Qs SHIMADZU jons for S sineé SHIMADZU GEL PERMEATION CHROMATOGRAPHY SYSTEM APPLICATION DATA BOOK CC a oy v ‘Lh hd heMore than two decades have passed since J.C. Moore developed gel permeation chromatog: raphy (GPC) in 1964, and the progress made in this period has been outstending ‘At the beginning, the GPC was mainly used {a8 the means for measurement of properties such as molecular weight and molecular weight distribution in polymer synthesis. Along with developments allowing better separetions and higher speed, GPC application fields have ex. panded as the means for separation of oligomers ‘and aditives, and it is now indispensable as the ‘means for characterization of synthetic polymers and analysis of polymeric: materials. ‘The principal components forming 3 polymeric material are closely related to its physical char- acteristics such as fluidity and workability, depending on their molecular weight and/or ‘molecular weight distribution. Furthermore, these. properties allow for separation of components of copolymers and separation of additive com ponents of polymers, and determination of com- ponent ratios, Iis well known that the properties of polymers, are largely affected by the type and amount of the additives (blends) they contain, aside from the properties of the principal components. As a typical example, hardness characteristics are chenged widely by adding plasticizers to polyvinyl chloride, Recently, among the advanced materials, higher performances are required in high molecular materials such as functional polymers: (fine plastics) and engineering plastics, and against this background GPC analysis is expected to be applied more and more widely in research and development and in process contro fields as the method of choice for comprehensive determination of characteristics. (On the other hand, high performance liquid chromatography (HPLC) coupled with gas chromatography (GCI, is indispensable as a means for separation and analysis. It is particular ly useful for high- boiling substances that are dif- ficult with just the conventional GC analysis, and in oligomers of high molecular weight materials and also raw materials and byproducts. This application data book compiles a number of GPC measurements of high molecular materials, together with exemples of separation and analysis of related compounds.Contents GPC 1 11 1-2 GPC ee Molecular weight distribution, average molecular weight Thermoplastics 24 a2 23 2-4 2-5 2-6 27 28 2-9 2-40 241 2412 243 2-14 2-15 2-16 Polyvinyl chloride (PVC) Polystyrene (PS) — —— Acrylic resins (PMMA) —— Acrylonitrile-butadiene-styrene copolymer (ABS) — Cellulosies —_____ Polycarbonate (PC) Polyesters ——__— Polyamides —___— Polymethylpentene Polyimides (Pl) ——_— —— Polyetherimide (PE1) Polysulfone (PS) Polyethersulfone (PES) __________ Poly(thioethersulfone) (PTES) — Poly(parabanic acid) ——________ Ethylene Vinylalcohol Copolymer — W 14 7 18 23 24 25 27 28 2s'3] Thermosetting resin 31 Phenol formaldehyde resins — 3-2 Epoxide resins (EP) ——____ 3-3 Polyurethanes — 3-4 Melamine resins — 35 Alkyd resins [4| Rubber and adhesives 4-1 Natural rubber (NR) — 4-2. Synthetic isoprene rubber (IR) 4-3. Styrene-butadiene rubber (SBR) 4-4 Butadiene rubber (BR) 4-5 Isobutylene-isoprene rubber (Halogenated isobutylene-isoprene rubber) 4-6 Ethylene-propylene rubber (Ethylene-propylene-diene rubber) 4-7 Chloroprene rubber (CR) 4-8 Adhesives 5| Functional high molecular materials 5-1 Photosensitive resins (photoresists) 5-2 Conductive resins ——— 32 34 39 és 28s SIs & 676| Surface active agents, oils, greases and lubricating oils 6-1 6-2 6-3 6-4 6-5 7) High molecular additives TA 72 73 7-4 75 Polyoxyethylene ethers (POE) Polyethylene glycols (PEG) ——______ Polyethylene glycol fatty acid amines Grease Lubricating oils Plasticizers Antioxidants — Lubricants. ———______ Vulcanization accelerators ———______ Flame retardants 8) Others 81 8-2 8-3 a4 Polyacrylonitrile Polyacrylamide Polylactic acid ____________ Silicate polymers 62 66 67 69 gyaagy S2saGPC J crc Of the many separation modes of HPLC, gel permeation chromatography (GPC! is the simplest. The Technique has been variously referred to by a number of names, but is now most commonly called “size exclusion chromatography’ (SEC). In this mode, the separation of substances proceeds according to the hydrodynamic radius, or effective ‘size’, of each solute molecule in solution, and is relatively independent of the chemical or electronic nature of the substances and their mobile phase carrier. This independence includes the idea that the column packing, usvally composed of porous particles ‘of controlled pore size, is also relatively inert toward the solutes end solvents employed so that ad- sorption/desorption phenomena do not enter into account. ‘A generalized description of how SEC works on an essentially mechanical basis (without resort to ‘chemical, van der Weal, and thermodynamic effects, and other considerations! is as follows: Seperation takes plece according to the effective size of molecules (conveniently represented by molecular weight ‘or chain length? relative to the pore diameter and volume of the porous stationary phase of the column For @ packing with @ given mean pore diameter, molecules larger than 2 particular size (called the ‘exclusion limit) are excluded from entering the pores. Their passage through the column is hindered ‘only by the tortuosity of the route between and around particles, with the result that they elute first ‘and do so completely with the first interparticle volume of the mobile phase. (Of course, molecules, ‘or more properly particulates, thet are too large to pass at all do not elute since the packing acts 285 a simple filter) On the other hand, molecules of a size below a specific value (called the permeation limith are equally free to enter @ pore and diffuse into the smallest of confinements within the pore, ‘and are thus equally likely to be retained by a molecular sieve effect, the result being that these molecules are retained longest and cannot be separated from one another by this mechanism. Assuming they are not trapped or adsorbed, these small molecules elute completely only with the totel mobile phase volume of the column. For molecules of sizes between the two limits described above, seperation proceeds by