CS230696B1 - Method of preparation of power polyesterraides - Google Patents

Abstract

The invention relates to a method of preparation powdered polyesteramides by polymerization and copolymers of lactams / ω-amino acids of formula NH- / CH 2 / x-teO where x is 3 to 11, initiated with anhydrous acid phosphorous in the form of their ions compounds and lactams of general formula Η? Ρ04. NH- / CH2 / x- (5o, where x is 3 to 11 having a concentration of 0.1 to 20 mol which it is that it is done in the present 0.1 to 20 wt. aliphatic aromatic or blended polyester possibly their mixtures at temperatures 200 to 330 C. The reaction product is washed water or solvents to remove unreacted lactam or a mixture of lactams and dried. The resulting powder Lymers can be used as sorption materials to prepare a dispersion, paste and hot melt adhesives.

Description

The invention relates to the preparation of powdered polyesteramides.

Polyamide powders are usually prepared by dissolving polyamides and then precipitating them. direct polymerization of polyamides can be obtained conventionally by solution powdered anionic polymerization or cationic polymerization and more recently by copolymerization, initiated anhydrous phosphoric acid in the form of compounds with lactams equimolar aminoacids of the formula H ^ PO ^ .lfe- / Ci ^ / _x CO, where x is 3 to 11, resulting in lower than equilibrium conversions.

The preparation of block polyesteramides based on aromatic or aliphatic polyesters is difficult and most often carried out by mixing both polymers above their melting point.

We have now found a process for the preparation of polyesteramides by polymerizing or copolymerizing lactam-amino acids of the general formula ΝΗ- (0Η2 ₎ χ-^ 0, wherein x is 3 to 11 or oligomers thereof initiated from 0.1 to 20 mol% of anhydrous phosphoric acid in the form of its equimolar compounds with lactams-amino acids of the general formula Η ΡΟ ΡΟ / / / / 2 / _χ -δθ, wherein x is 3 to 11, characterized in that it is carried out in the presence of aromatic aliphatic or mixed polyesters or mixtures thereof in a concentration of 0.1 to 20 wt. %, preferably 5 to 20 wt. at temperatures of 200-330 ° C and the resulting reaction product is washed with solvents, preferably with water to dissolve any unreacted lactam or lactam mixture and dried at max. 50 ^G C. The polymerization time at temperatures of 200 to 330 ° C range depending on the the initial composition of the reaction mixture and the desired conversion of several minutes to several hours. The molecular weight of the copolymers thus prepared depends on the initiator concentration, the time and temperature of the polymerization, the type of lactam used, the type and concentration of the polyester used.

- 3 230 691

Block copolymers of polyester-polyamide, polyester-copolyamide, copolyester-polyamide or copolyester-copolyamide are formed depending on the starting reaction mixture used. This is evidenced in addition to IR spectra (products in addition to the strips typical of polyamide also contain a belt of 720 to 1740 cm ^-1 ), in particular DSG analysis (single endotherm of melting value less than the endotherms of both homopolymers). According to nitrogen analysis, 100% incorporation of the polyester into the copolymer is not degraded as under hydrolytic polymerization conditions.

Optionally, a waste mixture of oligomers and 6-caprolactam from the production of polyamide 6 or correspondingly low-grade 6-caprolactam, recycled 6-caprolactam and the like can be used to prepare said polyesteramides within or with said lactams.

Furthermore, all of the waste polyester produced by the manufacture or processing of the polyesters can be used in the preparation of the polyesteramides.

The advantage of this process lies in the speed and simplicity of the preparation of the polyesteramide powders since the entire process can be carried out, for example, in a simple polymerization cauldron.

The resulting powdered polymers having a surface area of several m ² / g to tens of m 2 / g can be used as a sorption material characterized by both physical and chemical sorption. Physical sorption is given by the surface area, shape and pore size, chemical sorption by the amount of phosphoric acid bound, the content of terminal amino groups, the carboxyl or hydroxyl groups, and the content of amide and ester bonds in the polymer. Furthermore, this material can be used to prepare dispersions, pastes and hot melt adhesives.

The process according to the invention is described in more detail below on several exemplary embodiments.

