·sile/ (ses´il) attached by a broad base, as opposed to being pedunculated or stalked.
Permanently attached or fixed; not free-moving. droplet droplet
very small drop of fluid.
the finite particles of matter which are transmitted from animal to animal. was fitted by the ellipse ellipse, closed plane curve consisting of all points for which the sum of the distances between a point on the curve and two fixed points (foci) is the same. It is the conic section formed by a plane cutting all the elements of the cone in the same nappe. method. The contact angle was the average value of five individual test data at different places on the polymer surfaces.
SURFACE-FREE ENERGY: The surface-free energy of the films was calculated by the Owens-Wendt-Kaelble method. In this experiment, deionized water and ethylene glycol were selected as the probe liquid to determine the surface-free energies of polyester-based polyurethane coats. The values of [[sigma].sub.l.sup.d] (21.80 mN/m) and [[sigma].sub.l.sup.p] (51.00 mN/m) for water and [[sigma].sub.l.sup.d] (30.90 mN/m) and [[sigma].sub.l.sup.p] (16.80 mN/m) for ethylene glycol were used in the calculation by SCA21 software.
XPS SPECTRA: XPS spectra were measured by a PHI 5000C ESCA System (Perkin Elmer Inc., USA) using an Al [K.sub.[alpha]] X-ray source. The X-ray gun was operated at 14.0 KV and 250 W, and the analyzer chamber pressure was less than [10.sup.-6] Pa. Survey scans spectra (0-1200 eV) were recorded at pass energy of 93.9 eV. Narrow scan spectra of [C.sub.1s], [O.sub.1s], [N.sub.1s], and [Si.sub.2p] were collected and peak analysis was carried out using PHI-MATLAB software.
SEM WITH EDX: The surface morphology of polymer coats was determined by a scanning electronic microscope (XL30, Philips Corp., Netherlands) equipped with an EDX accessory. Also used in the measurement were 20-30 kV of beam accelerating voltage and 3.8 nm of resolution factor. The morphology of the cross-section of the corresponding polyurethane coats, prepared by fresh fracture in liquid nitrogen, was also observed with the scanning electronic microscope.
RESULTS AND DISCUSSION
Preparation of Silicone-Modified Polyester-Polyurethane
Hydroxyl-terminated PDMS was incorporated into polyester by substituting part of diol. The reaction is described as follows:
Then SPE was further reacted with IPDI and BDO as follows:
Figure 1 displays the [.sup.1.H]NMR spectra of sample PE-1 and sample SPE-1. A new peak at 0.07 ppm attributed to the proton in the methyl group connected to the silicon element (C[H.sub.3]-Si-) was found in the [.sup.1.H]-NMR spectrum of sample SPE-1, indicating that the hydroxyl-terminated PDMS was successfully incorporated into the polyester main chain. In addition, the peaks at 4.1 ppm and 3.6 ppm corresponded to the proton ([H.sub.[beta]]) in the methylene methylene /meth·y·lene/ (meth?i-len) the bivalent hydrocarbon radical —CH2— or CH2dbond.
n. connected with the ester group (-C[H.sub.2]-O-CO-) and the proton ([H.sub.[alpha]]) in the methylene next to the hydroxyl group hydroxyl group (hīdrŏk`sĭl), in chemistry, functional group that consists of an oxygen atom joined by a single bond to a hydrogen atom. An alcohol is formed when a hydroxyl group is joined by a single bond to an alkyl group or aryl group. (-C[H.sub.2]-OH), respectively. Table 2 lists the calculated actual composition of SPE series based on NMR spectra. Compared to the feeding composition in Table 1, it can be seen that a larger amount of PDMS can be copolymerized using HDO and DDO as diol. Moreover, the larger the amount of PDMS fed in condensation polymerization, the higher the PDMS content contained in SPE. Table 2 also shows that PDMS was more easily added to the polyester main chain with only AA rather than only PA as the diacid monomer monomer (mŏn`əmər): see polymer.