combination of size exclusion and diffusion permeation with the larger molecules spending less time within pores 50 that they are eluted ahead of smaller molecules, The shorter residence times for the larger molecules is due mostly to the steric hindrance they exhibit between each other and with the surfaces of the substrate; the smaller molecules being able to approach the walls of the pores much more readily, thus resulting in their having longer total free paths within pores and equivalently longer intrepore residence times (other factor being equal, Figure 1.1 is a simplified snapshot of the exclusion/permeation process, while Figure 1.2 shows a hypothetical plot of separable molecular weights against elution volume for 2 hypothetical packing material of some given pore size. The stationary phese or fiter of @ GPC column must meet 9 number of requirements including @ relatively large pore volume, controlled pore diameter, inertness toward sample and mobile phase, and Tigcity necessery to prevent collapse under high pressure. Both synthetic polymeric gels and porous silica gels are employed with the synthetic polymers being most common since selective pore size ‘nd pore size distribution are fairy easy to achieve. A typical example is a polystyrene gel (styrene- S 2 8 © 6 wo Fig. 2-12 Separation of acrylic resin (PMMA:MA copolymer) Analytical Conditions Colums Shinrpack GPC-208, 804, £03, 8025; 4 columns coupled {eech 8.0mm LD. x 300mm L) Mobile phase: THE Flow rate: 1.0mLmin Temperature: 45°C Detection:RI ' 1 ' L i 5 @ & 8 s © a s 2-13. Seperation of acrylic resin (PMMA-styrene copolymer) ais Analytical Conditions: Column: Mobile phase: Flow rate: Temperature: Detection: Shim-pack GPC-806, 804, 803, 8025: 4 columns coupled leach &Omm LD. x 300mm L) TH 1.0emLimin arc Bl, UV (254nm) Fig. 2:14 Separa of acrylate oligomer Analytical Conditions Column: ‘Shim-pack GPC-802(3), 801: 4 columns coupled (each 8.0mm 1.D. x 800mm L) Mobile phase: THF Flow rate: 1.0ml/min Temperature: 40°C Detection: UV (210mm) 134 [EX] Acrylonitrite-butadiene-styrene copolymer (ABS) ABS is characterized by @ heterogeneous structure having a rubber elastomer (8) dispersed in @ continuous phase cof a hard plastic resin (AS), and various grades with versatile characteristics can be produced by differing the proportions and MW of the components [ABS is widely used in VTR's, televisions, radios and other electric household appliances, automobiles, office equipment ‘and miscellaneous items. Figs. 2-15 and 2-16 show GPC chromatograms of ABS simultaneously recorded using Rl and UV detection. RI uw wo 6 » B 2 Sm, Fig, 2-18 Separation of acrylonitie-butadiene-styrene copolymer (a) ‘Shim-pack GPC-606, 804, 802; 3 columns coupled (each 8.0mm LD. x 800mm L) ‘Mobile phase: THF Flow rate: 1.0mLUmin Temperature: 40°C Detection: Fl, UV (254nm) uw Al Fig. 2-16 Separation of acrylonitile-butadiene-styrene copolymer (b) Analytical Condit Column: ‘Shim-pack GPC-806, 808, 802; 3 columns coupled (each 8.0mm 1.0 x 300mm L) Mobile phase: THF Flow rate: 1.0mL/min Temperature: 40°C Detection: Rl, UV (@54nm)By ceillulosics Callulosics include collulose esters (cellulose acetate, cellulose nitrate) and cellulose ethers methyl cellulose, ethyl cellulose, otc. Cellulose is chiotly propared by chemically denaturing plant fibers, and cellulosics are considered semisynthatic. The resins may be softenod by adding a plasticizer. Since cellulose is crystalline and is excellent in strength, cellulosics have similar strengths unless ex- tonsively substituted. The degree of substitution (o.g., mono, tr, of tetrascetete, etc.) determines the solubility of the resin so that the greater the amount of substitu- I | 1 1 0 5 10 15 Fig. 2:17 Separation of cellulosic (a) tion at hydroxyl groups of the cellulose, the more in- soluble is the resin in many solvents. This makes these plastics weather resistant and free from static electric charge so as to be dust-free. Excellent impact resistance is anothor characteristic. Cellulosics are used in films (for photography and package materials), daly goods (stationery, spectacle frames, toys, etc), automotive parts (steering whee, paints, otc. Figs. 2-17 to 21 show GPC chromatograms of collulosics, The analytical conditions in Figs. 2-18 to 21 are the same as those in Fig. 2-17. lytical Conditions Column: Shimepack GPC-80M, [Bomm LD. x 300mm Lp Mobile phase: THE Flow rate: 1.0mi/min Temperature: 40°C Detection: Rl Sample size: 0.43% (wh, Soul.16 +4 Fig. 2-18 Separation of cellulosic (b) Fig. 2-18 Separation of cellulosic (c) 1 t 1 1 1 1 ' 1 ‘ 5 ow 8 4 Seen Fig. 2:20 Separation of cellulosic (a) Fig. 2:21 Separation of collulosic (o)[EG Polycarbonates (PC) Polycarbonates have excellent mechanical strength, especially in impact resistance, and also possess numerous superior properties as electrically insulating materials. They are some of the most widely applied ‘engineering plastics, used in electronic appliances such {as video tape recorders and office automation devices, and in mechanical structural perts such a8 automobile Fig. 2-22 Separation of polycarbonate (a) Fig. 2:28 Separation of polycarbonate (b) bumpers, cameras and watches. In addition, owing 10 high transparency, heat resistance and dimensional stability, they are also used in optical data storage and transfer devices, GPC chromatograms of typical PCs are shown in Figs. 2:22 and 23. Analytical Conditions Column: Shimmpack GPC-806, 804, 802; 3 columns coupled {each 8.0mm 1.0, x 300mm L) Mobile phase: THF Flow ra 1.omumin Temperature: 40°C Detection: Analytical Conditions Column: Stimpack GPC-806, 604, 805, az 4 cola eave (nen 8.0m 4 to. x a00mm L} Mobis phose: THE Flow rate: 1. OnUlnin Temperature: 40% Detection: A Sample see: 059% ON, 10044EX] Polyesters ‘al Polyethylene terephthalate PET) PET ig not only a typical synthetic fiber material, but ‘also @ typical industrial material used in films, magnetic tape bases and capacitor insulation. Figs. 2-24 to 28 show GPC chromatograms of PET, and Figs, 2-29 to 31 relate to bis-f+hydroxyethy tereph= thalate resin (BHET). bb) Polybutylene terephthalate (PBT) PAT is a resin high in strength, heat resistance and electric insulation, and in only the 10 years or so after its development, it has become widely used in electronic components and automative parts