Polyester for the paper industry

Abstract

The invention relates to the use of polyesters for increasing the surface tension and improving the hydrophilic behavior of hydrophobic surfaces, wherein said polyesters are obtainable by polymerization of a) one or more unsulfonated aromatic dicarboxylic acids and/or salts thereof and/or anhydrides thereof and/or esters thereof, and b) ethylene glycol, c) 1,2-propylene glycol, and d) one or more polyalkylene glycols, and e) one or more compounds of formula (1)
R.sup.1O(CHR.sup.2CHR.sup.3O).sub.nH  (1) where R.sup.1 is a linear or branched, saturated or unsaturated alkyl group of 1 to 22 carbon atoms, preferably methyl, R.sup.2 and R.sup.3 are each independently hydrogen or an alkyl group of 1 to 4 carbon atoms, preferably hydrogen and/or methyl, and n is from 1 to 50, f) in the presence or absence of one or more crosslinking compounds having 3 to 6 functions capable of polycondensation, especially acid, alcohol or ester functions,
with the proviso that said components d) are used in weight quantities <80%, based on the weight quantity of the polyesters obtained by the polymerization.

Claims

1. A polyester capable of being used for increasing surface tension and improving hydrophilic behavior of hydrophobic surfaces, wherein said polyester is obtained by polymerization of a) one or more unsulfonated aromatic dicarboxylic acids and/or salts thereof and/or anhydrides thereof and/or esters thereof, and b) ethylene glycol, c) 1,2-propylene glycol, and d) one or more polyalkylene glycols, and e) one or more compounds of formula (1)
R.sup.1O(CHR.sup.2CHR.sup.3O).sub.nH  (1)  where R.sup.1 is a linear or branched, saturated or unsaturated alkyl group of 1 to 22 carbon atoms, R.sup.2 and R.sup.3 are each independently hydrogen or an alkyl group of 1 to 4 carbon atoms, and n is from 1 to 50, f) in the presence or absence of one or more crosslinking compounds having 3 to 6 functions capable of polycondensation, with the proviso that said components d) are used in weight quantities <80%, based on the weight quantity of the polyesters obtained by polymerization, wherein the weight fraction of residual monomers in the polyester due to components a) to e) and optionally f) is <1% based on the weight of the polyester.

2. The polyester as claimed in claim 1, wherein the polymerization comprises transesterification and condensation of components a) to e) in the presence or absence of component f) in the presence of one or more transesterification and condensation catalysts.

3. The polyester as claimed in claim 1, wherein one or more compounds selected from terephthalic acid, phthalic acid, isophthalic acid, their anhydrides and the mono- and dialkyl esters with C.sub.1-C.sub.6 alcohols of dicarboxylic acids are used as component a).

4. The polyester as claimed in claim 1, wherein one or more compounds selected from polyethylene glycols having weight-average molecular weights of about 200 to 8000 g/mol, and/or polypropylene glycols having weight-average molecular weights of about 200 to 8000 g/mol and polypropylene ethylene glycol having weight-average molecular weights of about 200 to 8000 g/mol are used as component d).

5. The polyester as claimed in claim 1, wherein compounds selected from the group consisting of citric acid, malic acid, tartaric acid, gallic acid, 2,2-dihydroxymethylpropionic acid, pentaerythritol, glycerol, sorbitol, mannitol, 1,2,3-hexanetriol, benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid) and benzene-1,3,5-tricarboxylic acid (trimesic acid) are used as component f).

6. The polyester as claimed in claim 1, which is obtained by polymerization of components a) to e) in the presence or absence of component f) in the following molar ratios, each based on 1 mol of component a): 0.2 to 0.8 mol of component b), and 1.0 to 2.0 mol of component c), and 0.05 to 2.0 mol of component d), and 0.01 to 1.0 mol of component e), and in the presence of 0.00001 to 1.0 mol of component f) or in the absence of component f).

7. The polyester as claimed in claim 1, wherein the polyester has a weight-average molecular weight in the range from 700 to 50 000 g/mol.

