Polymer Degradation and Stability 70 (2000) 4348

Chemical degradation of polyurethanes 3. Degradation of microporous polyurethane elastomer by diethyl phosphonate and tris(1-methyl-2-chloroethyl) phosphate
K. Troev *, G. Grancharov, R. Tsevi
Institute of Polymers, Bulgarian Academy of Sciences, Soa 1113, Bulgaria Received 16 February 2000; accepted 27 February 2000

Abstract Microporous polyurethane elastomer, based on diphenylmethane diisocyanate (MDI) and polyester polyol-Bayex 2003E has been converted into a liquid by treatment with diethyl phosphonate and tris(1-methyl-2-chloroethyl) phosphate. The structure of the degraded products has been studied by 1H, 13C and 31P NMR spectroscopy. The degraded products are phosphorus- or phosphorus and chlorine-containing oligomers. # 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Microporous polyurethane elastomer; Chemical degradation; Diethyl phosphonate; Tris(1-methyl-2-chloroethyl) phosphate

1. Introduction Our previous papers [15] describe a new method for chemical degradation of polyurethanes which diers from the well-known methods of hydrolysis [6], glycolysis [79] and aminolysis [10,11]. This paper describes the degradation of microporous polyurethane elastomer by diethyl phosphonate or tris(1-methyl-2-chloroethyl) phosphate treatment. The primary aim of these studies is to develop a novel, industry-oriented method for converting polyurethane waste materials and used polyurethanes into reusable products suitable as raw material in the preparation of polymers with reduced ammability. 2. Experimental 2.1. Materials Microporous polyurethane elastomer, based on MDI, Bayer AG, and polyester polyol-Bayex 2003E, Bayer AG (adipic acid,1, 4-butane diol, ethylene glycol), was

chosen for degradation. Diethyl phosphonate (C2H5O)2P(O)H, is commercially available (Fluka), or can be prepared from phosphorus trichloride and ethanol, tris(1-methyl-2-chloroethyl) phosphate {ClCH2CH(CH3)}3 P(O) is commercially available. 2.2. Instruments H, 13C and 31P NMR spectra were recorded on a 500 MHz Bruker instrument, in CDCl3. The viscosity was measured on a Brookeld LV viscometer. Phosphorus content was determined on a Specol spectrophotometer, at 420 nm wavelength. 2.3. Degradation by diethyl phosphonate Into a three-necked ask equipped with a stirrer, thermometer and reux condenser 40 g of microporous polyurethane cut into small pieces 35 mm in size and 120 g of diethyl phosphonate were placed. The degradation proceeded at 170 C. Then the temperature was lowered to 60 C, and the unreacted diethyl phosphonate was removed under vacuum (0.160.18 mm Hg). Experiments on the chemical degradation of microporous polyurethane were performed with heating for 4, 5, 6 and 8 h. The results from the degradation are presented in Table 1. The degraded products are soluble in CHCl3, CH2Cl2, THF, DMF, DMSO.
1

* Corresponding author. Tel.: +359-2-978-2203; fax: +359-2-707523. E-mail address: ktroev@bas.bg (K. Troev).

0141-3910/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved. PII: S0141-3910(00)00086-0

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Table 1 Conditions for the chemical degradation of microporous polyurethane elastomer (PU) by diethyl phosphonate (DEP) DEP (g) 118.4 119.4 119.7 118.8
a

PU (g) 39.9 39.9 40.0 39.9

Duration of degradation (h) 4 5 6 8

Reacted DEP (g) 15.6 18.3 20.7 23.8

Unreacted DEPa (g) 102.8 101.1 99.0 95.0

Degree of degradation (%) 100 100 100 100

Yield (%) 55.5 58.2 60.7 63.7

P (%) 6.2 7.0 7.5 8.4

Unreacted diethyl phosphonate was removed by vacuum distillation and reused for degradation.

