WO2017079206A1

WO2017079206A1 - Modified polyester

Info

Publication number: WO2017079206A1
Application number: PCT/US2016/060000
Authority: WO
Inventors: Uwe Bayer; Isaac Iverson; Stephan KRETSCHNER; Josef WIEDMAN
Original assignee: Invista North America S.Ar.L.
Priority date: 2015-11-03
Filing date: 2016-11-02
Publication date: 2017-05-11

Abstract

A polyester comprising 0.1 to 7 weight percent, based on the total weight of the polyester, of at least one monomeric component of formula (I): wherein R1 is independently chosen from H, methyl, and ethyl, R₂ and R₃ are independently chosen from -COOH, -COOMe, -COOEt, -COOIPr, -COOnPr, - CH₂OH, -CI, -Br, and NH₂, and J and K are independently chosen from 1, 2, 3, 4, 5, 6, 7, or 8; at least one dicarboxylic acid component other than the monomeric component of formula (I); and at least one diol component.

Description

MODIFIED POLYESTER

Field of Invention

[0001] The present disclosure generally relates to a modified polyester resin.

Background

[0002] Polyester resins are used in the production of a wide range of

materials such as films, fibers and molded products. For example, polyester resins are commonly used in the production of clothing fibers, carpet fibers, and other cloth-like materials. Examples of such polyester resins include

polyethylene terephthalate (PET), polybutylene terephthalate (PBT),

polytrimethylene terephthalate (PTT), polylactic acid (PLA), polyglycolic acid (PGA), polycaprolactone (PCL), polybutylene succinate (PBS); and polyethylene naphthalate (PEN). PET, for example, is a large volume, relatively low cost polymer used in many fields, and is among the most common polyesters.

[0003] Polyester polymers, such as PET, PBT, PTT, PLA, PGA, PBS and

PEN polymers, have been particularly used in the production of certain durable materials that are routinely subjected to conditions of elevated wear and use. Recently, some manufacturers have substituted known polyester fibers with other types of polymers that exhibit certain properties, such as improved stain recovery and higher elastic modulus. Other polymers, such as those which contain segments typically expected to undergo hydrogen bonding between polymer chains and chain segments, have thus replaced polyester fibers in the production of some durable materials. These other types of polymers, however, are relatively costly and may not be suitable in a variety of commercial applications. Thus, it would be advantageous to produce a polymer that exhibits improved mechanical properties while maintaining the cost advantage and certain other beneficial properties that are characteristic of polyesters.

Summary of the Invention

[0004] The disclosed modified polyester resin is directed to overcoming one or more of the problems set forth above.

[0005] In one embodiment, the present disclosure is directed to a polyester

comprising:

(a) 0.1 to 7 weight percent, based on the total weight of the polyester, of at least one monomeric component of formula (I):

wherein Ri is independently chosen from H, methyl, and ethyl,

R2 and R3 are independently chosen from -COOH, -OH, -CI, -Br, and NH2, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

(b) at least one dicarboxylic acid component other than the monomeric component of formula (I); and

(c) at least one diol component other than the monomeric component of formula (I).

[0006] In an additional embodiment, the present disclosure is directed to a polyester comprising: 0.1 to 7 weight percent, based on the total weight of the polyester, of one monomeric component of formula (I):

Ri (I)

wherein Ri is independently chosen from H, methyl, and ethyl,

R2 and R3 are independently chosen from -COOH, -OH, -CI, -Br, and NH2, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

(c) at least one diol component other than the monomeric component of formula (I),

and further wherein the number average molecular weight of the monomeric component of formula (I) is no more than 900.

[0007] In a further embodiment, the present disclosure is directed to a

polyester comprising:

wherein Ri is independently chosen from H, methyl, and ethyl,

R2 and R3 are independently chosen from -COOH, -OH, -CI, -Br, and NH2, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

(c) at least one diol component other than the monomeric component of formula (I) ,

[0008] In yet another embodiment, the present disclosure is directed to a polyester consisting essentially of:

wherein Ri is independently chosen from H, methyl, and ethyl, R2 and R3 are independently chosen from -COOH, -COOMe, -COOEt, - COOflPr, COO/Pr, COOnBu, COOsecBu, -COOffiu, -OH, -CI, -Br, and NH₂, and J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

(c) at least one diol component. In further embodiments, the monomeric component of formula (I) has a number average molecular weight of no more than 900.

[0009] Additional embodiments of the present disclosure are also directed to a polyester comprising:

(a) 0.1 to 7 weight percent, based on the total weight of the polyester, of at least one monomeric component of formula (II):

(I

(b) at least one dicarboxylic acid component other than the monomeric component of formula (II); and

(c) at least one diol component.