and is @ representative of engineering plastics. Figs. 232 and 33 show GPC chromatograms of PBT. O-0H-0Hs-0~ oj~ P ~t CH “40s / Fig. 2-24 Separation of polyethylene terephthalate (a) iu Fig. 2:25 Separation of polyethylene terephthalate (b) Polyesters are polycondensates of terephthalic acid ‘and ethylene glycol. A high purity grade terephthalic acid is required in order to avoid yellowing of the product ‘due to impurities in the acid. HPLC is used in the control ff trace intermediates formed in the terephthalic acid manufacturing process. ‘An example of analysis is shown in Fig, 2-34, Particular ly important is the detection of 4-carboxybenzaldehyde (4-CBA) and p-toluic acid, which are intermediate products in the final process. HFIP used in the mobile phase in the analytical con- ditions of GPC is an abbreviation of 1,1,1,3,3.3- hexatluoro-2-propancl Shim-pack GPC-804C, 022) 3 columns coupled leech 8mm 1D. x 300mm L) Column: Mobile phase: Chioroform HFIP (1) Flow rate: 1.0mLUmin Temperature: 40°C Detection: UV (280mm) ‘Shim-pack GPC-804C, soz) 3 colurmns coupled leach 8.0mm 1. x 300mm L}) Mobile phase: Chioroform:HFIP (2:1) Flow rate; 1.0mL/min Temperature: 40°C Detection: UV (280nm)' ' i Columns Shim-pack GPC-802Ct) ‘ | 1 4 columns coupled (each I te =) x 3 8.0mm LD. x 300mm Ly a Mobile phase: Chiorotorn Flow rate: 1.0mUmin Fig, 2-28 Seperation of polyethylene terephthalate (cl ‘Temperature: 45°C SS Detection: =A Analytical condtions for Figs. 2.27 20 ‘Analytical Conditions Column: ‘Shodex GPC HFIP-80M; (@.0mm 1D. x 300mm uy | | 1 1 i! ‘Mobile phase: Chioroform HFIP (82) 5 18 10 125 5 Flow 12 1.omLfmin rin Temperature: 40°C Detection: UV (270nm) Fig. 2.27 Separation of polyethylene terephthalate (a) Sample sizo: 0.3% (wh), 20,20 ' 1 1 1 ks iso ks Fig. 228 Separation of polyethylene Fig. 229 Separation of bis-B-hydroxyethylene terephthalate (e) terephthalate (a) \ 1 1 1 1 ' \ \ 1 1 S18 En a Fig. 2:30 Seperation of bis-Phydroxyethylene Fig. 231 Soparation of bis-P-hydroxyethylene terephthalate (b) terephthalate (c}+ ° n 0 Analytical Conditions Column: Shim-pack GPC-804C, 1802012); 3 columns coupled (each 8.0mm 1.0. x 300mm L} Mobile phase: Chloroform: HFIP (8:1) Flow rate: 1.0mi/min Temperature: 40°C Detection: UY (280nm) a2 Column: | Fig. 233 Separation of polybutylene terephthalate (b) Shim-pack GPC-802CI4h; 4 columns coupled (each 8.0mm LD. x 300mm L) Mobile phase: Chioroform:HFIP (9:1) Flow rate: Omnia Temperature: 40°C UY (280mm) Detection: 4-Carboxybonzaldohyde o-Toluic Acid Column: Shi pack CLC-ODS; (Gomm LO. x 150mm L.) Mobile phase: 10m NatisPOulpH 2.6) ‘acotonitrie (4:1) Flow rate: 1.5mLémin Fig. 234 Soparation of terephthalic acid intermediates Tomporature: 60°C Detection: UV (230nm)EE) Polyamides Polyamide is the name generally given to polymers possessing an amide bond LCONH4, which are clas- sified into natural polyamides and synthetic polyamides The natural polypeptides belongs to the former category Synthetic polyamides are roughly divided into LCORNH| types and LCORCONHA'NH-| types. The straight-chain aliphatic polyamides of which R in -CORNH-| is com- posed of (CHaln+ is called nylon n, The straight-chain aliphatic polyamide of which R in CORCONHR'NH is composed (CHaln.2" and A of (CHalm is called nylon nm. Recently, various polyamides containing R- ot R' branched aliphatic hydrocarbons, aliphatic groups or an ‘aromatic ring nucleus of benzene or cyclohexane, of a HNP Oh OT ohn 8 te — 8 4 48 $ hetero ring nucleus such as pyridine or benzimidazole have been synthesized, The biggest consumer of polyamides is the automo: tive industry, where die-cast zinc parts have been replaced by these resins. Polyamides are also used widely in glass fiber- and filer-reinforced nylons. A main feature of nylon is the excellent lubricity, and the resin is Used extensively in machine parts (bearings, gears, pulleys, chains, etc). By friction, the resin is melted and the surfece becomes smooth and thus is selfubricating, Fig. 2-35 shows a GPC chromatogram of an aromatic polyamide. i" 2 % “0 Fig. 2-35 Separation of an aromatic polyamide Analytical Conditions Coluran: Shim-pack GPC503C, 8026, 801C) 4 columns coupled (each 8.0mm 1.0. x 300mm L Mobile phase: Chioratorr HFIP (2:1) Flow rate: 1.0mL/min Temperature: 40°C Detection: UY (280nm) ‘Sample size: 0.1% (ws), 200uL 23a [EX] Polymethylpentene Polymethyl pentene is a stereotatic pohletin syn- __—Polymethylpentone exhibits good therm stabi, thesized in two steps from propylene. The staring special electrical properties, mold release properties, materi is fist cimerzed to 4methyizentene-1 which high chemical resistance, and others, and is used ex then undergoes polymerization t0 the tinal resin tensively in eral and chemical lebortory apparatus a CH=cie -4cH—cHayg BUEN 28 In syringes, blood separation vis, volumetc { dimere yy, Pahmerte evinders, beakers, ete. It also is found in electrical in CH= CHa SPS > Cite IE Ce skruments and in trays for microwave ovens, caps and duce davcrins containers for cosmetics and foodstulfs, ote sroptene fentoetene poymethypentene Fig. 2-28 Separation of polymethylpentene Analytical Conditions Column: Shimpack GPC-BOMC (2%; 2 columns coupled (8.0mm LD. x 30dmm L) Mobile phage: Chioroform-Trchlorotrfuoroetnane (8:2) Flow rate: 1,0mUJmin Temperature: 40°C Detector: RI Sample size: 0.5% (wi), 100uLERD Polyimides (1) Polyimides are thermoplastic which have the following chemical structure in common. change from low temperature to high temperature. 