- 4 Example 1 ^{230 8θβ}

475 g of 6-caprolactam and 25 g of polyethylene terephthalate in the form of a granulate were introduced into a polymerization duplicator kettle equipped with nitrogen inlet and outlet, stirrer, dosing and discharge port. The kettle was then gradually heated. After melting the 6-caprolatkaw, the stirrer was turned on to facilitate dissolution of the polyethylene terephthalate in the 6-caprolactam and the reaction mixture rapidly heated to 260 ° C. At this temperature, the initiator r - (- 0.05 mol per 1 mol of 6-caprolactam) was added and the temperature of 260 ° C was maintained for 60 minutes. Nitrogen was initially introduced into the reaction mixture. The reaction mixture was then discharged into a stirred water bath at 20 ° C. The precipitated powdered polymer was repeatedly extracted with water, filtered and dried at 50 ° C. 20 g of powdered polyesteramide having an intrinsic viscosity Z (? 7 = 0.27 (25 ° C), m-cresol), a nitrogen content of 10.94% by weight, a melting range of 182-208 ° C, a melting point of 200 ° were obtained. C and melting enthalpy Δ H = 51.4 J / g.

Example 2

A mixture of 450 g of 6-mercaprolactam and 50 g of polyethylene terephthalate fiber content was polymerized as described in Example 1. 246 g of powdered polyesteramide having a p-value of 0.20, a nitrogen content of 9.58% by weight, a melting interval of 158-190 ° C, a melting point of 181 ° C, and a melting enthalpy of A H of 56.4 J / g were obtained.

Example 5

A mixture of 425 g of 6-caprolactam and 75 g of ground waste polyethylene terephthalate in the form of semolina was polymerized as described in Example 1. 260 g of a polyesteramide powder of 0.14, a nitrogen content of 9.41% by weight, a melting interval of 152-182 [deg.] C., a melting point of 177 [deg.] C. and a melting enthalpy of [Delta] H = 57.5 J / g were obtained.

Example 4

In a glass evacuated and sealed ampoule was polymerized '- - -F- · ¹ A mixture of 4.95 g of 6-caprolactam and H3PO4.NH- / CH2 / 5- ^ 0/99 in molar ratio 1 / 0.05 g of polyethylene terephthalate containing 5 mol% of 5-sulfoisophthalate units in the polyethylene terephthalate chain.

After 4 hours of polymerization at 260 ° C, 5.1 g of polyesteramide powder (after extraction with water) with a melting interval of 201-221 ° C were obtained.

- 5 Example 5 230 090

Following the procedure of Example 4, the mixture was polymerized at 55 ° C.

4.5B of 12-dodecanlactam and H5PQ4.1 (-) - (0 ') (χχ-ΟΟ) in a 9: 1 molar ratio) and 0.5 g of polyethylene terephthalate for 20 minutes; (after extraction with methanol) 5.3 g of powdered polyesteramide were obtained.

Example 6

A mixture of 4.5 g of 6-caprolactam, 8-octanlactam, 12-dodecanlactam and H 2 PO 4 .NH- (CH 2) (7-CO) in a molar ratio of 5: 3: 5: 1 was polymerized by the procedure of Example 5 and 0. 5 g of polyethylene terephthalate at 26 ° C for 50 minutes. 2.7 g of polyesteramide having a melting interval of 95 to 120 ° C were obtained.

Example 7

A mixture of 4 g of 6-capro-lactams, 2-pyrrolidone and H5PO4 was polymerized as in Example 4. (5-G0) in molar ratio

8: 1: 1) and 1 g of polybutylene terephthalate at -200 ° C for 20 hours. A powdered polyesteramide of 1.1 g was obtained.

Example 8

Concentrated and dried mixture of waste water extractable fractions of polyamide silk, containing by weight 68% 6-caprolactam, 6.5 wt. % cyclic dimer of 6-caprolactam, wt. % cyclic trimmer, 8.0 wt. % cyclic tetramer of 6-caprolactam and 6.5 wt. The higher cyclic and linear oligomers were polymerized by the method of Example 1 in the presence of 5 wt. % H5PO4.NH- (CH2) 5-CO and 10 wt. adipic acid, sebacic acid and 1,2,6-hexanetriol ester aliphatic poles at 26 ° C for 60 minutes. Extraction with water gave polyesteramide powder in 41.5% yield.

Example 9

Using the procedure of Example 1, except that unsaturated copolyester based on maleic anhydride, phthalic anhydride and propylene glycol was used instead of polyethylene terephthalate, polyesteramide was obtained in a yield of 47.5% by weight.

Claims (1)

SUBJECT V YN N 1E2 U 230 696 A process for the preparation of powdered polyesteramides by polymerization and copolymerization of N-amino acid lactams of the formula NH- / CH 2 / _X -CO, wherein x is 5-11 or oligomers thereof, initiated from 0.1-20 mol% of anhydrous phosphoric acid in the form of its equimolar compounds with lactams amino acids of the formula H 2 PO 4 .NH- (CH 3) x -CO, wherein x is 5 to 11, characterized in that it is carried out in the presence of aromatic, aliphatic or mixed polyesters or mixtures thereof in a concentration of 0.1 to 20 % wt. at temperatures of 200 to 550 ° C and the resulting reaction product is washed with water or solvents.