[0010] In a further embodiment, the present disclosure is directed to

polyester consisting essentially of:

(II)

(c) at least one diol component.

Detailed Description of the Invention

[0011] In certain embodiments, the at least one dicarboxylic acid component can be chosen from terephthalic acid (TPA), dimethyl terephthalate (DMT), aromatic/aliphatic dicarboxylic acid, isophthalic acid, naphthalene 2,6-dicarboxylic acid, alkali sulfoisophthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic dicarboxylic acid, any monoester of these dicarboxylic acids, any diester of these dicarboxylic acids, and mixtures thereof.

[0012] In certain embodiments, the diol component can be chosen from

ethylene diol, diethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, neopentyl glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, p-xylene glycol, and mixtures thereof.

[0013] The chemical name of the monomeric component of formula (II) is 1 ,

3-bis(2-carboxyethyl)isocyanuric acid (BCI).

[0014] The monomeric component of formula (I) disclosed herein can have a molecular weight of no greater than 900. In certain embodiments, the molecular weight of the monomeric component of formula (I) can range, for example, from

500 to 900, from 550 to 900, from 600 to 900, from 650 to 900, from 700 to 900, from 750 to 900, from 800 to 900, from 500 to 850, from 550 to 850, from 600 to 850, from 650 to 850, from 700 to 850, from 750 to 850, from 500 to 800, from 550 to 800, from 600 to 800, from 650 to 800, from 700 to 800, from 500 to 750, from 550 to 750, from 600 to 750, from 650 to 750, from 500 to 700, from 550 to 700, from 600 to 700, from 500 to 650, from 550 to 650, and from 500 to 600.

[0015] The at least one monomeric component, represented by formulae (I) and (II), can be present in the modified polyester resin an amount ranging from 0.1 to 7 weight percent, based on the total weight of the modified polyester resin. In certain embodiments, the at least one monomeric component can be present in an amount ranging, for example, from 0.5 to 7 weight percent, from 1 to 7 weight percent, from 1.5 to 7 weight percent, from 2 to 7 weight percent, from 2.5 to 7 weight percent, from 3 to 7 weight percent, from 3.5 to 7 weight percent, from 4 to 7 weight percent, from 4.5 to 7 weight percent, from 5 to 7 weight percent, from 0.1 to 6 weight percent, from 0.5 to 6 weight percent, from 1 to 6 weight percent, from 1.5 to 6 weight percent, from 2 to 6 weight percent, from 2.5 to 6 weight percent, from 3 to 6 weight percent, from 3.5 to 6 weight percent, from 4 to 6 weight percent, from 0.1 to 5 weight percent, from 0.5 to 5 weight percent, from 1 to 5 weight percent, from 1.5 to 5 weight percent, from 2 to 5 weight percent, from 2.5 to 5 weight percent, from 3 to 5 weight percent, from 0.1 to 4 weight percent, from 0.5 to 4 weight percent, from 1 to 4 weight percent, from 1.5 to 4 weight percent, from 2 to 4 weight percent, from 0.1 to 3 weight percent, from 0.5 to 3 weight percent, and from 1 to 3 weight percent.

[0016] In some embodiments of the present disclosure, the dicarboxylic acid component other than the monomeric component of formulae (I) or (II) can comprise from 50 to 80 weight percent of the total weight of the modified polyester resin. For example, the dicarboxylic acid component other than the monomeric component of formulae (I) or (II) can comprise, based on the total weight of the modified polyester resin, from 55 to 80 weight percent, from 60 to 80 weight percent, from 65 to 80 weight percent, from 70 to 80 weight percent, from 50 to 75 weight percent, from 55 to 75 weight percent, from 60 to 75 weight percent, from 65 to 75 weight percent, from 50 to 70 weight percent, from 55 to 70 weight percent, from 60 to 70 weight percent, from 50 to 65 weight percent, from 55 to 65 weight percent, and from 50 to 60 weight percent.

[0017] In some embodiments, the diol can comprise from 20 to 80 weight percent of the total weight of the modified polyester resin. For example, the diol component can comprise, based on the total weight of the modified polyester resin, from 25 to 80 weight percent, from 30 to 80 weight percent, from 35 to 80 weight percent, from 40 to 80 weight percent, from 45 to 80 weight percent, from 50 to 80 weight percent, from 55 to 80 weight percent, from 60 to 80 weight percent, from 65 to 80 weight percent, from 70 to 80 weight percent, from 20 to 70 weight percent, from 25 to 70 weight percent, from 30 to 70 weight percent, from 35 to 70 weight percent, from 40 to 70 weight percent, from 45 to 70 weight percent, from 50 to 70 weight percent, from 55 to 70 weight percent, from 60 to 70 weight percent, from 20 to 60 weight percent, from 25 to 60 weight percent, from 30 to 60 weight percent, from 35 to 60 weight percent, from 40 to 60 weight percent, from 45 to 60 weight percent, from 50 to 60 weight percent, from 20 to 50 weight percent, from 25 to 50 weight percent, from 30 to 50 weight percent, from 35 to 50 weight percent, and from 40 to 50 weight percent.