Molecule of any of a class of mostly organic compounds that can react with other molecules of the same or other compounds to form very large molecules (polymers). . However, for the sample with the mixture of AA and PA, the PDMS content in SPE slightly increased with the increment of the amount of PA. In addition, the amount of PDMS in SPE prepared using the PDMS with high molecular weight (sample SPE-6) was lower than that using PDMS with low molecular weight (sample SPE-2), which may have been caused by the relatively lower activity and lower amount of silanol group for the PDMS with high molecular weight.
The degree of condensation, [d.sub.C], can be calculated from the peak area ratio of [H.sub.[alpha]] and [H.sub.[beta]]. (11)
[d.sub.C] = area ([H.sub.[beta]])/area ([H.sub.[alpha]])
Thus, the average molecular weight (Mn) of the polyester can be calculated by the following equation (11):
Mn = [d.sub.C] [M[W.sub.(diacid)] + M[W.sub.(diol)] - 2M[W.sub.(water)]] + M[W.sub.(diol)]
where M[W.sub.(diacid)], M[W.sub.(diol)], and M[W.sub.(water)] are the molecular weights of diacid, diol, and water, respectively. Table 3 summarizes the average molecular weight of polyester or the polyester segment of SPE.
In Table 3, it was found that the molecular weight of the polyester segment of SPE was greater than that of the corresponding polyester. It seems that the hydroxyl-terminated PDMS was favored for the polycondensation reaction. The effect of the dosage of silicone on the molecular weight of the polyester segment of SPE is displayed in Figure 2. It shows that the molecular weight of the polyester segment of SPE increased as the amount of silicone increased, further indicating the silicone's "catalysis catalysis
Modification (usually acceleration) of a chemical reaction rate by addition of a catalyst, which combines with the reactants but is ultimately regenerated so that its amount remains unchanged and the chemical equilibrium of the conditions of the reaction is not role" on the polycondensation.
[FIGURE 1 OMITTED]
Surface-Free Energies of Silicone-Modified Polyester-Polyurethane Coats
EFFECTS OF THE TYPE OF DIOL, DIACID, AND HYDROXYL-TERMINATED PDMS: The contact angles of water and ethylene glycol on polyurethane coats and the surface-free energies of the polyurethanes with different types of diol, diacid, and hydroxyl-terminated PDMS are summarized in Table 4. Comparing the data of samples from the SPU series with the corresponding PU series suggests that the surface-free energy obviously decreased after the incorporation of silicone.
Based on the surface-free energy data of samples SPU-1, SPU-2, SPU-3, and SPU-4, it shows that sample SPU-2 with HDO as the diol unit had the lowest surface-free energy (12.59 mN [m.sup.-1]). It may be a result of two factors: (1) SPE-2 used for preparation of SPU-2 had the highest PDMS content (see the data in Table 2); (2) the compatibility of PDMS segment with HDO segment may be more appropriate for the transfer of PDMS segment to the surface and homogenous homogenous - homogeneous distribution of PDMS segment at the surface of SPU coats, rather than that with a shorter chain (i.e., BDO) or a longer chain (i.e., DDO and NPG) of diol unit since greater or less compatibility will lead to a difficult transfer of PDMS segment to the surface or uneven distribution of the PDMS segment at the surface.
[FIGURE 2 OMITTED]
The data on samples SPU-2 and SPU-5 show that the surface-free energy of SPU coat with phthalic anhydride was greater than the sample with adipic acid, which may have occurred for two reasons: (1) sample SPU-2 had higher silicone content than sample SPU-5; (2) the benzene ring benzene ring
The hexagonal ring structure in the benzene molecule and its substitutional derivatives, each vertex of which is occupied and distinguished by a carbon atom.
n See aromatic ring. in the phthalic anhydride molecule weakened the facility of the whole system and consequently limited the transferring towards the surface of silicone segments. Figure 3 shows the effect of the composition of mixed diacids (AA and PA) on the surface-free energy of SPU coats. It can be seen that the surface-free energy of SPU coats increased with the amount of PA in mixed diacids, which further confirms that AA as diacid unit is better than PA at reducing the surface free energy of SPU coats. Since the sample with higher silicone content (see the data of samples SPE-11, SPE-12, and SPE-13 in Table 2) had higher surface-free energy, we can infer that the restraining role of the benzene ring in phthalic anhydride for the transfer of PDMS chain towards the surfaces of SPU coats was mainly responsible for the lower surface-free energy of SPU coats.
