Polymer Chemistry. Li Guang Hua ( 李光华 ) Lab: 材料楼 409#,321# Cell phone:

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1 Polymer Chemistry Li Gua Hua ( 李光华 ) Lab: 材料楼 409#,321# lighua@gmail.com Cell phone: School of Chemistry & Chemical Eineerin g

2 CHAPTER 10 Thermosetti Polymers : Fusible & soluble polymer Thermoplastic polymer Crosslinki Infusible & insoluble polymer Thermosetti polymer 1. Phenolic Resins 2. Amino resins 3. Unsaturated Polyester Resins 4. Epoxy Resins 5. Polyurethanes (1) School of Chemistry & Chemical Eineeri

3 1. PHELIC RESIS (I) F Phenolic Resins (Phenolics) Phenol-formaldehyde (PF) resins Commercialization : in 1909 (Bakelite company) f = 3 H H H H HCH H HCH H HCH HH 2 C H H H (2) School of Chemistry & Chemical Eineeri

4 1. PHELIC RESIS (II) H H HH 2 C H + H H H H H HH 2 C H 2 C HH 2 C H -HCH H H HH 2 C (3) School of Chemistry & Chemical Eineeri

5 1. PHELIC RESIS (III) ovolacs Conditions : formaldehyde : phenol = 0.8 :1 Catalyst : acid (H 2 S 4, oxalic acid) H +HCH H H H H H H H H H n ovolacs (MW : 700 ~ 1000) (4) School of Chemistry & Chemical Eineeri

6 1. PHELIC RESIS (IV) H H H Phenolic resin n ovolacs Filler Moldi powder hexamethylenetetramine 6 HCH + 4H 3 Catalysis & crosslinki (5) School of Chemistry & Chemical Eineeri

7 1. PHELIC RESIS (V) Resoles Conditions : formaldehyde : phenol = 1.25 :1 Catalyst : base (ah, H 3 ) H +HCH H H H H H H H Phenolic resin H H Resoles (MW : 500 ~ 1500) (6) School of Chemistry & Chemical Eineeri

8 1. PHELIC RESIS (VI) Properties of Phenolics Have good chemical and thermal resistance, dielectric streth, and dimensional stability. Most phenolics contain fillers or reinforcements General-grade phenolics are filled with mica, clay, mineral flour, cellulose, and chopped fabric Eineeri-grade phenolics are reinforced with glass or organic fibers, elastomers, graphite Products made with these resins are inherently low in flammability, are creep resistant, and have low moisture absorption (7) School of Chemistry & Chemical Eineeri

9 1. PHELIC RESIS (VII) Applications of Phenolics Adhesives Ex., the manufacture of plywood and fiberboard Coatis Ex., coatis on cans, drums, metal pipe, electrical insulation, varnishes, and metal primers Plastics Ex., printed-circuit boards, gears, cams protective, decorative surfaces for tables and furniture, switches, pump housis, and cutlery handles thers Ex., friction materials (brake lini, transmission bands), foam insulation, and carbonless copy paper (8) School of Chemistry & Chemical Eineeri

10 2. AMI RESIS (I) F Amino Resins urea-formaldehyde (UF) resins melamine-formaldehyde (MF) resins H 2 H 2 C H 2 H 2 H 2 urea (f = 4) melamine (f = 6) C H H C H 2 H 2 + HCH C H 2 H H H H (9) School of Chemistry & Chemical Eineeri

11 2. AMI RESIS (II) H 2 CHH H H H 2 C + H 3 3 H 2 C H 2 C H + H H H + H 2 H + H + H 2 H + H + HCH + H 2 (10) School of Chemistry & Chemical Eineeri

12 2. AMI RESIS (III) H H C H C H C H C H Methylene bridge H C H C H Methylene ether bridge H C H C H H C C H Cyclic bridge C H (11) School of Chemistry & Chemical Eineeri

13 2. AMI RESIS (IV) Properties of Amino Resins A distinct advantage of the amino resins over the phenolics is clearer and colorless They are harder than phenolics but have somewhat lower impact streth and resistance to heat and moisture The melamine resins have better hardness, heat resistance, and moisture resistance than the ureas Applications of Amino resins Adhesives (better performance than the phenolic resin) Ex., the manufacture of plywood and fiberboard Melamine resins are used to produce colored dinnerware and dinnerware with decorative patterns. Amino resins also find extensive as automotive parts; the cheaper ureas are used as primers while the melamines are used as topcoats (12) School of Chemistry & Chemical Eineeri

14 3. USATURATED PLYESTER RESIS (I) F Unsaturated Polyester (UP) Resins C C + C C CH 3 + 2H CHH toluene sulfonic acid 150 ~ 200 o C CH 3 CH 3 C C CH CCH CHC CH + 2H 2 Unsaturated polyester (MW 1000 ~ 2000) (13) School of Chemistry & Chemical Eineeri