[0018] In other embodiments, the at least one dicarboxylic acid component comprises: i. from 80 to 99.9 mole percent of terephthalic acid or an ester thereof; ii. from 0 to 20 mole percent of an aromatic/aliphatic dicarboxylic acid or ester thereof having up to 20 carbon atoms; and

iii. from 0.1 to less than 20 mole percent of at least one monomeric component of formulae (I) or (II).

[0019] In certain embodiments, the terephthalic acid or an ester thereof can be present in the dicarboxylic acid component in a mole percent, for example, ranging from 85 to 99.9 mole percent, from 90 to 99.9 mole percent, from 95 to 99.9 mole percent, from 80 to 99.5 mole percent, 85 to 99.5 mole percent, from 90 to 99.5 mole percent, from 95 to 99.5 mole percent, from 80 to 99 mole percent, 85 to 99 mole percent, from 90 to 99 mole percent, from 95 to 99 mole percent, from 80 to 95 mole percent, 85 to 95 mole percent, from 90 to 95 mole percent, and from 80 to 85 mole percent.

[0020] In other embodiments, the aromatic/aliphatic dicarboxylic acid or ester thereof, having up to 20 carbon atoms, can be present in the dicarboxylic acid component in a mole percent, for example, ranging from 0.1 to 20 mole percent, from 0.5 to 20 mole percent, from 1 to 20 mole percent, from 5 to 20 mole percent, from 10 to 20 mole percent, from 15 to 20 mole percent, from 0.1 to 15 mole percent, from 0.5 to 15 mole percent, from 1 to 15 mole percent, from 5 to 15 mole percent, from 10 to 15 mole percent, from 0.1 to 10 mole percent, from 0.5 to 10 mole percent, from 1 to 10 mole percent, from 5 to 10 mole percent, from 0.1 to 5 mole percent, from 0.5 to 5 mole percent, and from 1 to 5.

[0021] In further embodiments, the monomeric component of formulae (I) or

(II) can be present in the dicarboxylic acid component in a mole percent, for example, ranging from 0.3 to 20 mole percent, from 0.5 to 20 mole percent, from 1 to 20 mole percent, from 5 to 20 mole percent, from 10 to 20 mole percent, from 15 to 20 mole percent, from 0.1 to 15 mole percent, from 0.5 to 15 mole percent, from 1 to 15 mole percent, from 5 to 15 mole percent, from 10 to 15 mole percent, from 0.1 to 10 mole percent, from 0.5 to 10 mole percent, from 1 to 10 mole percent, from 5 to 10 mole percent, from 0.1 to 5 mole percent, from 0.5 to 5 mole percent, and from 1 to 5.

[0022] In other embodiments, the at least one diol component comprises i. from 80 to 100 mole percent of ethylene glycol; and

ii. from 0 to 20 mole percent of at least one other glycol chosen from diethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, neopentyl glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, and p-xylene glycol.

[0023] In certain embodiments, the ethylene glycol can be present in the diol component in a mole percent, for example, ranging from 85 to 100 mole percent, from 90 to 100 mole percent, from 95 to 100 mole percent, from 80 to 99.5 mole percent, 85 to 99.5 mole percent, from 90 to 99.5 mole percent, from 95 to 99.5 mole percent, from 80 to 99 mole percent, 85 to 99 mole percent, from 90 to 99 mole percent, from 95 to 99 mole percent, from 80 to 95 mole percent, 85 to 95 mole percent, from 90 to 95 mole percent, and from 80 to 85 mole percent. In other embodiments, the at least one other glycol can be present in the diol component in a mole percent, for example, ranging from 0.1 to 20 mole percent, from 0.5 to 20 mole percent, from 1 to 20 mole percent, from 5 to 20 mole percent, from 10 to 20 mole percent, from 15 to 20 mole percent, from 0.1 to 15 mole percent, from 0.5 to 15 mole percent, from 1 to 15 mole percent, from 5 to 15 mole percent, from 10 to 15 mole percent, from 0.1 to 10 mole percent, from 0.5 to 10 mole percent, from 1 to 10 mole percent, from 5 to 10 mole percent, from 0.1 to 5 mole percent, from 0.5 to 5 mole percent, and from 1 to 5.