From Table 4, it was unexpectedly found that the surface-free energy of sample SPU-6 was higher than that of sample SPU-2, indicating that the efficiency of long chain silicone (PDMS1000) was worse than that of short chain silicone (PDMS550) at reducing the surface-free energy of SPU coats when the same molar feed ratio was used. This should be attributed to the lower reactive activity of PDMS 1000 with diacid monomer and, correspondingly, lower PDMS content in SPU coats.
[FIGURE 3 OMITTED]
[FIGURE 4 OMITTED]
EFFECT OF THE DOSAGE OF HYDROXYL-TERMINATED PMS (Pantone Matching System) A color matching system that has a unique number assigned to more than 500 different colors and shades. This standard for the printing industry has been built into many graphics and desktop publishing programs to ensure color accuracy. : The effect of the dosage of hydroxyl-terminated PDMS on the surface-free energy of SPU is shown in Table 5. The surface-free energies of the SPUs first decreased then leveled off with increasing PDMS amount in feed composition. However, the change was very consistent with the change of the PDMS content in SPU coats. Namely, the higher the PDMS content in SPU coats, the lower the surface-free energy of SPU coats.
Surface Compositions of Silicone-Modified Polyester-Polyurethane
The atomic concentration of C, O, Si, and N for the airside air·side
The part of an airport directly involved in the arrival and departure of aircraft.
the part of an airport nearest the aircraft surfaces of SPU coats are summarized in Table 6. For the sake of comparison, the theoretical atomic concentration is also calculated in Table 6, based on the feed composition. For all SPUs, the experimentally determined Si contents were higher than their corresponding theoretical values, further validating that the incorporated silicone segments tend to enrich at the top layer surfaces of polymer coats. It can also be seen that the Si concentration of sample SPU-2 with 1,6-hexanediol is the highest, which was consistent with the results of the contact angles and the surface-free energies.
Surface and Cross-Section Morphology Of SPU Coats
The SEM pictures of the surfaces and cross-sections of SPU coats are shown in Figure 4. The surface and cross-section morphology of sample SPU-1 show the existence of micron scale particles, and these particles distribute in the coats uniformly. Figure 5 illustrates the EDX spectrum of the particles in sample SPU-1. The atomic concentrations of C, O, Si, N, and Si/C atom ratios are summarized in Table 7. Since the theoretical Si/C ratios of PDMS and the whole sample SPU-1 coats are 0.5 and 0.004, respectively, 0.27 of the Si/C atom ratio for the particles means that the silicone segments should be the predominant species in the particles. This is probably because the silicone segments were not compatible with other components and tended to aggregate in the SPU-1 sample. However, for sample SPU-2, no obvious microphase separation was found at both the surface and cross-section, suggesting that all components in bulk are compatible with each other. This means that silicone segments can homogeneously distribute and enrich on the surfaces of the SPU coats. Some submicron scale particles were also found in the surface and bulk of sample SPU-3, which suggests that the compatibility of the coats with 1,10-decanediol was worse than with 1,6-hexanediol. The uneven distribution of silicone segments at the top layer surfaces of samples SPU-1 and SPU-3 may be responsible for their high surface-free energies. The morphologies of surfaces and cross-sections of samples SPU-4 and SPU-5 were analogous to sample SPU-2, but their surface-free energies were higher. This is attributed to the reduced mobility imposed by the rigid groups (neo-amyl and benzene ring, respectively) of samples SPU-4 and SPU-5.