Table 2 Conditions for the degradation of polyurethane elastomer (PU) by tris(1-methyl-2-chloroethyl) phosphate (TCEP) TCEP (g) 119.3 121.2 118.6
a

PU (g) 39.9 39.9 40.0

Duration of degradation (h) 4 6 8

Reacted TCEP (g) 18.9 34.8 48.2

Unreacted TCEPa (g) 100.4 86.4 78.6

Degree of degradation (%) 100 100 100

Yield (g) 58.8 74.6 88.2

P (%) 3.04 4.41 5.17

1-chloro-2-propanol (%) 1.6 1.7 1.7

1,2-dichloropropane (%) 5.5 7.0 11.6

Unreacted tris(1-methyl-2-chloroethyl) phosphate was removed by vacuum distillation and reused for degradation.

2.4. Degradation by tris(1-methyl-2-chloroethyl) phosphate The degradation with tris(1-methyl-2-chloroethyl) phosphate was run under the same conditions: 40 g of microporous polyurethane cut into small pieces 35 mm in size were added to 120 g of tris(1-methyl-2-chloroethyl) phosphate. The degradation proceeded at 180 C for 4 h. Then the temperature was lowered to 130150 C. The unreacted phosphate was removed under vacuum (0.16 0.18 mm Hg). Experiments on the chemical degradation of microporous polyurethane were performed with heating for 4, 6 and 8 h. The results from the degradation are presented in Table 2. The degraded products are soluble in CHCl3, CH2Cl2, THF, DMF, DMSO.

3. Results and discussion Microporous polyurethane based on 4,4H -diphenylmethane diisocyanate and polyester polyol with the following repeating unit was subjected to degradation by diethyl phosphonate or tris(1-methyl-2-chloroethyl) phosphate.

3.1. Degradation by diethyl phosphonate It has been found that when heating microporous polyurethane elastomer with diethyl phosphonate at

Table 3 Phosphorus-containing products from the chemical degradation of microporous polyurethane elastomer by diethyl phosphonatea N 1 Structure
31

PNMR, d, ppm, J, Hz

H NMR, d, ppm, J, Hz

Content, % 9.1

9.48, quintet 3 J(P,H)=9.63 1 J(P,H)=704.8 9.26, quintet 3 J(P,H)=9.14 1 J(P,H)=703.2 9.02, quintet 3 J(P,H)=8.49 1 J(P,H)=703.7 4.98, t 3 J(P,H)=8.59 1 J(P,H)=646.3
a

6.38, d, P,H 1 J(P,H)=704.8 6.86, d, P,H 1 J(P,H)=703.0 6.80, d, P,H 1 J(P,H)=699.8 6.84, d, P,H 1 J(P,H)=647.6

3.3

18.2

51.6

The content of the free diethyl phosphonate is 17.8%.

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45

Fig. 1.

31

P{H} NMR spectrum of the degraded microporous polyurethane elastomer by diethyl phosphonate (duration of degradation: 8 h).

Fig. 2.

13

C {H} NMR spectrum of the degraded microporous polyurethane elastomer by diethyl phosphonate (duration of degradation: 8 h).

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K. Troev et al. / Polymer Degradation and Stability 70 (2000) 4348

Fig. 3. Viscosity vs. duration of degradation of microporous polyurethane elastomer by diethyl phosphonate.