[0024] In yet a further embodiment, the present disclosure is directed to a polyester comprising :

(a) from 50 to 80 weight percent of a dicarboxylic acid component comprising:

i. from 80 to 99.9 mole percent of terephthalic acid or an ester thereof;

ii. from 0 to 20 mole percent of an aromatic/aliphatic dicarboxylic acid or ester thereof having up to 20 carbon atoms; and

iii. from 0.1 to less than 20 mole percent of at least one monomeric component of formulae (I) or (II);

(b) from 20 to 80 weight percent of a glycol component comprising:

i. from 80 to 100 mole % of ethylene diol; and

ii. from 0 to 20 mole percent of at least one other glycol chosen from diethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, neopentyl glycol, 1 ,4- butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, and p-xylene glycol.

[0025] It is also contemplated that each of the modified polyester resin

generally disclosed above in the present disclosure, such as in paragraphs [0005] - [0010] and [0024], can be included in a polyester composition.

[0026] For example, certain embodiments of the present disclosure are

directed to a polyester composition comprising from 5 to 95 weight percent, based on the total weight of the polyester composition, of at least one modified polyester resin described herein; and from 5 to 95 weight percent, based on the total weight of the polyester composition, of at least one other polymer. The at least one other polymer can include, for example, polyolefins, maleic anhydride grafted polyolefins, polyamides, ionomers and polyethers. Non-limiting examples of polyolefins include polyethylene, polypropylene, polymethylpentene, and polybutene, non-limiting examples of ionomers include Surlyn® ionomer resins and non-limiting examples of polyamides include nylon-6; nylon-6,6; nylon-12; and Kevlar®.

[0027] In certain polyester compositions according to the present disclosure, the at least one modified polyester resin can be present in an amount, based on the total weight of the polyester composition, ranging from 10 to 95 weight percent, 20 to 95 weight percent, 30 to 95 weight percent, 40 to 95 weight percent, 50 to 95 weight percent, 60 to 95 weight percent, 70 to 95 weight percent, 80 to 95 weight percent, 10 to 85 weight percent, 20 to 85 weight percent, 30 to 85 weight percent, 40 to 85 weight percent, 50 to 85 weight percent, 60 to 85 weight percent, 70 to 85 weight percent, 10 to 75 weight percent, 20 to 75 weight percent, 30 to 75 weight percent, 40 to 75 weight percent, 50 to 75 weight percent, 60 to 75 weight percent, 10 to 65 weight percent, 20 to 65 weight percent, 30 to 65 weight percent, 40 to 65 weight percent, 50 to 65 weight percent, 10 to 45 weight percent, 20 to 45 weight percent, 30 to 45 weight percent, 10 to 35 weight percent, 20 to 35 weight percent, and 10 to 25 weight percent.

[0028] In certain polyester compositions according to the present disclosure, the at least one other polymer can be present in an amount, based on the total weight of the polyester composition, ranging from 10 to 95 weight percent, 20 to 95 weight percent, 30 to 95 weight percent, 40 to 95 weight percent, 50 to 95 weight percent, 60 to 95 weight percent, 70 to 95 weight percent, 80 to 95 weight percent, 10 to 85 weight percent, 20 to 85 weight percent, 30 to 85 weight percent, 40 to 85 weight percent, 50 to 85 weight percent, 60 to 85 weight percent, 70 to 85 weight percent, 10 to 75 weight percent, 20 to 75 weight percent, 30 to 75 weight percent, 40 to 75 weight percent, 50 to 75 weight percent, 60 to 75 weight percent, 10 to 65 weight percent, 20 to 65 weight percent, 30 to 65 weight percent, 40 to 65 weight percent, 50 to 65 weight percent, 10 to 45 weight percent, 20 to 45 weight percent, 30 to 45 weight percent, 10 to 35 weight percent, 20 to 35 weight percent, and 10 to 25 weight percent.

[0029] In certain of these embodiments, the polyester composition can further comprise at least one filler.

TEST PROCEDURES INTRINSIC Viscosity

[0030] Intrinsic viscosity (IV) was determined on a 0.01 g/mL polymer

solution in dichloroacetic acid. The IV values are typically reported in units of deciliters per gram (dl/g). One deciliter is 100 ml or 100 cm³.

[0031 ] Polymer chip was pressed for about 1 minute (pressure: 400 kN at

1 15°C; press model: PW40^® Weber, Remshalden-Grunbach, Germany).

Amorphous or pressed chips (approx.. 500 mg), were weighed on an analytical balance (Mettler AT 400^®) and dichloroacetic acid was added (via Dosimat^® 665 or 776, from Metrohm) in such an amount, that a final polymer concentration of 0.0100 g/mL was reached.