[FIGURE 5 OMITTED]
A series of SPU coats was successfully synthesized by substituting part of diol with low molecular weight hydroxyl-terminated PDMS and using a conventional method for synthesis of the polyester. The amount of PDMS incorporated into the polyester chain was relatively higher when HDO and DDO were used as diol and the PDMS with lower molecular weight as organosilicone compound. The concentration of silicone segments tended to be higher at the polymer/air interface. The higher the amount of hydroxyl-terminated PDMS incorporated, the higher the concentration of silicone segments in the top layer, and the lower the surface-free energy of polyurethane coat. For reducing the surface-free energy of SPU coats, AA as diacid unit was better than PA and long chain silicone was worse than short chain silicone when the same molar feed ratio was used. In addition, it seemed that the components of SPU with 1,6-hexanediol as the diol monomer had the appropriate compatibility, and thus this sample had the lowest surface-free energy and the highest Si content at its surface.
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Jun Yang, Shuxue Zhou, Bo You, and Limin Wu ([dagger]) -- Fudan University*
* Dept. of Materials Science, The Advanced Coats Research Center of China Educational Ministry, Shanghai 200433, People's Republic of China.
([dagger]) Author to whom correspondence should be addressed. Email: email@example.com.
Table 1 -- Codes and Molar Feed Ratios of Polyester and Silicone-Modified Polyester (Unit: %) Sample No. AA PA BDO HDO DDO NPG PDMS550 PE-1 41.7 -- 58.3 -- -- -- -- PE-2 41.7 -- -- 58.3 -- -- -- PE-3 41.7 -- -- -- 58.3 -- -- PE-4 41.7 -- -- -- -- 58.3 -- PE-5 -- 41.7 -- 58.3 -- -- -- SPE-1 41.7 -- 55.0 -- -- -- 3.3 SPE-2 41.7 -- -- 55.0 -- -- 3.3 SPE-3 41.7 -- -- -- 55.0 -- 3.3 SPE-4 41.7 -- -- -- -- 55.0 3.3 SPE-5 -- 41.7 -- 55.0 -- -- 3.3 SPE-6 (a) 41.7 -- -- 55.0 -- -- 3.3 SPE-7 41.7 -- -- -- 56.6 -- 1.7 SPE-8 41.7 -- -- -- 53.3 -- 5.0 SPE-9 41.7 -- -- -- 51.6 -- 6.7 SPE-10 41.7 -- -- -- 48.3 -- 10.0 SPE-11 27.8 13.9 -- 55.0 -- -- 3.3 SPE-12 20.9 20.8 -- 55.0 -- -- 3.3 SPE-13 13.9 27.8 -- 55.0 -- -- 3.3 (a) PDMS1000 was used here. Table 2 -- Actual Composition of SPE Series Based on [.sup.1.H]NMR AA PA Diol Hydroxyl-Terminated PDMS Sample No. (mol%) (mol%) (mol%) (mol%) SPE-1 43.0 -- 52.8 4.2 SPE-2 40.2 -- 51.0 8.8 SPE-3 41.3 -- 50.4 8.3 SPE-4 46.1 -- 50.6 3.3 SPE-5 -- 42.3 52.6 5.1 SPE-6 44.0 -- 53.4 2.6 SPE-7 41.7 -- 51.0 7.3 SPE-8 41.3 -- 49.3 9.4 SPE-9 40.4 -- 48.8 10.8 SPE-10 40.4 -- 49.0 10.6 SPE-11 30.3 11.8 51.7 6.2 SPE-12 19.5 22.5 50.9 7.1 SPE-13 12.6 29.7 49.8 7.9 Table 