A METHOD FOR RECOVERING POLYMER FROM PRINTED PETG SUBSTRATES

Abstract

A method for recovering polymer from printed glycol-modified poly(ethylene tefephtalate) (PETG) substrates, comprising the steps of: providing a printed PETG substrate with the print layer comprising pigments and/or dyes dispersed in a binder matrix; chopping the substrate into irregular strips and; treating the chopped substrate with a treating composition; wherein the treating composition is an aqueous azeotrope of an organic low molecular weight, polar solvent selected from the group consisting of ketones, aldehydes, alcohols and esters.

Claims

1. A method for recovering polymer from printed glycol-modified poly(ethylene tefephtalate) (PETG) substrates, comprising the steps of: providing a printed PETG substrate with a print layer comprising pigments and/or dyes dispersed in a binder matrix; chopping the printed PETG substrate into irregular strips; and treating the printed PETG substrate chopped into the irregular strips with a treating composition; wherein the treating composition is an aqueous azeotrope of an organic, low molecular weight, polar solvent selected from a group consisting of: ketones, aldehydes, alcohols and esters.

2. The method according to claim 1, wherein the solvent is an aliphatic having from 1 to 7 carbon atoms in each alkyl moiety.

3. The method according to claim 2 wherein the solvent is selected from a group consisting of: acetone, ethanol, propanol, methylethylketone and ethyl acetate.

4. The method according to claim 1 wherein the strips have a width of no more than 5 cm.

5. The method according to claim 1, comprising carrying out treating at an ambient temperature.

6. The method according to claim 1, comprising treating for 20 minutes.

7. The method according to claim 1, comprising repeating the step of treating from 3 to 5 times.

8. The method according to claim 1, comprising drying and granulating the printed PETG substrate chopped into the irregular strips after the step of treating, to obtain a PETG granulate.

9. The method according to claim 8, comprising heating the PETG granulate at a temperature from 10- to 15 C. lower than a melting temperature of PETG for a time from 5- to 24 hours, at a near-vacuum pressure from 1 to 15 hPa.

10. The method according to claim 8, comprising heating the PETG granulate at a temperature from 10- to 15 C. higher than a melting temperature of PETG and mixing it with an adduct of epoxy peroxide carbon nanotubes.

11. The method according to claim 1, wherein the PETG substrates comprises cyclohexanedimethanol-modified poly(ethylene terephthalate).

12. The method according to claim 1, wherein the PETG substrate comprises dimethylcyclohexyl glycol-modified poly(ethylene terephthalate).

Description

BRIEF DESCRIPTION OF DRAWINGS

[0023] The method is presented by means of exemplary embodiments and shown in a drawing, wherein:

[0024] FIG. 1 is a schematic flowchart of an example of a process;

[0025] FIG. 2 is a scheme of reaction of preparing an adduct to be used as an additive to the recovered polymer.

DETAILED DESCRIPTION

[0026] A method for removing print from printed thermoplastic glycol-modified poly(ethylene terephthalate) (PETG) substrates is presented herein. The PETG substrates which may be treated according to the method are, for example, cyclohexanedimethanol-modified poly(ethylene terephthalate) (CHMD-modified PET) substrates such as 1,4-cyclohexanedimethanol-modified poly(ethylene terephthalate) (1,4-CHDM-modified PET) substrates or 1,3-cyclohexanedimethanol-modified poly(ethylene terephthalate) (1,3-CHDM-modified PET) substrates or dimethylcyclohexyl glycol-modified poly(ethylene terephthalate) substrates. The PETG substrates are preferably thin-walled substrates, such as thin-walled containers, cups or plates, in particular foils.

[0027] The treating composition used in the presented method is an aqueous azeotrope of an organic polar solvent having low molecular weight, selected from the group consisting of ketones, aldehydes, alcohols and esters. Water in the composition can be either distilled water or demineralized water. The treating composition can be applied to the substrate by any suitable method, e.g. by rubbing, agitating, mixing or dipping the chopped substrate in the treating composition. It has been unexpectedly discovered that the aqueous azeotropic mixtures of above-mentioned polar solvents can be used to effectively remove a variety of printing compositions, without the necessity of addition of any auxiliary caustic compound such as acid, base as well as catalyst and highly hazardous chemicals such as aromatic solvents. Aqueous azeotropic mixtures of ketones, aldehydes, alcohols or esters are capable of removing substances utilized in any type of printing techniques upon the polymeric substrates without adversely affecting the polymer (e.g. prompting depolymerization of polymer backbones). In addition, the used azeotropic mixtures are sufficiently volatile so as to be removed from the polymer substrate without unnecessary energy outlay. A simple comprisal of the treating composition facilitates recovery of the composition after treatment of the chopped polymer substrate. According to the method of the invention, the post-process treating mixture, after the treating process, is recovered simply by distillation, wherein only simple apparatus is needed as the azeotropic composition after distillation keeps the same percentages of particular treating composition compounds.