[0032] The polymer was dissolved with agitation at 55°C (internal

temperature) for 2.0 hrs. After complete dissolution of the polymer, the solution was cooled to 20°C [0033] The viscosity measurement was performed with a micro-Ubbelohde viscometer from Schott (type 53820/11; 0: 0.70 mm) in a Schott AVS 500^® apparatus. The bath temperature was held at 25.00 ± 0.05°C. The micro- Ubbelohde viscometer was purged four times with pure dichloroacetic acid, then the solvent was equilibrated for two minutes. The flow time of the pure solvent was measured three times. The solvent was drawn off, and the viscometer was purged with the polymer solution four times. Before measurement, the polymer solution was equilibrated for two minutes, and then the flow time of this solution was measured three times.

[0034] The relative viscosity (RV) was determined by dividing the flow time of the solution by the flow time of the pure solvent. RV was converted into SV according to equation 1. IV was calculated according to equation II.

SV = (RV-1)*1000 Equation 1 IV (dl/g) = [(RV-1) x 0.691] + 0.063 Equation 2

Thermal analysis:

[0035] Melting temperature (T_m) was measured according to ASTM D 3418-

97. A sample of about 10 mg was cut from various sections of the polymer chip, and sealed in an aluminum pan. A Netzsch DSC 204 instrument was used for the analysis. The sample was heated under nitrogen from -30 °C to 300 °C, held for five minutes and cooled to -30 °C at a scan rate of 10°C/min prior to the second heating cycle. The melting point (T_m) was determined as the melting peak temperature and was measured on the second heating cycle where the second heating cycle is the same as the first. Melt Rheology

[0036] A RHEO-TESTER 1000 instrument was used to measure the melt viscosity of the polyester resins. A 30 mm long capillary having diameter = 1 mm was used. The polyester resins were dried for about 16 hrs at about 160°C under reduced pressure (< 1 mbar). The dried polyester resin was compressed to 100 barg, and melted for 5 minutes at the desired measurement temperature. The measurement was made once the polyester resin was melted. Material tested at 200 sec^-1 was collected, and the solution viscosity was determined. No Bagley or Rhabinowitsch-Weissenberg corrections were applied to the data thus obtained.

[0037] The disclosed polyester resins according to the present disclosure were produced by polycondensation via two synthetic methods described below. I. Examples of Polycondensation Procedure: DMT route

[0038] A pilot line ester interchange reactor having heating zones of 189,

210, and 228 °C was used. DMT and EG were fed continuously to the reactor at feed rates of 40.4 kg/hr and 49.1 kg/hr, respectively. EG was split into two flows- - one to the front end of the reactor, and the second to a later stage of the reactor. Mn(OAc)2*4H20 (13.0 g/hr) was added as catalyst in an EG solution at the beginning of the ester interchange reactor. The catalyst solution also contained acetic acid (1 .6 g/hr).

[0039] The reaction vapors were transferred to a column that separated

methanol (MeOH) from EG. The latter was sent back to the ester interchange reactor, while MeOH was removed from the system. The El product was dispensed from the reactor, and recovered after cooling in a drum. El product properties were determined using well-known analytical techniques to be as follows: IV; 0.122, CEG: 8.5 mmol/kg, DEG: 0.37%, El degree: 99.45%. The product was judged to be suitably pure bis(2-hydroxyethyl) terephthalate (BHET).

Example 1 - Polycondensation incorporating 1 % BCI in PET

[0040] BHET (2300 g) was melted in a 4 L flask under nitrogen. The molten monomer was stirred, and then the flask was charged with a solution of PPA (3.052 g, 5% in EG). After 10 minutes, the flask was charged with SD2O3 (97%) (0.807 g, reagent grade), and the contents were stirred an additional 10 minutes. The mixture was cooled to room temperature gradually over eight hours.

[0041] The mixture was remelted in the flask, and 3-bis(2- carboxyethyl)isocyanuric acid (BCI) (20 g, 73.2 mmol) was added as a slurry in 60 g EG. The contents were stirred for 30 min, then the melt was drained into a 4 L jacketed autoclave preheated to 215°C. After 30 minutes stirring at 35 rpm, the temperature of the heating jacket was increased to 281 °C for 1 hr, and the pressure was reduced to 2.5 mbar. Condensate was removed from the autoclave over a period of 2 hr. During this stage the torque at the agitator went up by 0.09 Nm. The final heating jacket temperature was 285 °C and the final pressure was 0.9-1.0 mbar. The temperature of the autoclave contents was estimated to be about 270 °C.

[0042] To drain the product, the agitator was stopped and the autoclave was charged with nitrogen. The modified polyester was pressed out of the autoclave as a strand, cooled in a cooling water bath, and cut into chip.

[0043] The product was found to have the following properties: IV = 0.542,

CEG = 14.7 mmol/kg, DEG = 0.56%, color: L* = 67.8, a* = 0.7, b* = 9.2, elemental N = 0.15%. Thermal analysis: The (1^st cooling): 185 °C / 205 °C; T_m (2^nd heating): 258 °C. Based on the elemental nitrogen content,

[0044] a BCI content of 1.0% in the polymer product was calculated.