8. An aqueous dispersion comprising 10% to 30% by weight based on the final aqueous dispersion of a polyester obtained by polymerization of a) one or more unsulfonated aromatic dicarboxylic acids and/or salts thereof and/or anhydrides thereof and/or esters thereof, and b) ethylene glycol, c) 1,2-propylene glycol, and d) one or more polyalkylene glycols, and e) one or more compounds of formula (1)
R.sup.1O(CHR.sup.2CHR.sup.3O).sub.nH  (1)  where R.sup.1 is a linear or branched, saturated or unsaturated alkyl group of 1 to 22 carbon atoms, R.sup.2 and R.sup.3 are each independently hydrogen or an alkyl group of 1 to 4 carbon atoms, and n is from 1 to 50, f) in the presence or absence of one or more crosslinking compounds having 3 to 6 functions capable of polycondensation, with the proviso that said components d) are used in weight quantities <80%, based on the weight quantity of the polyesters obtained by polymerization.

9. A method comprising adding a polyester as claimed in claim 1 in a papermaking process or in a paper recycling process to paper fiber furnish as a dispersion in an amount to form a homogeneous dispersion and take effect therein.

10. A method for enhancing dispersibility of hydrophobic fibers comprising adding and/or spraying the polyester of claim 1 on the fibers as a dispersion.

11. A method improving printing behavior of oil-based printing inks on hydrophobic surfaces comprising adding and/or spraying the polyester of claim 1 on the hydrophobic surfaces.

12. The polyester as claimed in claim 1, wherein R.sup.1 is methyl.

13. The polyester as claimed in claim 1, wherein R.sup.2 and R.sup.3 are each independently hydrogen and/or methyl.

14. The polyester as claimed in claim 1, wherein the 3 to 6 functions capable of polycondensation are acid, alcohol or ester functions.

15. The polyester as claimed in claim 1, wherein component e) has a weight-average molecular weight of about 150 to 2000 g/mol and is selected from the group consisting of polyethylene glycol monoalkyl ethers and poly[ethylene glycol-co-propylene glycol] monoalkyl ethers.

16. The polyester as claimed in claim 1, which is obtained by polymerization of components a) to e) in the presence or absence of component f) in the following molar ratios, each based on 1 mol of component a): 0.5 to 0.6 mol of component b), and 1.3 to 1.4 mol of component c), and 0.25 to 0.5 mol of component d), and 0.11 to 0.3 mol of component e), and in the presence of 0.0002 to 0.01 mol of component f) or in the absence of component f).

17. A method for increasing surface tension and improving hydrophiolic behavior of a hydrophobic surface comprising applying a polyester as claimed in claim 1 to the surface.

18. A method for increasing surface tension and improving hydrophiolic behavior of a hydrophobic surface comprising applying the aqueous dispersion as claimed in claim 8 to the surface.

19. The method of claim 9, wherein said amount is 200 to 1000 g of polyester (100% active) per metric ton of dry paper fiber.

Description

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

(1) In one preferred embodiment of the present invention, the transesterification and condensation of components a) to e) in the presence or absence of component f) takes place in the presence of transesterification and condensation catalysts of the prior art, for example titanium tetraisopropoxide/sodium acetate, dibutyltin oxide, or alkali metal or alkaline earth metal alkoxides.

(2) In a greatly preferred embodiment of the present invention, the polyesters used according to the present invention are obtainable by polymerization of components a) to f) without further components.

(3) In a further greatly preferred embodiment of the present invention, the polyesters used according to the present invention are obtainable by polymerization of components a) to e) without further components.

(4) Preference for use as component a) is given to one or more compounds selected from terephthalic acid, phthalic acid, isophthalic acid, their anhydrides and the mono- and dialkyl esters with C.sub.1-C.sub.6 alcohols of these dicarboxylic acids.

(5) Particular preference for use as component a) is given to one or more compounds selected from terephthalic acid, isophthalic acid and their dimethyl, diethyl, dipropyl and dibutyl esters.

(6) Dimethyl terephthalate is greatly preferred as component a).

(7) Preference for use as component d) is given to one or more compounds selected from the group consisting of polyethylene glycols having weight-average molecular weights of about 200 to 8000 g/mol, polypropylene glycols having weight-average molecular weights of about 200 to 8000 g/mol and polypropylene ethylene glycol having weight-average molecular weights of about 200 to 8000 g/mol.