170 C (Table 1) the polyurethane elastomer degrades. 31 P(H} NMR spectrum (Fig. 1) of the degraded microporous polyurethane after 8 h heating shows signals at 9.48, 9.26, 9.02, 8.49 and 4.95 ppm. The content of the phosphorus-containing products was calculated on the basis of the integration ratio of the corresponding signals in the 31P{H} NMR spectrum (Table 3). 31P NMR spectrum shows that the signal at 9.48 ppm represents a doublet of quintets with 3J(P,H)=9.63 and 1J(P,H)= 704.7 Hz and can be assigned to the phosphorus atom in structure 1 (Table 3). The signal at 9.26 ppm represents a doublet of quintets with 3J(P,H)=9.14 Hz and 1J(P,H)=703.2 Hz and can be assigned to the phosphorus atom in structure 2 (Table 3). The signal at 9.02 ppm represents a doublet of quintets with 3J(P,H)=8.49 Hz and 1J(P,H)=703.7 Hz and can be assigned to the phosphorus atom in structure 3 (Table 3). The signal at 8.49 ppm represents a doublet of quintets with 3J(P,H)=9.14 Hz and 1J(P,H)=703.26 Hz and can be assigned to the phosphorus atom in the molecule of diethyl phosphonate. The signal at 4.98 ppm represents a doublet of triplets with 3J(P,H)=8.59 Hz and 1 J(P,H)=646.3 Hz and was assigned to the phosphorus atom in structure 4 (Table 3). The data from the 1H NMR spectrum conrm the structure of the degraded products. In the 1H NMR spectrum of the degraded product there are ve types of PH protons which present a doublets at: 6.88 ppm with 1J(P,H)=704.8 Hz; 6.86 ppm with 1 J(P,H)=703.0 Hz; 6.80 ppm with 1J(P,H)=699.8 Hz and at 6.84 ppm with 1J(P,H)= 647.6 Hz which can be assigned to products 14, respectively. The doublet at 6.81

ppm with 1J(P,H)= 692.3 Hz can be assigned to the PH proton of diethyl phosphonate. The presence of signals at 52.96 ppm for +N-CH2CH3 carbon atom, at 10.45 ppm for +N-CH2CH3 carbon atom, at 60.28 ppm for HN-C(O)OCH2CH3 carbon atom and at 14.23 ppm for HN-C(O)OCH2CH3 carbon atom in 13 C{H} NMR spectrum (Fig. 2) of the degraded product conrm the formation of the above mentioned structures. The experimental results show that increasing the duration of the degradation process lowers the viscosity of the nal product (Fig. 3) whilst the content of phosphorus increases (Table 1). 3.2. Degradation by tris(1-methyl-2-chloroethyl) phosphate Tris(1-methyl-2-chloroethyl) phosphate was chosen as a degrading agent because this ester of phosphoric acid is widely used as a ame retardant for rigid polyurethane foams. The treatment of microporous polyurethane elastomer with tris(1-methyl-2-chloroethyl) phosphate at 180 C results in the formation of product 5.

Its structure was determined by 31P, 13C and 1H NMR spectroscopy. The content of 5 is 20% and was

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Fig. 4. Viscosity vs. duration of degradation of microporous polyurethane elastomer by tris(1-methyl-2-chloroethyl) phosphate.

calculated on the basis of the integration ratio of the corresponding signals in the 31P{H} NMR spectrum. 31 P{H} NMR spectrum shows that the nal product obtained after 8 h heating consists 4.0% free tris(1methyl-2-chloroethyl) phosphate. The signal at 2.67 ppm in the 31P NMR spectrum which represents a quintet with 3J(P,H)=8.4 Hz can be assigned to the phosphorus atom of the product 5. The multiptet at 4.014.10 ppm in the 1H NMR spectrum of the degraded product is characteristic for P-OCH2- protons in product 5. The signal at 64.27 ppm in the 13C{H} NMR spectrum can be assigned to POCH2-carbon atoms in product 5. It was established that the degradation of the microporous polyurethane elastomer by tris(1-methyl-2-chloroethyl) phosphate is accompanied by the formation of 1-chloro-2-propanol and 1,2-dichloropropane. Both compounds are separated from the reaction mixture by distillation. The compounds are identied by 1H NMR spectroscopy. 1-Chloro-2-propanol is formed as a result of hydrolysis of tris(1-methyl-2-chloroethyl) phosphate [Eq. (1)].

Dealkylation of tris(1-methyl-2-chloroethyl) phosphate gives 1,2-dichloropropane [Eq. (2)] [12].