3 -- Molecular Weight of Polyester and the Polyester Part of Silicone-Modified Polyester Sample No. [d.sub.c] [M.sub.n] (a) Sample No. [d.sub.c] [M.sub.n] (a) PE-1 2.8 651 SPE-1 4.1 901 PE-2 2.6 712 SPE-2 3.7 952 PE-3 2.6 900 SPE-3 4.2 1366 PE-4 3.4 722 SPE-4 4.6 1080 PE-5 2.7 735 SPE-5 3.4 897 (a) Calculated from [.sup.1.H]NMR. Table 4 -- Effects of the Type of Diol, Diacid, Hydroxyl-Terminated PDMS on Contact Angle, and Surface-Free Energy of Polymer Coats [[theta].sub.[H.sub.2]O] [[theta].sub.EG] Sample No. ([degrees]) ([degrees]) PU-1 82.1 61.8 PU-2 78.2 53.4 PU-3 84.6 63.2 PU-4 80.5 60.3 PU-5 84.5 61.9 SPU-1 99.6 81.1 SPU-2 101.8 88.7 SPU-3 102.3 83.0 SPU-4 98.0 78.9 SPU-5 95.6 77.6 SPU-6 94.5 74.6 [[sigma].sup.da] [[sigma].sup.pa] [[sigma].sub.s] Sample No. (mN [m.sup.-1]) (mN [m.sup.-1]) (mN [m.sup.-1]) PU-1 17.82 8.39 26.31 PU-2 25.01 7.19 32.20 PU-3 20.75 5.89 26.64 PU-4 17.27 9.62 26.89 PU-5 23.17 5.03 28.20 SPU-1 17.38 1.76 19.14 SPU-2 8.18 4.42 12.59 SPU-3 19.15 0.86 20.01 SPU-4 18.49 1.89 20.38 SPU-5 16.09 3.28 19.37 SPU-6 19.79 2.52 22.31 (a) [[sigma].sup.d] and [[sigma].sup.p] are the disperse and polar contribution to the surface energy. Table 5 -- Effects of the Quantity of Hydroxyl-Terminated PDMS on the SPUs PDMS Content PDMS Content in SPE in SPU Coats [[theta].sub.[H.sub.2]O] Sample No. (mol%) (mol%) ([degrees]) PU-3 -- -- 84.6 SPU-7 7.3 1.8 87.8 SPU-3 8.3 2.1 102.3 SPU-8 9.4 2.4 103.0 SPU-9 10.8 2.7 105.1 SPU-10 10.6 2.7 104.8 [[sigma].sub.EG] [[sigma].sup.d] [[sigma].sup.p] Sample No. ([degrees]) (mN [m.sup.-1]) (mN [m.sup.-1]) PU-3 63.2 20.75 5.89 SPU-7 67.4 19.59 4.96 SPU-3 83.0 19.15 0.86 SPU-8 83.2 19.81 0.65 SPU-9 86.7 17.30 0.70 SPU-10 86.0 18.13 0.62 [[sigma].sub.s] Sample No. (mN [m.sup.-1]) PU-3 26.64 SPU-7 24.55 SPU-3 20.01 SPU-8 20.46 SPU-9 18.00 SPU-10 18.75 (a) The molar percentage of hydroxyl-terminated PDMS in SPU calculated on the actual composition of SPE. Table 6 -- Surface Atomic Concentration and Theoretical Values of SPU Coats C (mol%) O (mol%) Sample No. Determined Calculated (a) Determined Calculated (a) SPU-1 52.3 70.0 29.6 23.5 SPU-2 52.2 70.9 28.1 22.3 SPU-3 51.6 71.9 29.7 21.4 SPU-4 58.8 70.6 27.8 23.0 SPU-5 56.2 72.4 29.9 21.1 SPU-6 63.8 71.1 25.7 22.5 Si (mol%) N (mol%) Sample No. Determined Calculated (a) Determined Calculated (a) SPU-1 17.4 0.3 0.7 6.2 SPU-2 19.0 0.6 0.7 6.2 SPU-3 17.8 0.5 0.9 6.2 SPU-4 9.6 0.2. 3.8 6.2 SPU-5 12.0 0.3 1.9 6.2 SPU-6 8.1 0.2 2.4 6.2 (a) Based on the actual composition of SPE. Table 7 -- Atomic Concentration of the Particles in Sample SPU-1 Sample C (mol%) O (mol%) Si (mol%) N (mol%) Si/C SPU-1 54.1 30.1 14.7 1.1 0.27