3) Impact-resistance and dimensional stability are excellent, 6 The resins have the following cheracteristis: 1) Ther- ‘mal stability is excellent. $) structures which entrap bubbles of COz (released from the action of water on the isocyanate group) giving @ polyurethane foam, The rigidity and thermal insulating properties of these foams makes them valued for use in re'rigeration and building materials as well as in cryotechnology. ‘Typical GPC chromatograms are shown in Figs. 311 and 12. Since the polyols greatly determine the characteristics of the product resins, care- ful process and quality control of these substances is also necessary. Fig. 3-13 shows the GPC chromatogram of polypropylene glycol which is widely used in polyurethane, and Figs. 3-14 to 16 relate 10 glycol adipinate. Column: ‘Shim-pack GPC-206(2, 804; 3 columns coupled loach B.omm LD. x 300mm Ly Mobile phase: THF Flow rate: 1.0mL/min Temperature: 40°C Detection: A Column: Shim-pack GPC-806, 804, 803, £02; 4 columns coupled leach B.omm LO. x 300mm L) Mobile phase: THF Flow rate: 1.0ml/min Temperature: 40°C 39op w. | l | | | | 10 5 2 a 0 3 rin HO-CH-CHsf-ooHoHs |-oH oH), RI | | | | | | 10 15 a B 0 3 Fig, 9-13 Separation of polyol (a) Analytical Condit Column: Shim-pack GPC-802(4) 4 columns coupled (each 8.0mm 1D. x 300mm L.) Mobile phase: THF Flow rate: 1 0miJmin Temperature: 40°C Detection: A, UV (220am),w. woorscrefo-e-( ot), -0-OcHaCHe fon fl g BS al | | Fig. 3-14 Separation of polyot (b) Analytical Condit Column: Shimpack GPC-802(a); 4 columns coupled (each 8.0mm |.. x 300m Ld Mobilo phase: THF Flow 1 10min Temperature: 40°C Detection: Rl, UV (220am) 35 3 aa w. Rt Column: Mobile phase: Flow rate: ‘Temparature: Detection: 10 15 20 2% x 3 0 | I | | | | | 10 5 2 5 0 5 “0 Fig. 3.18 Separation of polyo! (e) ‘Shim-pack GPC-802(4 4 columns coupled (each 8.0mm 1.D. x 300mm L) THF 1 Ortfmin aoc Fi, UV (220am)w. 10 15 a % 0 40 45 RI | | | | | I | 10 15 2 e 30 3 0 Fig. 346 Separation of polyol (d) Column: Shim-pack GPC-802(¢); 4 columns coupled (each 8.0mm 1.0, x 300mm L.) Mobile phase: THF Flow rate: 1.0mL/min Tomperature: 40°C Detection: I, UV (220nm) 2Melamine resins ‘A melamine-formaldehyde primary condensate is hard: ly soluble in an organic solvent, but 2 melamine resin obtained by reaction of methylol melamine with an al ‘cohol in the presence of an acid is soluble in general ‘organic solvents, and it can be analyzed by GPC. | 1 | | 10 5 a B Analytical Conditions Column: Shim-pack GPC-808, 804, 803, 802 Fig, 3-17 shows a GPC chromatogram of a repre- sentative melamine resin used in peints and adhesives, 1 1 1 3 0 45 3417 Separation of butylated polymethylol melamine resin 4 columns coupled (each 8.0mm LD. x 300mm L) Mobile phase: THE Flow rated: 1.0mUUmin Temperature: 45°C Detection: AER] Alkyd resins Aukyd resins, used extensively in paints and adhesives, ‘are obtained by condensation of a polyhydric aleahol and fan unsaturated acid, Figs. 3-18, 19 show type typical GPC chromatograms of denatured fatty acid alkyd phtha- late resins mobile phase w I I l I I IL I H 10 5 a a a 3 0 5 rin mobile phase AI l 1 I l i 1 I Il 10 5 2 B x % 40 45 Fig. 3-18 Separation of alkyd rein (a) Column: Shimpack GPC-808, 804, 803, 802; 4 columns coupled (each 8.0mm 11D. x 900mm L.) Mobile phase: THF Flow rate: 1.0mL/min Temperature: 40°C Detection; Fl, UV (254am) 9mobile phase w N IL 1 1 1 1 1 1 10 8 a B 20 5 40 6 ‘mobile phase Al 1 f i 1 ' L 1 H 10 5 a 2B 2 z 0 5 | Fig. 319 Separation of alkyd resin (b) Column: Shimpack GPC-808, 804, 803, 802; 4 columns coupled (each 8.0mm 11D. x 300mm L.) Mobile phase: THF Flow ra 1.OmLimin Temperature: 40°C Detection; A, UV (254nm)4 Rubber and adhesives As compared with other high-molecular polymeric materials, those having elasticity are limited to natural and synthetic rubber, and their applications are many, ranging from sundries to industrial products. Depending on the specific application, the characteristics of @ rubber can be varied. In order t0 compensate for the intrinsic weaknesses of rubber in terms of temperature dependence and durabilty, blending with other macromolecules, as copolymers andor additives, is important. The role of chromatography is very significant in the measurement (of molecular weight distribution, and in qualitative and quantitative analyses, ‘A rubber generally has a high molecular weight and wide molecular weight distribution, ‘and the degree of uistribution depends greatly on fluidity and viscoelasticity in kneading. EG] natural rubber (NR) With today’s level of technical progress, natural Fig, 4.1 shows a GPC chromatogram of natural rubber products tend to be regarded only as rare materials, The principal component of natural rubber is however in comprehensive performance synthetic —_polyisoprene (98% cis-1,4 bonding), and its strength materials are not always equal to natural products, and depends on the degree of crosslinking and molecuiar not a few natural products still maintain a lead even if chain length. synthetics supersede them in production quantities. typical example of a natural product in large demend is natural rubber ~{one ga0H ~0H / ; A CH, Fig. 41. Seperation of natural rubber Column: Shir pack GPC-806 (2), 804 3 columns coupled (each 8.0mm |.D. x 300mm L) Mobile phase: THF Flow rate: 1.0ml/min Temperature: 40°C Detection: Sample size: 0.2% (wl, 300uL a[2] synthetic isoprene rubber (IR) As ced sync natal ner, the ane exnibt a those of NR Fig, 42 shows GPC ctvomstogams tneca.4bondin pt 97 poten andthe Scbord of urwaiaed prane bbe with simutones UN Insbeut 1 poeent Popertes ae basealy the some Al acorn w 1 ] ! 1 ® 5 a B 2 fo geome pw bas ] 1 i ' a zB 2 Fig. 42 Separation of isoprene rubber (a) Analytical Condition Column: Shimpack GPC-804, 80212) 3 columns coupled each 8.0mm LD. x 300mm L) Mobile phase: THF Flow rate: 1.0mL/min Temperature: Room temperature Detection: Al, UV (254nm) 48Analytical Condition Column: Mobile phase: Flow rate: “Temperature: Detection: Sample size: ‘Shim-pack GPCBOMC (2); 2 columns coupled leach 8.0mm 1.0, x 300mm L) Chiroform 1.0L fin arc AI 1% (wie), 1OOML 9[J styrene-butadiene rubber (SBR) This is a representative generel-purpose rubber. SBR From SBR (6), @ low molecular woight region eluted, is generally 2 copolymer of about three quarters and was further separated by HPLC. The HPLC butadiene and a quarter styrene, and has about 70% ‘chramategram of the fraction is shown in Fig. 4.8. From trans-1,4 bonding. this, the phenolic antioxidant BHT was qualitatively Fig. 4-4 shows GPC chromatograms of SBR determined by the IR spectrum shown in Fig. 4.6 SBR (a) is highly aromatic oil-extended SBR used wide- ly in tire manufacture, and SBR (b) is a normal SBR. BS BH) Nb pi cored oncr= cnet tom RI uw SBR(a) santo) 3 Bee 50Burylated hydroxy toluene (BHT) Fig. 45 HPLC so Analytical Condit Column: Mobile phase: Flow rate: Temperature Detection: Shinmpack CLC-ODS; (60mm LD. x 160mm L) A = water B = methanol THF B, 75-9 95%, 1%/min, linear gradent 1.0mLmi| 50°C Uy (254nm) tion of cut fraction of SBR (b) 51e-var ao-oor -eos, a-envz, e-aoae, e-aaae eae Fig. 46 IR spectrum of HPLC peak from separated fraction of SBR (b) 2Figues 4.7 and 48 are GPC separations of two other SB rubbers. 