The assignments of the chemical shifts of phosphorus, carbon atom and protons of degraded products are based on the data published by Penczek [13], Ignatious [14] and Troev [15]. Increasing the duration of the degradation lowers the viscosity of the nal product (Fig. 4). The experimental results show that the exchange reaction between urethane groups and 1-methyl-2-chloroethoxy groups of tris(1-methyl-2-chloroethyl) phosphate proceeds at a lower rate than that between urethane groups and ethoxy groups of diethyl phosphonate. In the case of tris(1-methyl-2-chloroethyl) phosphate after 8 h heating the viscosity of the nal product is 36 000 mPa s and in the case of diethyl phosphonate it is 900 mPa s. 3.3. Mechanism of degradation of microporous polyurethane elastomer by diethyl phosphonate and tris(1-methyl-2-chloroethyl) phosphate Products 1, 2, 3 and 5 are formed in the result from the exchange reaction between ethoxy groups of diethyl phos-

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K. Troev et al. / Polymer Degradation and Stability 70 (2000) 4348

phonate or 1-methyl-2-chloroethoxy groups of tris(1methyl-2-chloroethyl) phosphate and urethane groups. The mechanism is the same as when dimethyl phosphonate [1] is used as a degrading agent. This exchange reaction results in breaking down the main polymer chain of microporous polyurethane elastomer and in the formation of oligomers. Product 4 is formed as a result from the alkylation of urethane group by diethyl phosphonate [1]. The a-carbon atom of the alkoxy groups of the phosphonic or phosphoric acids participate in the alkylation reaction. The rate of the alkylation reaction depends on the type of the a-carbon atom and decreases in the order: primary>secondary>tertiary. Signals related to the alkylated product are absent in the 31P NMR spectrum of the nal product obtained after heating of microporous polyurethane elastomer with tris(1-methyl-2-chloroethyl) phosphate. In tris(1-methyl-2-chloroethyl) phosphate the a-carbon atom is tertiary. 4. Conclusions The results show that diethyl phosphonate and tris(1methyl-2-chloroethyl) phosphate can be used as degrading agents for microporous polyurethane elastomer. NMR studies of the degraded products clearly show that the

liquefaction of the microporous polyurethane elastomer results from the proceeding of exchange reaction between ethoxy groups of diethyl phosphonate or 1-methyl-2chloroethoxy groups of tris(1-methyl-2-chloroethyl) phosphate and urethane groups. The rate of the exchange reaction depends on the type of the a-carbon atom of the degrading agents. Degraded products are phosphorusor phosphorus and chlorine-containing oligomers. References
[1] Troev K, Atanassov VI, Tsevi R, Grancharov G, Tzekova A. Polym Degrad Stab 2000;67:159. [2] Troev K, Tsekova A, Tsevi R. J Appl Polym Sci, in press. [3] Troev K, Atanassov VI, Tsevi R. J Appl Polym Sci, in press. [4] Troev K, Tsekova A, Tsevi R. Polym Degrad Stab 2000;67:397. [5] Troev K, Grancharov G, Tsevi R, Tsekova A. Polymer 2000; 41:7017. [6] Campbell GA, Meluch WC. J Appl Polym Sci 1975;21:581. [7] Simioni F, Modesti M, Reinzi SA. Cell Polym 1987;6:2741. [8] Bauer G. In: Polyurethane world congress, 1991. p. 872. [9] Takashi S. Polym Prepr Jpn 1992;41(6):2195. [10] Patent Fr. 1429011, 1966; C. A. 65 9124c, 1966. [11] Patent Fr. 1484107, 1968; C. A. 68 13679g, 1968. [12] Sher S, Rubtsova I, Gefter E. Vysokomol Soed 1965;7:1684. [13] Penczek St, Pretula J. Macromolecules 1993;26:2228. [14] Ignatious F, Sein A, Cabasso I, Smid J. J Polym Sci, Part A Polym Chem 1993;31:239. [15] Troev K. Heteroatom Chem 1994;11:89.