Polyesters Consisting of TMCD, CHDM, Ethylene Glycol and Manufacturing Process

US2007/0142615A1
Expiry - 2027/06/05
 Field of Invention

This invention relates to polyester composition made from TPA and mixtures of TMCD , CHDM and
EG that have certain combinations of two or more high notched impact strength , certain Tg ,
certain flexural modulus , good clarity and good colour which allow them to easily formed into
articles like thermoformed sheet and film applications
 Dicarboxylic acid component :
• 90 to 100 mole % of terephthalic acid residues
• 0 to 10 mole % of aromatic/aliphatic dicarboxylic acid residues up to 20 carbon atoms (IPA , 1,4 naphthalene dicarboxylic acid, adipic
acid )
• Total 100 mol %

 Glycol component :
• 20 - 40 mol % of TMCD residues
• 20 - 40 mol % of CHDM residues
• 30 - 60 mol % Ethylene gycol residues
• Less than 2 mol % of modifying glycol containing 2-16 carbon atoms (1,3 propane diol , 1,4 butane diol)
• 40 < Mol % CHDM + Mol % TMCD < 70
• Cis/trans (CHDM) - 50:50 - 0:100
• Cis/trans (TMCD) - 50:50 - 0:100
• Total 100 mol %
• Acid : Glycol : 1 : 1.01 -3
Catalyst Metals :
•Ti and Sn compound (10 - 20000 ppm, 15 - 400 ppm)
•Sn : Mn2(Sn(OR)4) , Sn(OR)2 , SnR2 Where M is alkali metal : Na , K and R is alkyl radical with1 to 8 C atoms (dibutyl tin , dihexyl tin ,
dimethyl tin oxide)
•Ga/Zn/Sb/Co/Mn/Mg/Ge/Li/Al compounds
• Aluminium compound with LiOH/NaOH
• Phosphorous compound (H3PO4 , H3PO3 , Esters : alkyl , aryl , branched , Ethers : alkyl , aryl , Salt : KH2PO4 , Zn3(PO4)2) - (1 - 5000 ppm)
• Total Catalyst : 10 - 20000 ppm

Phosphate Ester :
• Act as a thermal stabilizer or colour stabilizer: (triphenyl phosphate, tributyl phosphate etc (1 - 5000 ppm)

Branching Agent :
•Branching agent having 3 carboxyl/hydroxyl substituents (glycerol, citric acid, tartaric acid etc) (0 -10 mol %)

Chain Extenders :
• Isocyanates, epoxylated novolacs, phenoxy resins (0.1 - 10 wt %)


Toner : Blue - Organic and Inorganic (to reduce b) and Red - Organic (To adjust a) (0.5 - 15 ppm) - Added in the esterfication zone or
polycondensation zone

Flame retardants (0.01 - 25 wt%)

Plasticisers (0.01 - 25 wt%)

Nucleating Agents (0.01 - 25 wt%)
• The process can be batch or continuous
• Sn is added to the polyester composition in the form of Sn compound. Amount of Sn compound added is measured in the form of
Sn atoms in the final polyester measured in ppm (dibutyl tin , dihexyl tin , dimethyl tin oxide)
• Ti is added to the polyester composition in the form of Ti compound. Amount of Ti compound added is measured in the form of
Ti atoms in the final polyester measured in ppm (tetra ethyl titanate , titanium butoxide , titanium dioxide)
• P is added to the polyester composition in the form of P compound. Amount of P compound added is measured in the form of P
atoms in the final polyester measured in ppm (triethyl phosphate , tributyl phosphate , tricresyl phosphate)
• Total catalyst amount is from 10 - 20000/10 - 10000/10 - 5000 based on the catalyst metal and based on the weight of the final
polymer.
• At least one phosphate ester
• At least one tin compound
• At least one titanium compound
• Amount of Ti atoms in the polyester can be from 1- 400 ppm
• Amount of Sn atoms in the polyester can be from 1 - 400 ppm
• Amount of P atoms in the polyester can be from 1 - 500 ppm
• Weight ratio of P:Sn in the polyester is 0 - 20:1
• Weight ratio of P:Ti in the polyester is 0 - 15:1
 Process :

• Step 1 : Heating the mixture of (TPA) and glycol (TMCD , CHDM etc) in the melt in presence of Ti/Sn or both catalyst at an
elevated temperature : (150 - 250 0C) , Pressure : (0 - 75 psig) , Time : f ( temperature, pressure , mole ratio)

• Esterfication/transesterfication in the melt , homogeneous solution or two phase interfacial process

• Step 2 : Heating the product of step 1 at a Temperature : (230 0C - 320 0C) , Pressure : (0.02 torr) at an inert atmosphere under
vaccum for a Time period : (1 - 6 hrs) to form the final polyester

• Step 3 : Removal of unreacted glycol

 Properties :

• Tg ( 100 - 110 0C)