15 3. USATURATED PLYESTER RESIS (II) CCH CHC + CH peroxide glass fiber CCH CHC CH CCH CHC Glass fiber reinforced UP resin Properties & Applications of UP resins Have a good combination of resistance to softeni and deformation at high temperature, electrical properties, resistance to corrosion, weak alkalies, and stro acids and possess very good weatherability Construction : Ex., tub and shower units, buildi facades, and specialty floori Transportation and marine industries: Ex., truck cabs, auto body repair, and boat hulls (14) School of Chemistry & Chemical Eineeri

16 4. EPXY RESIS (I) Epoxy Resins (n+2) H 2 C CH Cl + (n+1) H CH 3 C CH 3 H ah aq -HCl CH 3 H CH 3 H 2 C CH C CH C CH CH 3 CH 3 n = 0 ~ 12 (MW = 340 ~ 3800) n Ar + H 2 C CH Cl Ar CH Cl Ar CH Ar Ar Ar CH + Cl (15) School of Chemistry & Chemical Eineeri

17 4. EPXY RESIS (II) CH + H 2 R H 2 H CH H CH R H CH CH H CH 3 C CH CH 3 H + R C C CH 3 C CH CH 3 C R C CH 3 C CH CH 3 (16) School of Chemistry & Chemical Eineeri

18 4. EPXY RESIS (III) Properties of Epoxy Resins Possess high chemical and corrosion resistance, toughness and flexibility, good mechanical and electrical behavior, and outstandi adhesion to many different substrates A wide rae of products varyi in properties and curi temperature are obtained for specific applications by proper selection of the monomers, additives, and curi agents. Applications of Epoxy resins Adhesives Coatis : Ex., marine, maintenance, drum, and can coatis Structural composites : Ex., military (missile casis, tanks), aircraft (rudders, wi skins), automobiles (drive shafts), and pipe Laminates : Ex., electrical and electrons industries (circuit-board substrate) (17) School of Chemistry & Chemical Eineeri

19 5. PLYURETHAES (I) F Polyurethanes (PU) nc R C + n H R' H CH R HC R' n diisocyanate glycol polyurethane CH 3 C C 2,4-tolulenediisocyanate (TDI) C C methylene-4,4 -diphenyldiisocyanate (MDI) 2 C + H 2 R'' H 2 HCH R'' HCH diamine urea linkages (18) School of Chemistry & Chemical Eineeri

20 5. PLYURETHAES (II) H C + H C H + C R' C C Allophanate C H R' Biuret H C C H 3 C trimerization catalyst H 2 -C 2 C C C HCH C H 2 HCH (19) School of Chemistry & Chemical Eineeri

21 Elastomers 5. PLYURETHAES (III) CH 3 C C excess + B CH 3 C HC B CH CH 3 C HC B CH CH 3 H 2 R'' H 2 or H R' H C HCH R'' HCH C Crosslinked PU B (MW = 1000 ~ 2000) : H CH 3 CH n H poly(propylene glycol) H C( ) 4 C poly(diethylene glycol adipate) n H (20) School of Chemistry & Chemical Eineeri

22 5. PLYURETHAES (IV) Properties of PU elastomers Extremely good abrasion resistance and toughness, combined with good elasticity and resistance to greases, oils, and solvents. Applications of PU elastomers Forklift tires & skateboard wheels Automobile parts Ex., bumpers, fenders, door panels, gaskets for trunk, windows, windshield, steeri wheel, instrument panel Sporti goods Ex., golf balls, ski boots, football cleats (21) School of Chemistry & Chemical Eineeri

23 5. PLYURETHAES (V) Fibers H H + C Ar C B (MW = 2000 ~ 3000) excess C Ar HC CH Ar HC CH Ar C C Ar C H 2 R H 2 (unreacted) CH Ar HCH R H CH Ar HC Hard segment spinni Soft segment Crosslinked PU fibers (22) School of Chemistry & Chemical Eineeri

24 5. PLYURETHAES (VI) Polyurethane fibers have unusually high elasticity Lightweight foundation garments and swimsuits They do suffer from limited resistance to hydrolysis Foams H H H or + C Ar C C C excess H MW ~ 3000 H H 2 C HCH -C 2 C H 2 Flexible foams or Rigid foams C Ar C (unreacted) HCH (23) School of Chemistry & Chemical Eineeri

25 5. PLYURETHAES (VII) Applications of PU foams Flexible foams Ex., insulators, automobile crash panels, upholstery, beddi, carpet underlays, and synthetic spoes Rigid foams Ex., commercial roofi, residential sheathi, and insulation for water heaters, tanks, pipes, refrigerators, and freezers. (24) School of Chemistry & Chemical Eineeri

26 5. PLYURETHAES (VIII) Coatis H H H + C Ar C excess C C atmospheric moisture C H 2 -C 2 C HCH HCH C Ar C (unreacted) one-pot coatis Have very good resistance to abrasion and solvent attack plus good flexibility, impact resistance and weatherability They can be applied by dip, spray, or brush and adhere well to a wide variety of materials Gymnasium and dance floors and bowli pins, in magnet wire coatis, etc. (25) School of Chemistry & Chemical Eineeri

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