[0028] The printed polymeric PETG substrates, from which the print substances can be removed, may constitute any kind of polymeric waste e.g. post-industrial waste, domestic waste and the like.

[0029] The print to be removed can be the print applied by any suitable printing technology e.g. flexography printing, inkjet printing, laser/toner printing, intaglio printing, screen-printing, rotogravure printing and the like. The printing compositions can be any print suitable for use in these printing methods. The printing compositions may comprise dyes or pigments or mixtures thereof. The pigments or dyes can be dispersed in uncrosslinked or crosslinked binder matrix. Exemplary of binder systems capable for being removed according to the method are styrene acrylic copolymers, or polyamides.

[0030] The printed polymeric substrate is preferably foil, or a thin-walled waste article e.g. containers or plates chopped into irregular strips of width less than 5 cm. The applicant has unexpectedly discovered that shape and dimensions of the chopped polymeric substrate both have of great importance for the efficiency of polymer recovery process when the substrate is mixed or agitated with the treating composition. Irregularly strip-hopped polymeric substrate of width less than 5 cm causes formation of larger areas of empty spaces throughout the treating composition can act to remove the print of polymeric substrate.

[0031] As set out above, the treating composition constitute the aqueous azeotropic mixture of organic, low molecular weight, polar solvent selected from the group consisting of ketones, aldehydes, alcohols and esters. Preferably said solvents are aliphatic compounds having from 1 to 7 carbon atoms in each alkyl moiety, more preferably from 1 to 5 carbon atoms in each alkyl moiety, and the most preferably from 1 to 3 carbon atoms in each alkyl moiety. Exemplary organics solvents which can be used, according to the present invention, are acetone, ethanol, propanol, methylethylketone and ethyl acetate. Generally, each aqueous azeotropic composition of above mentioned solvents can be used as the treating composition.

[0032] Preferably, solvents used according to the invention are halogen-free solvents as well as they do not contain aromatic moieties.

[0033] Exemplary embodiment of treating method according to the invention is schematically shown in the FIG. 1. The polymer to be recovered from the printed polymeric substrate, for example a waste PETG foil, is chopped into irregular strips of width less than 5 cm at the chopping station 10, e.g. a cutter mill. The chopped irregular substrate strips enter a reactor chamber at the treating station 20 by means of a suitable conveyor device (not shown in FIG. 1 for clarity). An inlet piping system 21 delivers the treating composition to the reaction chamber at the treating station 20. In the reaction chamber, the chopped polymer substrate is treated by mixing, or otherwise contacting the chopped substrate with the treating composition, e.g., an aqueous azeotropic ethanol composition or an aqueous azeotropic propanol composition or an aqueous azeotropic acetone composition or an aqueous azeotropic methylethylketone composition or an aqueous azeotropic ethyl acetate composition. The treatment is preferably carried out by mixing, but it can be carried out by rubbing or agitating or dipping the substrate in the treating composition as well.

[0034] The print-free polymer can be separated from the treating composition using any suitable mean. For example, the post-process treating composition can be pumped out from the reactor chamber by using an outlet piping system 22 connected to the reactor. The post-process treating composition can be further recycled by a simple distillation process. In FIG. 1 a closed-looped system is shown, wherein the processed treating composition is passed via the distillation station 30 and then it is returned to the reactor chamber as a recovered treating composition. The process for recovering the polymer from the printed plastic substrate can be implemented in either a bath or in a continuous manner. The process can be repeated from 3 to 5 times to ensure complete print removal from the chopped substrate. For example, a plurality of reactor chambers may be arranged in series, so that the chopped polymer can be removed from the first reactor chamber and then it can be introduced into the second reactor chamber for contacting with another volume of the treating composition and so on. Alternatively, the chopped polymer substrate can be maintained in the same reactor chamber while new volumes of treating composition can be input to the reaction chamber after pumping out the post-process treating composition. The new portion of treating composition may be the same treating composition as used in previous treatment process, or the new portion of treating composition may be provided as different treating composition of different organic solvent. For example, an aqueous azeotropic ethanol composition may be used as the first treating composition, and an aqueous ethyl acetate composition may be used as the second treating composition.

[0035] The post-process treating composition may pumped out and distilled after 5-10 cycles of polymer treating, and then the composition may be re-introduced e.g. to the last reactor chamber of the series of reactor chambers to be re-used in the treating process.

[0036] As shown in FIG. 1, the recovered polymer can be further processed to provide recycled product, e.g. the recovered polymer may be dried at a drying station 40, then plasticized and granulated at station 50. For example, granulate of PETG can be obtained at station 50 in the step of plasticizing PETG at a temperature 180-250 C. followed by molding of plasticized PETG to obtain a rod shape or a strand of diameter of 2-5 mm, then cooling the polymer to a of 25-15 C. followed by cutting the rods or the strands into granulate.

[0037] The PETG granulate thus obtained may be used as a raw material for production of new plastic articles or the granulate may be further modified.

[0038] The modification of the recovered PETG is carried out by addition an additive to the polymer. The additive is represented by formula I shown in FIG. 3.