Example 2 - Polycondensation incorporating 2.5 % BCI in PET

[0045] The same general procedure was applied as described in Example 1.

A mixture of 50 g BCI in 120 g EG was added.

[0046] Condensate was removed from the autoclave over a period of 66 min.

During this stage the torque at the agitator went up by 0.09 Nm. The final heating jacket temperature achieved 284°C and the final pressure 0.8 mbar. The product temperature was estimated to be about 270°C.

[0047] The product was found to have the following properties: IV = 0.560,

CEG = 30.5 mmol/kg, DEG = 0.50%, color: L* = 72.6, a* = -0.4, b^* = 13.1 , elemental N = 0.39%. Thermal analysis: The (1^st cooling): 183 °C; T_m (2^nd heating): 252.8 °C. Based on the elemental nitrogen content, a BCI content of 2.5% in the polymer product was calculated.

Example 3 - Polycondensation incorporating 5 % BCI in PET

[0048] The same general procedure was applied as described in Example 1.

A mixture of 100 g BCI in 200 g EG was added. Condensate was removed from the autoclave over a period of 50 min. During this stage the torque at the agitator went up by 0.09 Nm. The final heating jacket temperature achieved 276°C and the final pressure 0.6mbar. The product temperature was estimated to be about 260°C.

[0049] The product was found to have the following properties: IV = 0.629,

CEG = 58.9 mmol/kg, DEG = 0.48%, color: L* = 69.3, a* = 2.0, b^* = 16.3, elemental N = 0.75%. Thermal analysis: T_hc (1^st cooling): 177 °C; T_m (2^nd heating): 243.2 °C. Based on the elemental nitrogen content, a BCI content of 5% in the polymer product was calculated.

Comparative Example 4 - Control PET resin

[0050] The same general procedure was applied as described in Example 1 , except that no BCI/EG slurry was added. The polycondensation reaction took place over 3 hr, 20 min, during which time the torque at the agitator increased by 0.09 Nm. The final heating jacket temperature was 285°C, and the final autoclave pressure was 1 .2 mbar. The product temperature was estimated to be about 270°C.

[0051 ] The product was found to have the following properties: IV = 0.587;

CEG = 12.6 mmol/kg; DEG = 0.56%; color: L* = 56.4, a* = -0.9, b* = 3.9.

Thermal analysis: T_hc (1^st cooling): 184 °C / 208 C; T_m (2^nd heating): 256 °C.

II. Examples of Polycondensation Procedure: PTA route

Example 5 - Polycondensation incorporating 1 % BCI in PET

[0052] The polycondensation is preceded by preparation of PTA/EG

oligomer, herein referred to as "primary esterifier product," or "PE product."

[0053] To make PE product, PTA/EG slurry (54.7 kg/hr, 1 :1.1 PTA: EG mol ratio) and water (1 kg/hr) were fed to the primary esterifier of a continuous polycondensation apparatus. The esterification was performed at 260°C product temperature at 1.2 bar (g), at a calculated residence time of approximately 1.3 hours. The PE product was drained from the reactor outlet pipe via a drain valve, and collected after cooling in a drum. PE product properties were determined as follows: IV = 0.131 , CEG = 888 mmol/kg, DEG = 0.92%. This material was then esterified using a 4 L steel vessel equipped with a heating jacket, a stirrer, and a Vigreux glass column. The vessel was charged with PE product (2.18 kg) and EG (0.1 kg). The reaction was performed at atmospheric pressure. The vessel was heated using thermal oil at 250 °C. Agitation was initiated when the mixture was molten. The esterification of residual carboxylate end groups was indicated by the formation of condensate water. After 30 min, BCI (20 g) and EG (100 g) were added. When the water condensate flow ceased, Sb203 (0.617 g, 97% grade) was added and the mixture was stirred for 15 min. The melt was then drained into the preheated autoclave for subsequent polyesterification.

Polycondensation:

54] Over the course of half an hour, the oil temperature in the heating jacket was increased from 237 °C to 287 °C, and the vessel pressure was reduced to approximately 4 mbar. In the subsequent polycondensation step, the IV build-up was monitored by the increase of the agitator torque. The final polycondensation temperature in the heating jacket was 290 °C. The

polycondensation run time was 62 min. The BCI modified product was drained from the autoclave by nitrogen overpressure of about 0.5 barg, was cooled in a cooling water bath and cut into chip form. The properties of this product were determined to be: IV = 0.576, CEG = 38.0 mmol/kg, DEG = 1.01 %, color: L* = 68.1 , a* = 0.8, b* = 15.2.