(8) Particular preference for use as component d) is given to one or more compounds selected from polyethylene glycols having weight-average molecular weights of about 1000 to 2000 g/mol.

(9) Polyethylene glycol having a weight-average molecular weight of 1500 g/mol is greatly preferred as component d).

(10) Preference for use as component e) is given to one or more compounds selected from one or more compounds from the group of one-sidedly endcapped polyalkylene glycols (end plugs), preferably polyethylene glycol monoalkyl ethers or poly[ethlyene glycol-co-propylene glycol] monoalkyl ethers having weight-average molecular weights of about 150 to 2000 g/mol. Particular preference for use as component e) is given to one or more compounds selected from polyethylene glycol monomethyl ethers having weight-average molecular weights of about 1050-1350 g/mol.

(11) Polyethylene glycol monomethyl ether having a weight-average molecular weight of 1250 g/mol is greatly preferred as component e).

(12) Preference for use as component f) is given to compounds selected from the group consisting of citric acid, malic acid, tartaric acid and gallic acid, 2,2-dihydroxymethylpropionic acid, pentaerythritol, glycerol, sorbitol, mannitol, 1,2,3-hexanetriol, benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid) and benzene-1,3,5-tricarboxylic acid (trimesic acid).

(13) Compounds selected from pentaerythritol and glycerol are particularly preferred for use as component f).

(14) Pentaerythritol is greatly preferred for use as component f).

(15) Preference is given to polyesters obtainable by polymerization of components a) to e) in the presence or absence of component f) in the following molar ratios, each based on 1 mol of component a):

(16) 0.2 to 0.8 mol, preferably 0.3 to 0.7 mol, more preferably 0.4 to 0.6 mol and most preferably 0.5 to 0.6 mol of component b), and

(17) 1.0 to 2.0 mol, preferably 1.1 to 1.6 mol, more preferably 1.2 to 1.5 mol and most preferably 1.3 to 1.4 mol of component c), and

(18) 0.05 to 2.0 mol, preferably 0.10 to 1.0 mol, more preferably 0.2 to 0.8 mol and most preferably 0.25 to 0.5 mol of component d), and

(19) 0.01 to 1.0 mol, preferably 0.05 to 0.8 mol, more preferably 0.1 to 0.5 mol and most preferably 0.11 to 0.3 mol of component e), and

(20) in the presence of 0.00001 to 1.0 mol, preferably 0.00001 to 0.5 mol, more preferably 0.0001 to 0.01 mol and most preferably 0.0002 to 0.01 mol, of component f) or in the absence of component f).

(21) The polyesters generally have weight-average molecular weights in the range from 700 to 50 000 g/mol, preferably in the range from 800 to 25 000 g/mol, more preferably in the range from 1000 to 15 000 g/mol and even more preferably in the range from 1200 to 12 000 g/mol. Weight-average molecular weight is determined by size exclusion chromatography in aqueous solution by using a calibration with narrowly distributed sodium polyacrylate as standard.

(22) The polyesters of the present invention are preferably nonionic polyesters.

(23) In one preferred embodiment, the polyesters used according to the present invention contain no residual monomers selected from polyethylene glycols and methyl polyethylene glycols having weight-average molecular weights below 1000 g/mol, which are toxicologically and ecotoxicologically undesirable.

(24) In one preferred embodiment of the polyesters used according to the present invention, the weight fraction of residual monomers in the polyester of components a) to e) and f) used for the polymerization is in each case <1% based on the weight of the polyester.

(25) In a further preferred embodiment, the polyesters used according to the present invention are used in the form of an aqueous dispersion in which the polyesters used according to the invention are present in concentrations of 10% to 30% by weight based on the final aqueous dispersion, more preferably of 15% to 25% by weight and most preferably in a concentration of 20% by weight, based on the final aqueous dispersion.

(26) The polyesters described above modify surfaces of materials having low surface energy and pronounced hydrophobic behavior, such as polyester fabric, felts, wires and rolls, such that, by adsorption of the polyesters described above, the surface tension is increased and the surfaces become more hydrophilic.

