Phosphorus-containing polymers from THPS. II: synthesis and property of phosphorus-containing hyperbranched aromatic-aliphatic polyamides

Abstract

Phosphorus-containing hyperbranched aromatic-aliphatic polyamides are prepared via direct polymerization of triacid (B 3 ) with different diamines (A 2 ), which for improving the processability of aromatic polyamides while keeping exellent thermal and mechanical property. The triacid (B 3 ), tris(2-carboxyethyl)phosphine oxide (TCEPO), is synthesized from tetrakis(hydroxymethyl)phosphonium sulfate and its structure is verified by Fourier transform infrared, 1 H, 13 C and 31 P NMR spectroscopy. Then, the polycondensation reaction of TCEPO with p-phenylene diamine, 4,4′-oxyphenylene diamine and 4,4′-methylenedianiline result in three phosphorus-containing hyperbranched aromatic-aliphatic polyamides, and the degree of branching is found between 0.66 and 0.71. Gel permeation chromatography measurement reveal that all hyperbranched aromatic-aliphatic polyamides have moderate number-averaged molecular weights and narrow molecular weight distribution. The Dynamic mechanical thermal analysis results show all polymers have two glass transition temperatures (T g ) in the temperature range 85.3-128.0°C and have high storage modulus about 1.52-3.19 GPa at 50°C. The TGA results reveal the initial degradation temperatures (T 5 ) and the temperatures for 10% gravimetric loss (T 10 ) for the hyperbranched aromatic-aliphatic polyamides are in the range of 214-250 and 256-333°C, and the maximum decomposition temperatures (T m ) are about 500°C, and also the char yields of polymers at 850°C are about 39.4-48.4%, which indicate good thermal stability.

Main-chain/side-chain type phosphine oxide-containing reactive polymers derived from the same monomer: controllable RAFT polymerisation and ring-opening polycondensation

“…4-Vinylbenzyl-bis(hydroxymethyl) phosphine oxide (VBzBHPO) and tris(2-cyanoethyl) phosphine (TCP) were synthesized in our laboratory. 50,51 Bis (tetrabutylammonium) sebacate (TBAS) and n-butyl benzyl trithiocarbonate (BBTC) were synthesized according to the literature methods. [52][53][54] All other chemical solvents and reagents were used as received: NaOH (>96%, Sinopharm), sulfuric acid (95%-98%, Sinopharm), butanedioic acid (>99%, Sinopharm), triethylamine (>99%, Sinopharm), diethylamine (DEA, 98%, Aladdin).…”

“…† Then, TBAS was used under similar experimental conditions and polymerisation produced a polymer with a yield of 64%. In addition, TCP was successfully synthesized on a large scale in our laboratory 51 and also promoted the ring-opening polymerisation with 18% yield under the same reaction conditions. The SEC elution curves are shown in Fig.…”

Liquid crystalline hyperbranched polyesters with phosphorus functional groups

“…The PDI values are close to 1 (Table 1), similar values being obtained for related hyperbranched polymers reported in the literature. 48,49 The experimental molecular weights determined by GPC measurements for hyperbranched polymers P-1 and P-2 is expected to be lower than the real ones because of the smaller radius of chain gyration in comparison with linear counterparts. However, the ellipsoidal architecture of hyperbranched polymers causes considerable errors in the measurement of molecular weights by GPC method, for which calibration is performed with linear polystyrene as a standard.…”

“…[35][36][37][38][39][40][41][42][43][44][45][46][47] To date, several papers described the preparation of phosphorus-containing hyperbranched polymers appealing for flame retardancy applications. [48][49][50][51][52] As a rule, a high content of phosphorus in a polymer brings better fire performances, thus, current work aimed to prepare hyperbranched polyesters derived from A 2 and B 3 monomers, as a facile route to novel phosphorus-containing hyperbranched polyesters. The synthesis of hyperbranched polyesters that are derived from 2-(6-oxido-6H-dibenz <c,e><1,2>oxaphosphorin-6-yl)1,4-naphthalene diol (DOPONQ) and 1,3,5-benzenetricarbonyl trichloride is reported herein.…”

Tri(3‐alkoxyl‐3‐oxopropyl) phosphine oxides derived from PH3 tail gas as a novel phosphorus‐containing plasticizer for polylactide

“…TCEPO is a derivative of PH 3 tail gas and shows high hydrolysis resistant owing to the absence of the P O single bond in its structure. 29 Furthermore, TCEPO is an oxidative product of tris (2-carboxyethyl)phosphine hydrochloride, which is a disulfide bondreducing agent with low toxicity widely utilized in biochemistry. 30,31 Three new plasticizers (PC4, PC6, and PC8; Figure 1) were mixed with PLA to form a transparent film.…”