0 5 10 15 2 0 Fig. 47 Separation of SBR (c) 1 1 1 ' 1 1 5 0 5 20 % 30 Fig. 48 Separation of SBR (4) Analytical Conditions Column: Shimmpack GPC-8OMC (2); 2 columns counled (each 8.0mm 1.0. x 300mm Li Mobile phase: Chloroform Flow rate: 1.0mL/min Temperature: 40°C Detection: = Sample size: 15 (wh, 100sL Analytical Conditions Column: Shinmpack GPC-80MC (2); 2 columns coupled (each 8.0mm 1D. x 300mm Li} Mobile phase: Chloroform Flow rate; 1.0mLmin Temperature: 40°C Detection: RL Sample size: 1% (w/l, TOOKL54 [EZ] Butadiene rubber (BR) Fig. 4-7 shows a GPC chromatogram of 2 predominantly cis bonded 8R obtained by solution polymerization, | l I I 10 5 2 2% Fig. £9 Separation of butadiene rubber Column: Shinmpack GPC-804, 80221; Mobile phase: Flow rate: Temperature Detection: Sample size: 3 columns coupled {each 8mm LD. x 300mm L} THE 1. Omnia 40°C Al (0.2% (wh, 200K.[E5}] sobutylene-isoprene rubber (Halogenated isobutylene-isoprene rubber) Isobutyleneisoprene rubber is a rubber which is property and gas non-permeability are unique. copolymerized from a small quantity of isoprene with _Isobutylene-isoprene rubber is widely used in tires, {a small quantity isobutylene by cationic polymerization. tubes, belts and rubber vibration isolators, etc. Isobutylene-isoprene rubber has the following ‘There are also a brominated isobutylene-isoprene rub specialties. 1) Thermal stabilty, weatherabilly, ozone ber and a chlorinated isobutylene-isoprene rubber resistance, and chemical resistance and electrical insule- (halogenated isobutylene-isoprene rubber) tion properties are excellent. 2) Impact absorption oh oh 4 CHe=C Jat CHe~C=CH~CH: i om Aryl Cone Column Smack GPC-SOMC (2 2 caus coved feech rm Psat, eee 1D 300mm ee ee) Chron on ‘oun aoe ig, 410. ‘Separation of iobuytneisoprane rer Fig 410. separa tleneisorene bb Tenpsroure; 40 Gh ] €CHr Gant CH=C—CH—CHe Or bx x Xo ar Column: Shimek GPCS0MC 2 elon coud sch Oren ea pm tx 200m (0 8 Botte phase Creator . Flow rate: 1.0mUmin wore Fig. 411 Separation of halogenated isobutyler RI[4] Ethylene-propyiene rubber (Ethylene-propylene-diene rubber) Ethylene-propylene rubber has better thermal stability, ‘ozone resistance and weatherablity than diene rubber, because it doesn't have a double bond in the polymer chain, Also, it has excellent water resistance, good low temperature and electrical characteristics, and can be sed as a filler. Ethylene-propylene rubber is widely used CH CH, It CH GH I oh, 1 1 1 ' 1 1 o 5 10 15 a B Fig. 412 Separation of ethylene-propylene rubber EO OH Ie OH GH Ie CX I= cH, X: the third component Exhlidone-norbornene Dieycionentadione bexadi 5 10 1% 20 Fig. 4-13 Separation of ethylone-propylene-die in ties, tubes, weterprooting sheets and various parts for motors Ethylene -propylene-diene rubber is © rubber which was introduced 2s a double-bond unsaturated compound 25 the third component in an ethylene-propyiene copolymer, Analytical Conditions Column: Shimpack GPC-OMC (2) 2 colurmns couplad leach 80mm LD. x 300mm L.) 1 Mobile phase: Chloroform 0 Flow rate: 1.0mU/min rnin Temperature: 40°C Detector: AL Sample size: 1.0% (wiv, 100uL Analytical Conditions Column: Shimmpack GPC-EOMC (2), | 2 columns coupled (each .omm LD. x 300mm L} ' Mobile phase: Chiroform Flow rate: 1.0mijmin Temperature: <0°C Detector: I | Sample size: 1.0% (wid, 100Chloroprene rubber (CR) This is an ollproof rubber developed many years ago, but is stil used widely. Chioroprene readily undergoes radical chain-reaction polymerization and is likely to undergo sell-crossiinking. Control of its polymerization is. thus important. Applications include electric wire insulation and ‘weather covering, hoses and automotive parts Fig. 4-14 shows a GPC chromatogrem of chioroprene rubber. z f 04 bo1- ome —(04- be 1-08 ane, 2104 92108 1 1 I | 1 bo of 8 & & 8 Fig. 4-14 Separation of chioropr Analytical Conditions Column: ‘Shimaack GPC-80M (® 0mm 1.0. > 300mm Li, Asanipak GS-10 (7.6mm LD. x Sd0mm LI, 2 columns coupled Mobile phase: THF Flow cate: 1.0mL/min Temperature: Room temperature Detection: Sample size: 10-fld diluted, SOuL 7EE) adhesives Basic requirements for adhesives are, regardless of the form of supply, to be in a liquid state at the moment of use so as to wet, spread, and fill up the geps of a solid surface (adherend), and to then solidify 10 build Up the adhesion property suitable for the purpose of use The means far liquefaction may include formation of solution or emulsion by using water or an organic sok vent, the use of a liquid monomer or oligomer, or by heating. The means for solidification includes evapora- tion of solvent, cooling, chemical reaction, or decompression, Applications for adhesives cover all industrial fields such as in plywood manufacture, building, civil engineer- 1 1 a 5 10 5 Fig. 418 Separation of (rubber + phenol resin) adhesive (a) Analytical Conditions Column: Shinvpack GPC-8025, 80112); 1 a ing, packaging and in rubber products, and they are also used in the household. n addition to the general-purpose adhesives, there are advanced products, including the structural adhesives having high strength, as well as functional adhesives presenting other functions aside from adhesion (electrical conductivity, heat transfer, etc.). Figs, 4-16 and 4-16 show GPC chromatograms of (rubber + phenol! adhesives, and Fig. 4-17 relates to a phenol resin adhesive The analytical conditions in Figs. 416 and 4-17 are the same as those in Fig, 4-15. 