(27) Thus, in the presence of the polyesters used according to the present invention, the hydrophobic surfaces of the adhesive contaminants present in the pulp of the paper recycling process become more hydrophilic and the tendency for the tacky particles to deposit on hydrophobic surfaces, for example wires, felts and rolls, is reduced.

(28) The polyesters used according to the present invention can also modify hydrophobic surfaces, for example wires, felts and rolls, and endow them with more hydrophilic properties, which minimizes the deposition tendencies of stickies.

(29) The use which the present invention provides for the polyesters described above further effects a significant improvement in the wettability of hydrophobic surfaces, as of polyester fabrics for example.

(30) It is further advantageous that the polyesters described above possess outstanding dispersing power. Using the polyesters described above it is possible to produce aqueous dispersions of hydrophobic fibers, as of polyester fibers or glass fibers for example.

(31) It is similarly advantageous to use the polyesters described above for improving the printing behavior of oil-based printing inks on hydrophobic surfaces.

(32) In the use of the esters described above, they are added in the papermaking process or in the paper recycling process to the paper fiber furnish as a dispersion in amounts of preferably 200 to 1000 g of polyester (100% active) per metric ton of dry paper fiber to form a homogeneous dispersion and take effect therein. The polyesters of the present invention are added in the form of an aqueous dispersion, preferably as a 20% strength aqueous dispersion. The specified quantity is based on 100% polyester.

(33) The polyesters described above can also be used during the papermaking or paper recycling process by spraying surfaces, as of rolls or felts, for example, with aqueous solutions containing the polyesters described above. These aqueous solutions preferably contain the polyesters used according to the present invention in weight quantities of 0.01 to 0.05%, based on the sprayable solution.

(34) The examples which follow are provided for further elucidation, but not limitation of the invention. Unless explicitly stated otherwise, all percentages are by weight (wt %).

Examples

Preparation of Inventive Polyester 1

(35) A 1-L four-neck flask equipped with KPG stirrer, internal thermometer, Vigreux column, distillation bridge, N.sub.2 supply (5 l/h) and Anschütz-Thiele adapter was initially charged with 164.4 g (0.85 mol) of dimethyl terephthalate, 87.9 g (1.155 mol) of 1,2-propanediol, 29.5 g (0.475 mol) of ethylene glycol, 1.14 g (0.008 mol) of pentaerythritol and 0.75 g (0.0009 mol) of sodium acetate and the reaction mixture was subsequently heated up to 60° C. internal temperature under N.sub.2 blanketing (5 l/h), with stirring at a stirrer speed of 50-100 rpm. The N.sub.2 line was closed and then 0.2 g (0.0007 mol) of titanium tetraisopropoxide was added. Stirrer speed was subsequently raised to 300 rpm and the batch was heated up to an internal temperature of 150° C. in the course of 2 h and to an internal temperature of 200° C. in the course of a further 2 h. The N.sub.2 line was reopened at an internal temperature of 170° C. The reaction mixture was heated at 200° C. for 2 h and the methanol formed was distilled off and condensed in an ice-cooled receiver. The reaction mixture was subsequently cooled down to room temperature and 328.7 g (0.219 mol) of polyethylene glycol 1500 and 137.8 g (0.11 mol) of polyethylene glycol monomethyl ester 1250 were added. The mixture was heated up to 215° C. internal temperature under N.sub.2 blanketing (5 l/h) with stirring at a stirrer speed of 300 rpm, the N.sub.2 line was closed and the pressure was reduced to 150 mbar in the course of 2 h and to 10 mbar in the course of a further 2 h while glycol was distilled off. After supplementary condensation at 215° C. and 10 mbar for 2 h the melt was cooled down to 140-150° C. The system was then vented with N.sub.2 and the hot melt was discharged. A solidified beige polymer melt was obtained.

Preparation of Comparative Polyester 1

(36) A 1-L four-neck flask equipped with KPG stirrer, internal thermometer, Vigreux column, distillation bridge, N.sub.2 supply (5 l/h) and Anschütz-Thiele adapter was initially charged with the following starting materials: 41.53 g (0.25 mol) of dimethyl terephthalate, 27.13 g (0.437 mol) of ethylene glycol, 362.5 g (0.29 mol) of methyl polyethylene glycol 1250, 0.5 g of sodium acetate anhydrous (NaOAc) and 0.13 g of titanium tetraisopropoxide (Ti(iPr).sub.4.