[0039] The additive of formula I consists an adduct compound of epoxy peroxide carbon nanotubes. In FIG. 2 the process for preparation of the adduct compound is shown wherein the carbon nanotubes undergo addition to the epoxy peroxide represented by formula II.

[0040] The adduct-forming reaction is conducted at 50 C., by 24 hours in the presence of catalyst in amount of tetrabuthyl titanate, antimone oxide etc. Preferably, the catalyst is cobalt salt of alpha-methyl caproic acid. Prior to being added with the adduct, in order to improve of PETG performance and physical properties which have deteriorated during recovering process of the polymer, the polymer (PETG) is heated at the temperature 10-15 C. lower than the polymer melting temperature, by 5-24 hours, in vacuum of 15-1 hPa; in an alternative embodiment, treating of the PETG granulate can be carried out at the temperature 10-15 C. higher than the polymer melting temperature. After temperature treatment, the polymer is plasticized and mixed with the adduct in weight ratio of 99.5:0.5 to 99:1. Alternatively, the adduct can be added to melted polymer granulate without any additional treatment. Addition of the adduct to polymer materials can affect their higher viscosity and higher thermal stability

[0041] PETG modified with the adduct of carbon nanotubes with epoxy peroxide as well as the mixture of the modified PETG and PET (poly(ethylene terephthalate)) may be further processed using any known technology to produce new plastic articles.

[0042] Below there are presented non-limiting examples of carrying out the presented method.

EXAMPLE I

[0043] PETG foil was chopped into irregular strips by a guillotine provided with rolls 2 meters long. The frizzy strips having a width of about 5 cm were introduced to a chamber provided with a wire basket, a stirrer and a hermetic cover. Then, the treating composition consisting of acetone and water in volume ratio of 90:10 has been input to the chamber. The mixture was mixed by 20 min at an ambient temperature. The stirring direction was changed every 5 min. Next, the cover was removed and a wire basket filled with the polymeric foil strips was removed from the chamber. The recovered polymer strips were then transported to an air dryer and dried to be subsequently used in other process.

EXAMPLE II

[0044] PETG foil with intense amount of printing was chopped into irregular strips by a guillotine provided with 2 meter long rolls. The frizzy strips of width of 4 cm entered a chamber provided with a wire basket, an anchor stirrer and a hermetic cover. Next, the treating composition consisting of ethanol and water in a volume ratio of 94:6 was added to the chamber. The mixture was mixed by 20 min at ambient temperature. The stirring direction was changed every 5 min. Next, the cover was removed and the wire basket filled with the polymeric foil strips were removed from the chamber. The wire basket was transported to the other container of the same dimensions as the dimensions of wire basket, wherein the treated polymer was rinsed by mixing with rinsing liquid by 20 min. Rinsing was repeated five times, then the recovered polymer strips were transported to an air dryer and dried to be subsequently used in other process.

EXAMPLE III

[0045] After treatment, recovered PETG foil strips were dried and visually assessed. Then the foil strips were introduced to the container being an extension of a feeder of counter-rotating twin screw extruder. There was provided, in the extruder chamber, two-parts screw-conveyor having one smaller and one larger screw; the foil strips were pressed into the extruder chamber. The plasticizing zone and the homogenizing zone of the extruder were heated to the temperature of 180-250 C. Rotary screws speed was set to 30 revolutions per minute. The extruder was provided with additional feeder for feeding extruded material with additional components concentrate. Further, the extruders were provided with degassing vacuum system. Titanium white in the amount of 2% by weight and the adduct of epoxy peroxide carbon nanotubes in the amount of 0.5% by weight were provided by the additional feeder to the screw-conveyor chamber to be mixed with the plasticized PETG. The plasticized mass was extruded as strands of 3 mm diameter. Then the polymeric strands were cooled in a water bath and the cooled polymer was granulated by cutting into scraps of 3 mm length. The granulate was dried under vacuum conditions at 50 C. for 8 hours, to be subsequently processed by injection molding to produce new articles.

EXAMPLE IV

[0046] After treatment process, the recovered PETG foil strips were dried and visually assessed. Then the foil strips were introduced to a container being an extension of a feeder of counter-rotating twin screw extruder. There was provided, in the extruder chamber, two-parts screw-conveyor having one smaller and one larger screw; the foil strips were pressed into the extruder chamber. The plasticizing zone and homogenizing zone of extruder were heated to the temperature of 180-250 C. Rotary screws speed was set to 30 revolutions per minute. The extruder was provided with additional feeder for feeding extruded material by additional components concentrate. The plasticized mass was extruded into strands of diameter of 2 mm. Then the polymeric strands were cooled in the water bath and cooled polymer was granulated by cutting into scraps of 2 mm long. The obtained transparent polymeric granulate was dried and decrystalized under vacuum at 50 C. for 5 hours. Afterwards, polycondensation of the polymer was conducted at 180 C. for 12 hours under vacuum of 5 hPa, while mixing the polymer by means of repouring. The treated granulate was subsequently used in a foil production process.