1 1 i N % 0 B 4 3 columns coupled (each 0mm |.D. x 300mm L} Mobile phase: THF Flow rate: 1.dmLUmin Temperature: 40°C Detection: UW (25dne) Sample size: Gold diluted, SOuL1 1 1 1 i 1 n 1 5 0 5% © & w B 4 Fig. 416 Separation of (rubber = phenol resin) adhesive (b) 1 1 1 1 1 ' L ‘ 1 a 5 @ 6 02 8 0 % 4 Fig. 417 Seperation of phenol resin adhesive5 Functional high molecular materials Fine polymers are high molecular materials possessing unusual characteristics which sive them functional uses completely different from the high molecular materials mentioned 50 far, These polymers may be understood as high molecular materials capable of reacting in a certain way by responding to a certain external stimulation from light, ai, magnetism, pressure or the like. Also, the substrate carrying a macromolecular film may also be ‘categorized as a fine polymer. Examples of GPC analysis of two fine polymeric materials are introduced below. Edi photosensitive resins (photoresists) ‘When one of these resins is exposed to light, which causes chemical changes, it may dissolve (positive type) Cr solidify (negative type). This is used in formation of images of circuits of electronic elements and is one of the indispensable tools for fabrication of fine, complex circuit patterns of IC's, LSI's, and super-LSI's. The photoresist is changed by light or temperature, which isturbs the stable formation of the high molecular film. ‘The GPC anaiysis of photoresists is applied in the quality Control, and research and development for adherence to wafers or for etching effects. Fig. 5-1 shows GPC of a positive-type photoresist, in which (a) is the normal chromatogram of the unreacted material, and (b) is the result after direct exposure to sunlight. In (6), the profile is slightly shifted to the higher molecular weight side, and changes are noted in the lower molecular region (photosensitizer, te) I 1 1 1 1 1 ow 6 8 5 D 8 fa) ' t 1 ' 1 L mo 6 2 a yn 8 Fig, 51 Separation of photoresist" io. par Column: ‘Shim-pack GPC-€04, 80212) 3 columns coupled (each 8mm 10, x 300mm L) Mobile phase: THE Flow rate: 1.0ml/min Temperature: 40°C4 conductive resins Fine polymers are generally electrically insulating _of poly(2.5-pyroll which is one of the conductive resins materi, but conductive resins have special chemical having an electric conductivity of as high as 100S/em structures giving them similarities to metals for conduc- obtained by doping with BFa tion of electricity. Fig. 5-2 shows @ GPC chromatogram oH—cH 1 I I 1 I a 5 10 15 2 Fig. 52 Soparation of conductive resin i Column: Shimpack GPC-804, 802 2 columns coupled leach 80mm 1.0. x 800mm L) Mobile phase: Chioroform Flow rate: 1.Gmi/min Temperature: Room temperature Detection: a6 Surface active agents, oils, greases and lubricating oils [EE] Polyoxyethylene ethers (PC Figs. 6-1 and 6-2 show GPC chromatograms of a HPLC. polyoxyethylene phenylether and alkylether, respective: Fig, 6-4 shows separation of polyoxyethylene Iy. In both cases, the addition mol number of the _phenylether by akky! chain length. In this case, regardless oxyethylene is 20. of the addition mol number of the oxyethylene Fig. 63 shows separation of an octy’phenylether by monomer, it is possible to elute them all. CsH»{O)- © fon.one -ofn | | | | 1 » % x 38 “0 Fig, 6-1 Separation of polyoxyethylene phenyiether Column: ‘Shim-pack GPC-802 (4), 801; 5 columns coupled leach 8.0mm I.D. x 300mm L) Mobile phase: THF Flow rate: 1.0mL/min Temperature: 45°C Detection:Caateo-foHcH40 +s | | | 1 | I 1 10 15 a % 0 3 40 | Fig. 62 Separation of polyoxyethylene alkylether Column: ‘Shirmpack GPC-8024); 4 colurmns coupled leach 8.0mm 1.0. x 300mm LI Mobile phase: THE Flow rate; 1.0mlJmin Temperature: 40°C Detection: il 6Column: Mobile phase: Flow rate: Temperature: Detection: Sheela Cama ha Fig, 63 Separation of polyoxyethylene octyipheno! ‘Shim-pack CLC-SIL; (Gorm LO. x 180mm L) rHexanerethanol (95:5) .5mbjmin oom temperature UY (2540)octyl Fig. 64 Separation of polyoxyethylene phenylether by alkyl chain length Column: Shimmpack CLC-O0S, (6.0mm 1.0. x 160mm L Mobile phase: Methanotwater (4:1) Flow rate: Temperature: Detection: UV (254nm) 6[Polyethylene glycols (PEG) GPC chromatograms of typical PEGs are shown in Figs. 68 and 66. v-focny-cn, 0" Columm: Shim-pack GPC- 2, @cokrms coupled (oach B0mm 1D. x 200mm LI Mobile phase: THF oe 2 & * * & Flow rate, 1.0mUinin aration of lone aly! (a Temperature: 40% Fig. 65. Separation of polythyiene veo! (a) Temperate: a — = Column: Shim-pack GPC | ana. ‘cokes coupled (aach Som LO. x acon L) i 1 Mobile phase: THE 0 ~~ Flow rate: 1.0mLimin, to Temperature: 40°C Detection: Al[EX Polyethylene glycol fatty acid Fig. 6-7 shows separation of polyethylene glyco! stoaryl amine by HPLC. Fig. 67 Separation of polyethylene glycol fatty acid amine. Analytical Condit Column: Shim pack CLC-ODS; (6.0mm LD. x 150mm Lp Mobile phase: 0.05% phosphate aqueous solution methanol (2°) Temperature: Room temperature Flow rate: 1.2m\/min Detection: UY (220nm) a7[El] Grease Fig. 6-8 shows the deterioration of grease 2s _the base oil, and shows the consumption of certain ad: measured by GPC. The grease in the deteriorated state dives. (b) has changed inthe molecular weight distribution of ous | a- Sam Eee | Toa ate etna 1 fesk normaton Time in) mw. von ae reer sna 3 ‘oo zw zer ‘teres oo yon 238 2 Numberavecage MM.= 1729 Woghtevenge MW.= 388 Powage tive B08 Diversity ANAM 193222 Oparivty ZIM 3.401 “ot gta enamel 2 ok intrmatn Time din) ave vse ae Tas oo 3 ‘o> Pw Sab seH8 on Sows 28 ? Numbecverage M.vt= 1602 Woighteage MMe 355, Ravage MWe 23 Dispersivty MWIMNA 1.85786, Elution curve Dlopersivty MZMIN 224858 : 7 = yor oF ou! “ + } \ . | Analytical Condon f Colum: Shenoack GPC-BO4 / va) fmm 10, x 200m LI | Mobile prose: THF Beep eaciey wl ooo Flow rate: 1.OmLnin | Fig. 6-8 Separation of g Temperature: Room temperature[BQ Lunricating oils A lubricating il is intended to form a thin oil film be tween two solid bodies to support the whole load, and separote the two bodies completely to reduce abrasion. The lubricating oil is required to have a proper viscosity, physical and chemical stability, low coefficient of friction ‘and low oxidation potential. Lubricating oils are made Fig. 69 Separation of lubricating oil (al Fig. 610 Separ ion of lubricating oll (a) from petroleum, animal oils, or vegetable oils, and syn- thetic lubricating ils are made from dibasic acid esters (or silicones, Solid meterials include grephite and talc, and ‘greases are used as semisolid materials. Figs. 69 and 6.10 are GPC chromatograms of the ‘same lubricating oll measured with UV and Ri detection 2 Analysis Conditions Column: Asahipak GS310; (7.6mm LO. x 00mm L Mobilo phase: THF Flow rate: 1.0mL/min ‘Temperature: Room tomperature Detection: UV (254nm) Sample size: 1% (w/v), SOuL Analytical Conditions Column: Asahipak GS-310 (7.8mm 1. x 500mm Li Mobile phase: THF | Flow rate: 1.0mtmin Temperature: Room temperature Detection: = | Sample size: 1% (wiv 200LColumn: Asahipak GS310, (7.8mm |.D. x 500mm L) rnin Mobile phase: THF Flow rate: 1.0mL/min oom temperature al Sample size: 1% (wh), 200,L Sa Fig. 6-11 Separation of lubricating oil (b) 2 Aavaly tons mn Colum: Asahipak GS-10; {7.6mm LD. % 500mm L) Mobile phase: THF Flow rate: .0rnrin TTempersture: Room temperature Fig, 612 Soparation of lubricating oil (e) Detection: RI Sample size: 1% (wd, 200iLHigh molecular additives EQ] Plasticizers A plasticizer is an addltive for giving a desired flexibility ‘at some temperature by lowering the elasticity or glass transition point of a high molecular substance. It is also used for making a polymer easier to work at higher temperatures by lowering the mel viscosity. Plasticizers are added to various high molecular materials, especially Vinyl polymers, and in overall quantity consumed they are most widely used in polyvinyl chloride. 