(37) The mixture was heated to about 160° C. (about 15-20 min) and the methanol produced was distilled off. During the distillation, the temperature was gradually raised to 210° C. in the course of 3 h (N.sub.2 (5 l/h) was passed over from an internal temperature of about 180° C.). Methanol was distilled off until the head temperature was below 55° C. (min. 4 h/210° C. subsequent stirring). This was followed by cooling down to 195° C., pressure reduction to 10 mbar in the course of one hour and distillative removal of glycol (head temperature up to about 150° C.). This was followed by supplementary condensation at 10 mbar/195° C. for 4 h (the head temperature was below 75-80° C. at the end). The vacuum was reduced to 5 mbar for 5 min and then the apparatus was vented with N.sub.2 (oil bath below flask, T.sub.i 185-195° C.) and the hot melt was discharged onto a metal tray.

(38) Measurement of Surface Tensions:

(39) TABLE-US-00001 TABLE 1 Surface tension of untreated polyester fiber X (polyester fiber X is not made of the inventive polyesters) and of a polyester fiber X treated with a 0.04 wt % aqueous dispersion of inventive polyester 1 and of comparative polyester 1. Polyester fiber X Surface tension [mN/m] untreated 45.5 inventive polyester 1 61.2 comparative polyester 1 53.3 instrument: SITA Pro Line T15 bubble pressure tensiometer setting: Auto Mode bubble life: 15 ms to 15 s measurement: at 15 s sample solution: 0.04 wt % inventive polyester 1 or comparative polyester 1 in distilled water temperature: 20° C.
Measurement of Deposits:

(40) TABLE-US-00002 TABLE 2 Deposition of a paper stock which contains adhesive material on a polyester wire a) having an unmodified surface, b) modified with inventive polyester 1, c) modified with comparative polyester 1 Polyester Polyester wire after Polyester wire 15 min Reduction concen- before contact Weight in tration deposition time increase deposit Sample [wt %] [g] [g] [mg] [%] a 0 308.7 315.9 7.2 0 (control) b 0.1 311.0 311.7 0.7 90.3 (inventive polyester 1) c 0.1 305.6 310.2 4.6 36.1 (comparative polyester 1) The polyester wire used is not made of the inventive polyesters.

(41) An adhesive label consisting of 75 g of paper and 25 g of an acrylic pressure-sensitive adhesive which in turn consists of 80 wt % of poly(2-ethylhexyl acrylate-acrylic acid) copolymer and 20 wt % of styrene-butadiene copolymer is applied to a 10 g pulp sheet from bleached birchwood. This sheet has 750 ml of tap water added to it and is stirred at 50° C. for 2 minutes in a mixer at a high speed to form a homogeneous paper stock. The mixture obtained is bulked with tap water to an overall volume of 1000 ml and split into 200 ml samples.

(42) Inventive polyester 1 and comparative polyester 1 are each made up into 0.1 weight percent solutions with 100 ml of tap water in each case. 3 polyester wires of the Primobond SF brand (Heimbach), measuring 30×50 mm, are weighed out to the nearest decimal. Each polyester wire is dipped for 10 seconds at room temperature either into pure tap water or into the 0.1 weight percent inventive polyester 1 solution or into the 0.1 weight percent comparative polyester 1 solution for 10 seconds at a time and then removed from the tap water or the 0.1 weight percent solutions and placed into an empty 400 ml glass beaker. The 400 ml glass beakers are each filled with 200 ml of paper stock. Each polyester wire, which is either untreated (tap water, control) or else treated (with inventive polyester 1 or comparative polyester 1) in the above-described manner, is placed into the 200 ml sample a), b) or c) and the sample is stirred at 200 revolutions/minute for 15 minutes. The polyester wires are removed from the samples, rinsed off with cold water, air dried and weighed.

(43) The results show that the use of inventive polyester 1 causes a distinctly smaller amount of adhesive to adhere to the polyester wire (90.3% improvement), compared with the untreated polyester wire (0% improvement) or compared with the use of comparative polyester 1 (36.1% improvement).