Example 6 - Polycondensation incorporating 2.5 % BCI in PET [0055] The esterifier vessel was preheated using oil at 265 °C. The vessel was charged with PE product (750 g) and EG (50 g). Agitation was initiated when the mixture was molten, then a slurry of PTA (1 197 g), EG (590 g) and BCI (53.25 g) was added to the esterifier in 50-100 g portions over approximately 6 h. The reaction was carried out under atmospheric pressure. This procedure required the column head temperature to be no greater than 1 10-115°, to prevent significant loss of EG from the apparatus. Towards the end, additional EG (100 g) was added to complete the esterification. Sb203 (0.657 g, 97% grade) was added and the mixture was stirred for 15 min. The melt was then drained into the preheated autoclave.

[0056] Over the course of half an hour, the oil temperature in the heating jacket was increased from 237 to 294°C, and the vessel pressure was reduced to approximately 4 mbar. The IV build up was monitored by the increase of the agitator torque. The final polycondensation temperature in the heating jacket was 294 °C. The elapsed time for polycondensation was 27 minutes. The BCI modified product was drained from the autoclave by nitrogen overpressure of about 0.5 barg, run through a cooling water bath, and cut into chip. Product properties were determined to be the following: IV = 0.600, CEG = 46.6 mmol/kg, DEG = 2.18%, color: L* = 68.2, a^* = 0.7, b^* = 13.5.

Example 7 Polycondensation incorporating 2.5 % BCI in PET

[0057] The same procedure as Example 5 was applied, except that 50 g BCI was added without any additional EG. The polycondensation time was 35 minutes at approximately 275 °C. Product properties were determined to be the following: IV = 0.590, CEG = 48.4 mmol/kg, DEG = 1.05%, color: L* = 63.3, a* = 1.8, b^* = 17.8.

Comparative Example 8 - Control PET resin prepared from PE product

[0058] The same procedure as Example 5 was applied, except that no

BCI/EG mixture was added. The polycondensation time was 1 h 26 minutes, and the final polycondensation temperature was estimated to about 280°C. Product properties were found to be the following: IV = 0.574, CEG = 25.6 mmol/kg, DEG = 1.15%, color: L* = 64.9, a* = -0.5, b* = 10.6.

III. Solid State Polymerization Procedure

[0059] The products obtained in Examples 1 , 2, 3, 6, and Comparative

Example 4 were each subjected to solid state polymerization (SSP) routines to increase sample IV. SSP was performed under reduced pressure (about 1 mbar) and elevated sample temperature (215°C). The SSP routine was performed for 8 and 24 hours.

[0060] Abbreviations

Claims

What Is Claimed Is:

1 . A polyester comprising:

Ri (I)

wherein Ri is independently chosen from H, methyl, and ethyl,

R2 and R3 are independently chosen from -COOH, -COOMe, -COOEt, - COO/^'Pr, -COO/?Pr, -OH, -CI, -Br, and NH2, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

2. A polyester comprising:

wherein Ri is independently chosen from H, methyl, and ethyl,

R2 and R3 are independently chosen from -COOH, -COOMe, -COOEt, - COO/Pr, -COOnPr, -OH, -CI, -Br, and NH₂, and J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

(c) at least one diol component other than the monomeric component of formula (I), wherein the molecular weight of the monomeric component of formula (I) is no more than 900 g/mol.

3. A polyester consisting essentially of:

(I)

wherein Ri is independently chosen from H, methyl, and ethyl,

R₂ and R₃ are independently chosen from -COOH, -COOMe, -COOEt, - COO/Pr, -COOnPr, -OH, -CI, -Br, and Nhb, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

4. A polyester consisting essentially of:

(I) wherein Ri is independently chosen from H, methyl, and ethyl,

R₂ and R₃ are independently chosen from -COOH, -COOMe, -COOEt, - COO/Pr, -COOnPr, -OH, -CI, -Br, and NH₂, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

wherein the molecular weight of the monomeric component of formula (I) is no more than 900 g/mol.

5. A polyester comprising:

(c) at least one diol component.

6. A polyester consisting essentially of:

H

(ii);

(c) at least one diol component.

7. A polyester comprising:

(I)

wherein Ri is independently chosen from H, methyl, and ethyl,

R2 and R3 are independently chosen from -COOH, -COO e, -COOEt, - COO/Pr, -COOnPr, -OH, -CI, -Br, and NH₂, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

(b) 50 to 80 weight percent, based on the total weight of the polyester, of at least one dicarboxylic acid component other than the monomeric component of formula (I); and

(c) from 20 to 80 weight percent, based on the total weight of the polyester, at least one diol component other than the monomeric component of formula (I).