2 Gs ‘Among the popular plasticizers, the dialkyl phthalates ‘are shown in Fig. 7-1, and aliphatic dibasic esters in Fig, 72, Polyesters and epoxies of relatively high molecular weight are also used. A separation example of adipic acid polyester (M.W. about 2000) is shown in Fig. 7-3. DMP (Oimethy! phtnaiate ) DEP ( iethy! phhalate ) DAP (bial phthalate ) DPP ( Dipropyt phuhaiate ) DBP ( Dibuyl phthalate ) TCP (Teehledy! phosphate ) DOP (Dicey! phthalate) DDNP ( Dinonyl phthalate ) Fig. 7-1 Separation of plasticizers Analytical Condition Column: Shirypack CLC-ODS, (6.0mm LD. x 150mm L) Mobile phases: Water acetonitile (3:2) — acetonitrile 100%, 2%%/min, near gradient Flow rato: 1.om\jmin Temperature: 40°C Deteotion: UY (254nm) 1BPBG (Buty phthall butyl glycoiste! BBP {Benayl nbutyl phthalate) Beso DOA. 1Diocty! adipated DOS {Diocty! sebacate) . Samm 10 a 150mm LI Z Mobi phase = Methanol:water Methanol Bo ter vein Dower Yetta 3. en som 0 5 m & 2 8 Tati” hes eaine Fw coe Yanun 7-3. Separation of polyester plasticizer Detection: UV (220nm)Antioxidants 2) Radical inhibitors (hindered phenols) ‘agent, a separation example for a dipropionate fatty ‘These are added in order to increase resistance to acid ester is shown in Fig. 7-5 oxidation of high molecular substances. Recently, in- __¢} Ultraviolet wavelength absorbents hibitors of a considerably high molecular weight tend This is added to absorb UV light energy to convert to be used, Antioxidants of high molecular weight are it into a lower energy form to suppress radical geners- superior to thase of low molecular weight in votatility, tion which would otherwise load to further polymeriza transfer property and extractability tion and/or crossiinking. Salicylic acid, benzophenone ‘A separation example for a typical phenolic an- and benzotriazole compounds are used. These absoro- tioxidant is shown in Fig. 7-4 ents are generally used together with radical prohibitor b) Hydroperoxide decomposing agents and hydroperoxide decomposing agent, A separation As a typical example of a peroxide decomposing exemple is given in Fig. 76. 1. 2,2-Bis shyckoxyphenvi propane 2. 2,8Dit-buty-4-methylphenol 3. 2,2°-Methylene-bis(-methyi*-butylphenol 4. 44°Butylidenebis (--butylrcresol) 5. 4,4:Thiobis (@-methyi6-t-butyiphenol 6 2. 8 1,1.9-Tris (butyl hydrony-2-methyiphenyb butane 1.3,5-Tis (-methy-4+nycroxy-o-Hbutyipenol butane 1,3,5-Trimothy12.4,6:0s 2,5:dh-buty4-hydroxybenayl benzene Fig. 7-4 Separation of phenolic antioxidant Analytical Conditions Column: Shim-pack CLC-ODS; (60mm 1D. x 150mm L) Mobile phases: A= 10mM acatic acid B = acetoniilecTHF (1:1) B, 60 -+ 100%, 2%/min, #1 gradient Flow tate: 1 5mi/min Temperature: 50°C Detection: UY (270nm) 2” ANALG Fig. 75 9 i paiTop (cH.0H1,0}0 on oLTOP postop 5 10 15 Separation of dipropionate fatty acid ester on Ki 1 OLIN cl mM ‘CH 9 2S Orooun ai Bu 5 10 15 Fig. 7-6 Separation of ultraviolet light absorbent Column: ‘Shimpeck CLC-ODS; (6.0mm 1D. x 180mm L) Mobile phase: Watermethano! THF (2:11) Flow rate; 1.0mLmin Temperature: 50°C Detection: UY (210nm) 1. 242:Hydroxy-5-methyt phen) ‘S-chiorobencotnazole 2. 2-Hydroxy-4n-oetyloxybenzophenone 3, 249-Tent-butyl.2"nydioxy-Samethyt- phenyl Sehlorobenzoviazole 4. 2.8'5'Ditertbutyi2"hydroxy-phonyS hlofdbenzotazole Column: Shire pack CLC-ODS, (6.0mm |.D. x 150mm L) Mobile phase: 10miM acetic acciacetonitile STHE (1:22) Flow rate: 1.0mUJmin Tomperature: 45°C Detection: UY (254nm)Lubricants Lubricants are additives for improving the workability A GPC analysis example of denatured castor oils is of high molecular materials by allowing chains to slip shown in Fig, 78 past one enother, and their offective use enhances productivity. From among the numerous lubricants (in- temal lubricants), lubricity, is shown in Fig. 7-7. Laurie ROONHs Eroirie. Fig. 7-7 Separation of fatty acid amine Analytical Concitions Column: Shims pack CLC-ODS; (6.0mm 1.D. x 150mm L) Mobile phase: Acetonitilo:THF (9:1) Flow rate: 1.0mLimin Temperature: 50°C Detection: UV (210nm) %% st x 1 0 1 st 1 Column: Mobile phase: Flow rate: Temperature: Detection: @ o) Fig. 7-8 Separation of denatured castor oils (a), b) Shiny pack GPC-802K4 4 columns coupled each 80mm 1.D. x 8OGmm L) THE 1.OmLimin asc RI[EZ] vulcanization accelerators Used to lower and shorten the vulcanization tempera ture and time, They also function to enhance the phys cel properties of vuleanized rubber and improve deterioration resistance Column: ‘Shiew-pack CLC-ODS; (Gomm 1. x 160mm Ly Mobile phase: 1bmiMI NaHaPOs ipl 2.6} methanol (1:4) Flow rate; 1SmLimin Temperature: 40°C Detection: UV (2540) Fig. 7-9 shows a separation example of a thiazole vul canization accelerator. oar swt 2 GLY 5 Ce ee a on Nou, 4, ©LSo-s-miOD 2-Mercaptovenzimidazote 2-Metcapicuenzothiazole Thivam Cyclonexysulfenamide 1 20 7-9 Separation of vulcanization accelerator 7[EZ Flame retardants One of the demerits of high molecuiar materials used as structural materials is their inferiority in fre resistance. Thus, flame retardance is an important subject in the fields of building materials, electricity, automobile and ‘exile industries. Resistence to combustion is achieved sither by adding flame retardants such as alkylphosphate esters or halogenated paraffins to the high molecular on 10-46) Gr cH, BF Fig. 7-10 Separation of flame retardant mixture bob b & & & Fig. 7-11 Separation of brominated epoxide resin 7 9 paration of brominated epoxid: materials, or by directly introducing a halogen into the monomer unit used for forming the polymer. Figs. 7-10 and 7-11 show a separation example for @ mixed bromineted phenyl flame retardant, and a GPC chromatogram of epoxide resin synthesized using brominated bisphenol A as the monomer. 