Nylon 6, Nylon 66, and PET Depolymerization

Dr. Malcolm B. Polk Georgia Tech School of Textile and Fiber Engineering

Depolymerization of PET
An important source of PET for rocy cling is physically cleaned post-consumei bottles which are ground to form flake, d spolymerized, purified, and repolymerizec to form recycled resin/bottles. Commercial depolymerization approaches include methanolysis and glycolysis. Hydrolysis although feasible is not a commercial process because of the costs associated with purification of the terephthallc acid

Depolymerizaticm of PE

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Methanolysis
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Methanolysis involves two steps. In step 1, the PET flake is dissolv xl. In step 2, reaction with methanol results in the formation of dimethyl terephtl lalate (DMT) and ethylene glycol (EG). DMT is purified by recrystallizati on and distillation to produce a monomer which meets the minimum specifications for producing PET.

Glycolysis
Because of the reversibilty of the polyesterification process, the addition of ethylene glycol to PET flake at high temperatures results in the formation of the monomers used in the original polymerization, EG and bis(hydroxyethyl)terephthalate. Also oligomers (n=ca. 2-10) are formed. The monomers and oligomers are purified by vacuum distillation and repolymerized.

Shell Chemical Process

Terephthalic acid and ethylene glycol are added to cleaned PET post-consu ner flake at temperatures greater than 260 C, follow-ed by melt polymerization at temperatures greater than 270 C, and solid state poly-merization at temperati ires greater than 200 C.

Depolmerization of Nylon 6
NHCH2CH2CH2CH2CH2CO n
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NH

Allied Process for Nylon 6

Two-stage process Ground scrap nylon is dissolved > vith high pressure steam at 125-130 psig at 175-180 C for 0.5 hours and then continuously hydrolyzed with steam at 350C anc 100 psig to form e-caprolactam. The monomer recovered could be repolymerized without further purificati 3n.

BASF Process for Nylon 6

BASF's carpet recycling process involves six steps: Collection, Separation, Monomer Recovery, Polymerization, Spinning, and Carpet Manufacture. Collection and identification of Nylon face carpet. For Carpet separation BASF is working with Shred-Tech Ltd.

BASF Process for Nylon 6

Carpet is shredded and granulated. An air classifier separates the Nylon 6fiom backing. Nylon 6 is pelletized for shipment. Nylon 6 is converted to caprolact im by treatment with steam and phosph* >ric acid at 230-325C. After purification by distillation i nd treatment with KMn0 4 , the capro lactam is suitable for repolymerization.

Depolymerization of Nylon < 6 >

Nylon waste fiber may be treated with sulfuric acid at 120C to recoveri ulfliric acid. HMDA is recovered by add ng lime. T Nylon waste may be hydrolyzed vith NaOH, with HMDA recovered by distillation and adipic acid recove red by acidification. Nylon waste may be reacted with molten adipic acid at 232C to form the z mine salt.

PHASE TRANSFER CATALYSIS

A phase transfer agent can be used in catalytic amounts in a two-phase reaction to cause transfer of one of the reactants into the normal phase of the other reactant in such a form that high reaction rates are obtained. The requirements are that the phase transfer catalyst must be cationic and must have enough organic character such that it and the desired anion are partitioned into the organic phase with high potential reactivity. Crown ethers, quaternary ammonium salts, and N-alkyl phosphoramides have been used as phase transfer catalysts.

Depolymerization of PET
PET fibers were hydrolyzed w ith 5% NaOH @ 80C in the presence if trioctyl methyl ammonium bromide. Reaction time: 60 min. Yield: up to 93%

Depolymerization of Nylon 4,6

Nylon 46 fibers were depolym erized with 50% NaOH and phase transfer agent for 24 hours at 165C to form a soluble product along with ca. 62% undissociated fibers. On cooling of the solution, a powder settled to tl e bottom of the flask. The powder form id turned out to be a mixture of oligome rs, adipic acid and 1,4-diaminobutane

Repolymerization of Nylon 4,6 Oligomers

Solid state polymerization was carried out on the nylon 46 oligomers it 210C for 16 hours. The viscosity average molecular weight increased from 1846 g/mole to 16,343. The melting 3oint of the repolymerized Nylon 46 was 2 ?0C.

DEPOLYMERIZATION OF NYLON 66 WITH 7% HCl SOLUTION

Nylon 66 fibers were depolymerized with 7% HCl solution at 80C for 24 hours to produce adipic acid and HMDA-2 HCl in 85.3 and 70.9% yields, respectively. The blank run produced a 29.6% yield of adipic acid and a mixture of HMDA-2 HCl, oligomers and adipic acid. Adipic acid was isolated by extraction with ethyl ether and HMDA-2 HCl was obtained by evaporation of the remaining aqueous solution.