8. A polyester comprising: (a) 0.1 to 7 weight percent, based on the total weight of the polyester, of at least one monomeric component of formula (I):

wherein Ri is independently chosen from H, methyl, and ethyl,

R2 and R3 are independently chosen from -COOH, -COOMe, -COOEt, - COO/^'Pr, -COOnPr, -OH, -CI, -Br, and NH2, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

(c) from 20 to 80 weight percent, based on the total weight of the polyester, at least one diol component, other than the monomeric component of formula (I),

wherein the molecular weight of the monomeric component of formula (l) is no more than 900 g/mol.

9. A polyester consisting essentially of:

wherein Ri is independently chosen from H, methyl, and ethyl, R2 and R3 are independently chosen from -COOH, -COOMe, -COOEt, - COO/Pr, -COOnPr, -OH, -CI, -Br, and NH2, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

10. A polyester consisting essentially of:

(a) 0,1 to 7 weight percent, based on the total weight of the polyester, of at least one monomeric component of formula (I):

(I)

wherein Ri is independently chosen from H, methyl, and ethyl,

R2 and R3 are independently chosen from -COOH, -COOMe, -COOEt, - COO/Pr, -COO/iPr, -OH, -CI, -Br, and NH₂, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

(c) from 20 to 80 weight percent, based on the total weight of the polyester, at least one diol component other than the monomeric component of formula (I).,

1 1 . The polyester according to any of claims 1 -14, wherein the dicarboxylic acid component comprises terephthalic acid.

12. The polyester according to any of claims 1 -14, wherein the dicarboxylic acid component comprises dimethyl terephthalate.

13. The polyester according to any of claims 1-14, wherein the glycol component comprises ethylene glycol.

14. A polyester comprising:

(a) from 50 to 80 weight percent of a dicarboxylic acid component comprising:

i. from 80 to 99.9 mole percent of terephthalic acid or an ester thereof;

iii. from 0.1 to less than 20 mole percent of at least one monomeric component of formula (I):

wherein Ri is independently chosen from H, methyl, and ethyl,

R2 and R3 are independently chosen from -COOH, -COOMe, -COOEt, - COO/Pr, -COOnPr, -OH, -CI, -Br, and NH₂, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

(b) from 20 to 80 weight percent of a glycol component comprising: i. from 80 to 100 mole % of ethylene diol; and ii. from 0 to 20 mole percent of at least one other glycol chosen from diethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, neopentyl glycol, 1 ,4- butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol and p-xylene glycol.

15. A polyester consisting essentially of:

(a) from 50 to 80 weight percent of a dicarboxylic acid component comprising:

i. from 80 to 99.9 mole percent of terephthalic acid or an ester thereof;

Ri (I)

wherein Ri is independently chosen from H, methyl, and ethyl,

R2 and F¾ are independently chosen from -COOH, -COOMe, -COOEt, - COO/Pr, -COO/iPr, -OH, -CI, -Br, and Nh , and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

(b) from 20 to 80 weight percent of a glycol component comprising: i. from 80 to 100 mole % of ethylene diol; and

ii. from 0 to 20 mole percent of at least one other glycol chosen from diethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, neopentyl glycol, 1 ,4- butanediol, 1 ,5-pentanediol, or 1 ,6-hexanediol. and p-xylene glycol.

16. A polyester composition comprising:

a. from 5 to 95 weight percent, based on the total weight of the polyester composition, of at least one polyester according to any of claims 1-14; and b. from 5 to 95 wt % of at least one other polymer chosen from polyolefins, maleic anhydride grafted polyolefins, polyamides, and polyethers.

A polyester composition comprising:

(1 ) from 5 to 95 weight percent, based on the total weight of the polyester composition, of at least one polyester comprising:

(a) from 50 to 80 weight percent of a dicarboxylic acid component comprising:

i. from 80 to 99.9 mole percent of terephthalic acid or an ester thereof;

ii. from 0 to 20 mole percent of an aromatic/aliphatic dicarboxylic acid or ester thereof having up to 20 carbon atoms; and iii. from 0.1 to less than 20 mole percent of at least one monomeric component of formula (I):

wherein Ri is independently chosen from H, methyl, and ethyl,

R2 and Rz are independently chosen from -COOH, -COOMe, -COOEt, - COO/Pr, -COOnPr, -OH, -CI, -Br, and NH2, and

J and K are independently chosen from 1 , 2, 3, 4, 5, 6, 7, or 8;

ii. from 0 to 20 mole percent of at least one other glycol chosen from diethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, neopentyl glycol, 1 ,4-butanediol, 1 ,5-pentanediol, or 1 ,6-hexanediol. and p-xylene glycol; and (2) from 5 to 95 weight percent, based on the total weight of the polyester composition, of at least one other polymer chosen from polyolefins, maleic anhydride grafted polyolefins, polyamides, and polyethers.