1. 28,5,6Tettabromep-cresol 2. Tetrabroma bisphenol A Analytical Conditions Column: ‘Shim pack CLC-ODS; (6.0mm 10. x 150mm L) Mobile phase: 10mM acetic acid meth- anol (8:1) Flow rate: 1.5mL/min Temperature: 40°C Deteetion: UY (270nm) Column: Shim-pack GPC-803, 80202); 3 columns coupled leach 80mm 10. x 300mm L) ‘Mobile phase: THF Flow rate: 1.0mLmin Temperature: 40°C Detection: UY (280nm)Others EX] Polyacrylonitrite Polyacrylonitrle (~CH —CH:—) forms extensive in- T oN termolecular hydrogen bonding, and is therefore tough {next to nylon and Tetron), and has a very high softening temperature (over 200°C) and melting point (sbout 317°C). Furthermore, this polymer is likely to form con- jugate double bonds, and is decomposed by heat before being melted. Therefore, polyacrylonitile fibers cannot i I i I ° 5 10 15 Fig. 6-1 Separation of polyacrylonitile (a) i 1 | I o 5 10 15 Fig. 82 Separation of polyacrylonitile (b) bbe prepared by melt spinning, but ere made by wet spin- ning. The main applications of polyacrylonitie fibers are jerseys and carpets, and as a special application they may be used as the base material for carbon-reinforced fibers, GPC chromatograms of polyacrylonittile fiber are shown in Figs. 8-1 and 8-2. Column: Shodex GPC AD 80M. (@omm 1D. x 250mm L) Mobile phase: Dimethytormamice Flow rate: 1.0mL/min Temperature: 40°C Sample size: 0.2% (wl, 200uL Column: Shodex GPC AD-BOMIS; Mobile phase: Dimethyformamide Flow rate: 1.0ml/min Temperature: 40°C Detection: Rl Sample size: 0.2% (wh), 200uL[EE] Polyacrylamide Polyacrylamide is obtained by polymerization of acrylamide (CH=CHCONHD). Polymerization is initiated by light, radiation or heat, aside from the usual radicel polymerization initiator. Aqueous solution polymerization i's most widely employed because the monomer and the product polymer are soluble in water. Polyacrylamide is amorphous, and is a nonionic polymer soluble in cold water. The most typical applice- EH GH Ie c=0 Nie 0 5 10 15 Fig. 83 Separation of polyecrylamide (a) Fig. 8-4 Separation of polyacrylamide (b) tion is 28 paper reinforcement, and the COOH group fr CONH2 group bond to pulp fibers to increase overall bonding strength. Additionally, in relation to the pollution problem, this substance is also noticed as a soil sedimentation agent. It is also used in sizngs, paints and edhesives, Figs.8-3 and 8-4 show GPC chromatograms of polyacrylamides. Column: Asahipak GS-510; (7.8mm LD. % 500mm L) Mobile phase: 10mM phosphate buffer, pH 26 Flow rate: 1 OmLJmin Temperature: Room temperature Detection: A Sample size: 0.1% (wis), 200uL. Column: Shodex OHpak KB-B0M: (BOmm LD. x 300mm L) Flow rate; 0.5mL/min Temperature: 40°C Detection: A Sample size: 201d diluted, 200uLEEX) Polylactic acid Lactic acid possesses both hydroxyl and carboxy! groups, and a self-esterification reaction occurs to produce a lingar polyester. The frst esterification product on is 2 dimer lactyHlactic acid yyy Ay O~ COOH oO CH However, as the concentration is increased, conden- sation is promoted, and a linear polylactic acid, oF tr, tetra- oF other polymeric lactic acid is formed, The Il 1 10 5 2 B 0 Fig. 86 Soparation of denatured polylactic acid (b) Fig. 85 Separation of denatured polyiactic acid (a) general structural formula of a polylactic acid 1s ex: pressed es follows cHscHCOOH (CHsCHCOO), 1 (CHyCHOHCOO Polylactic acid polymers are mainly used in various medical equipment. Figs. 8-5 and 6 show GPC chromatograms of denatured polvlectic acids Column: Shim-pack GPC-808, 804, 202; 3 columns coupled (each BOmm LD. x 300mm L) ‘Mobile phase: THF Flow 1.0mL/min Temperature: 40°C Detection: Al Sample size: 0.4% (wi), SOL Column: Shim-pack GPC-806, 804, 02 3 columns coupled (each 80mm LD. x 300mm Ld Mobile phase: THF Flow rate: 1.0ml/min Temperature: 40°C Detection: Sample size: 0.4% (wi), SOUL. 8[EZ] Silicate polymers Of the compounds expressed by R'nSi(ORe- silicate testers are those of which a is 0, that is, SHORI4, while those of which n is 1 to 3 ate called organcalkoxysilanes CF siloxanes. In preparation of silicate esters, alcohol or phenol is made to react with silicon tetrachloride. The polymerization product of a silicate ester is called @ cate polymer, Applications of alkoxysilanes are varied, bbut they are roughly divided into two types, that is, whether the S-O-R bond is left intact or is hydrolyzed fat the final point of application. Applications for the hydrolyzed form include bonding agents for firebrick and ‘others. Applications for the former include lubricating oils and water hardening agents. Compounds with small molecular weight such as tetrasthoxysilane and tetramethoxysilane are common laboratory reagents. By ‘contrast, compounds with large molecular weight, such as tetrabutoxysilane and tetrabenzyloxysilane are used in mechanical applications. Of ihe silicate esters, tetraethoxysilane forms a silicone paint when combined ‘with alcohol, water and pigment, and itis used in paint- ing and sealing of coarse porous products, mortars for rofractories, and castings. Figs. 8-7 to 8-16 show GPC chromatograms of verious silicate polymers. Analytical conditions for Figs. #7 to 8-16 Column: Asehipak GS-310 (7.6mm 1D. x 500mm L) Mobile phase: Methanol Flow rat 1.0mLmin Temperature: Room temperature Detection: il Sample size: Stock solution 20, 1 1 1 1 1 1 1 1 1 1 o 5 0 6% 0 Fig. 67 Separation of silicate polymer (a)1 r L 1 f o 5 0 6 2 8 4% 0 5 0 | Fig. 89 Separation of silicate polymer (c) Fig. 8-10 Separation of silicate polymer (d) fl 1 1 t 1 1 j 1 1 1 o 5 0 6 @ o 5 0 5 2 Fig. 811, Separation of silicate polymer (e) Fig. 812 Separation of silicate polymer (f)1 1 1 1 1 1 1 1 n 1 0 5 © 6 @ Fig. 814 Separation of silicate polymer (h) o 5 0 6 a 0 § 0 1 2 Fig. 8.18 Separation of silicate polymer (i) Fig. 818 Separation of silicate polyme a&) SHIMADZU ‘SHADED CORPORATION. wnat Warttng Den 4 Hanes tame Cheah Tne TOLER Jan Pree OGSRIOST Fa YOHOTESTIO ‘ae as SHMADZU TORO SHMOZY SCENT METRES We 12 Rico iw, Caro, Mays 2108, USA Pete F0981427 Foe 122 0017 a7 saADZY DEUTSCHLAND Gr ‘batt Sse 60, ATE Dubay, FR. 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