ALKALINE DEPOLYMERIZATION OF NYLON 66

A series of experiments were run in order to examine the applicability and efficiency of benzyl trimethyl ammonium bromide (BTEMB) as a phase transfer catalyst in the depolymerization of Nylon 6,6. A known amount of Nylon 6,6 fiber ( MW= 30,944) was mixed with 200 ml of a 50% aqueous solution of NaOH and 0.2 g of BTEMB in 5 different runs. The mixture was heated at 143C for 24 hours under reflux. After 24 hours, on cooling, a white powder mixed with short whiskers settled at the bottom of the flask. The solid was collected by filtration.

DEPOLYMERIZATION OF NYLON 6,6 EFFECT OF FEED RATIO

Experiment Feed Ratio of Nylon to PTA (wt/wt)

1 5

2 10.3

20.6 29.4 59.8 no PTA

Percent Decrease in 40.3 49.5 55.5 42.5 40.8 +15.9 Weight of Oligomers Molecular Weight 1556 1912 1697 2396 1644

Original Nylon Molecular Weight 30,944

Depolymerization of Nylon 6,6 with BTEMB

Stepl 6g of Nylon 6,6 200 ml 60% NaOH 0.2g BTEMB Reflux for 24 hrs Add 320 ml o : 37% HCI to Solu ion Extract Filtrate with Ether 0.55g Adipic A id

4.62 g of Nylon 6,6 Oligomer

Depolymerization of Nylon 6,6 with BTEMB

Step 2 4.52g Oligomer 200ml NaOH 0.2g BTEMB Reflux for 24 hrs

I
1.62g of Nylon 6,6 Oligomer Add 320 ml of 37% HCI to Solution Extract Filtrate with Ether 0.72g Adipic Acid

Depolymerization of Nylon 6,6 with BTEMB

Step 3 1.62g of Oligomer 50 ml 50% NaOH 0.054g BTEMB Refluxfor24 hrs

Total Yield of Adipic Acid 2.32g (59.6%)

Evap of wr Distillati Producec Extraction-1.

n& Attempted ar
n of Residue no HMDA-On 5g of Adipic Acid

Depolymerization of Nylon 6,6 w th BTEMB Step 1-1.48g of Nylon 6,6 yields 0.55g of Adipic Acid (57.8% yield) Step 2- 2.9g of Nylon 6,6 Oligomer yields 0.72g of Adipic Acid (38.7% yield) Step 3- 1.62g of Nylon 6,6 Oligomer yields 1.05g of Adipic Acid (101% yield)

VITA MALCOLM B. POLK, Professor School of Textile and Fiber Engineering Georgia Institute of Technology, Atlanta, GA 30332-0295 Tel (404)894-2535, FAX (404)894-9766, e-mail: malcolm.polk@textiles.gatech.edu

Dr. Malcolm Polk received the B.S. degree in Chemistryfromthe University of Illinois in 1960 and the Ph.D. degree in Organic Chemistryfromthe University of Pennsylvania in
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1972. In 1973, he accepted a position as Associate Professor and Director of the Industrial Chemistry Program in the Chemistry Department at Atlanta University. He was promoted to the rank of Professor in 1979. In 1985, he accepted a position as Associate Professor in the School of Textile and Fiber Engineering at Georgia Tech. He was promoted to the rank of Professor with tenure in 1991.His area of research is the synthesis and characterization of liquid crystalline polymers. Dr. Polk is a member of the American Chemical Society, Phi Lambda Upsilon, and the Fiber Society. He has received research funding from ONR, DOE, NASA, EPA, and the Department of Commerce. He was a member of the National Research Council Committee on Liquid Crystalline Polymers in 1987-1989. RECENT PUBLICATIONS: Hu, X , Kumar, S., and Polk, " Synthesis and Characterization of a Poly(benzobisthiazole) with a Substituted Biphenyl Moiety in the Main Chain", Macromolecules. 29, 3787 (1996). Lian, G. and Polk, M., " Convenient Synthesis of 2,7-Diamino-9,9-Bis(4-aminophenyl)fluorene " .Synthetic Communications. 26(10). 2031, (1996). Mehta, V.R., Kumar, S., Polk, M.B., Vanderhart, D.L., Arnold, F.E., and Dang, T.D.," On the Evidence of Crosslinking in Methyl Pendent PBZT Fiber", J. Polym. Sci.:PartB: Polvm. Phvs.. 34, 1881 (1996). "Synthesis and Characterization of Processable Polymeric Precursors to Aromatic Polyimides", Harruna, I.I., Alvarado, M., Bota, K., Rodriguez, A, Polk, M., and Muzzy, J., "Polyimides:Trends in Materials and Applications. Proceedings of the Fifth International Conference on Polyimides", Feger,C, Khojasteh, M.M., and Molis, S.E., eds., S.P.E. pub., 221 (1996). Thammongkol, V., Warner, S., and Polk, M., " Characterization of a Melt Processable Liquid Crystal Copolyester", J. Polvm. Sci.: Part A: Polvm. Chem. Ed.. 33, 189 (1995). Datta, R.K., Polk, M.B., and Kumar, S., " Reactive Compatibilization of Polypropylene and Nylon", Polvm.-Plast. Technol. Eng.. 34(4), 571 (1995).