• Flexural Modulus 290000 - 350000 psi (230C ASTM D790)
• Inherent Viscosity 0.50 - 1.2 dL/g (60/40 wt% phenol/tetrachloroethane)
• Impact Strength > 500 J/m
• Density > 1.2 g /ml (230C)
• Virtually clear (No haze)
• -12 < b > 12 with or without toner
• 50 < L > 90
• t1/2 : 5-10 min at 1700C
• Amorphous/Crystalline/Semicrystalline
 Polyesters containg Ethylene glycol, TMCD and CHDM comprising of thermal stabilizers, reaction products are superior to commercial
polymers :

• Impact strength
• Inherent viscosities (IV)
• Glass Transition (Tg)
• Flexural modulus
• Good clarity
• Good colour

 Applications :

• Thermoformed film
• Sheet Applications
• Extruded articles
• Calendered Articles
• Melt spinning
• Thermoformed Articles
• Blow Molded Articles
• Compression Moulded articles
 Features :
• No Bubbling
• No Splay formation
• No Color formation
• No Foaming
• No Off gassing
• No Erratic melt levels
 Composition, Color and Inherent Viscosity of Polyesters

No IV TMCD CHDM DEG Ti Sn TPP P P Tg L a b

(dL/g) (mol %) (mol %) (mol %) (ppm) (ppm) (g) (ppm) (ppm) (0C)
Theory measured
A 0.670 29.8 30.1 0.6 34 33 0.500 430 165.8 106.5 79.51 -1.35 4.9

B 0.751 35.1 31.0 0.2 36 33 0.150 129 56 115.3 78.29 -1.42 8.55
C 0.953 38.3 28.7 0.4 34 31 0.024 21 16 117.7 77.69 -2.37 13.3
D 0.691 34.0 28.6 0.7 33 32 0.303 261 121.8 109.9 78.9 -1.74 5.71
E 0.647 37.2 28.6 0.3 NM NM 0.200 172 NM 112.6 NM NM NM
F 0.774 34.3 29.9 0.4 37 32 0.125 107 61 117.2 78.02 -1.37 6.63
G 0.792 37.3 29.5 0.1 36 36 0.075 64 40 118.2 77.57 -1.64 9.85
H 0.688 33.8 32.5 0.4 NM NM 0.200 172 NM 112.4 NM NM NM

Example 1 :Polyester prepared from 100 mol % DMT with varying amount of TPP , with CHDM , TMCD and EG
glycols. The glycol/acid 1.5:1. The glycol feed contains 20 mol % CHDM , 35 mol % TMCD and 45 mol % EG.
 Effect of Phosphorous content on the color and Viscosity

No IV TMCD CHDM DEG Ti Sn TPP P P Tg L a b

(dL/g) (mol %) (mol %) (mol %) (ppm) (ppm) (g) (ppm) (ppm) (0C)
Theory measured
A 1.011 37.1 29.2 0.4 34 33 0 0 2 117.7 70.76 0.15 18

B 0.913 36.5 29.1 0.5 33 34 0.052 45 28 115.9 76.18 -1.71 11.2

C 0.777 37.2 29.2 0.1 33 36 0.100 86 49 117.5 73.43 -1.5 6.23
D 0.744 38.5 28.3 0.5 34 31 0.205 176 78.7 113.1 77.73 -1.4 6.2
E 0.722 31.2 29.2 0.8 34 33 0.396 340 152.2 109.3 78.51 -1.22 4.84

Example 2 : Polyester prepared from 100 mol % DMT , 30 mol % CHDM , 40 mol % EG. The glycol/acid 1.5:1.
The glycol feed contains 20 mol % CHDM , 35 mol % TMCD and 45 mol % EG.
 Effect of Catalyst and TPP on color and Viscosity

No TIIP Ti (ppm) DBTO (g)/Sn (ppm) TPP (g) TMCD (mol %) CHDM (mol %) b IV (dL/g)
A 0 0.0154/60 0.00 40 29.1 15.1 0.78
B 0 0.0154/60 0.20 28.5 31.2 2.6 0.18
C 0 0.0154/60 0.50 24.1 30.7 3.7 0.17
D 0.042/60 0 0.00 28.7 29.4 21.1 0.91
E 0.042/60 0 0.20 27.7 31.0 11.1 0.78
F 0.042/60 0 0.50 25.5 31.0 10.6 0.56
G 0.021/30 0.077/30 0.00 37.1 29.2 18.0 1.01
H 0.021/30 0.077/30 0.21 38.5 28.3 6.2 0.74
I 0.021/30 0.077/30 0.50 29.8 30.1 4.9 0.67

Example 3 : Polyester prepared from 100 mol % DMT , 30 mol % CHDM , 40 mol % EG
 Characteristics of Polyester

Property A B C
IV 0.67 0.84 0.69
Tg (0C) 100.8 102.2 108.4
Sn (ppm) 197 225 293
TMCD 27.8 30.0 20.4
CHDM 20.0 nil 79.6
EG 51.5 69 nil
DEG 0.5 1.0 nil
L 73.28 61.76 70.76
a -1.30 5.66 -0.95
b 20.04 25.28 5.37
Haze 1.16 1.40 1.22
Flexural Modulus (psi) 299958 325469 239671
Impact Strength (ft-lb/in) 17.2 1.49 19.76
Ternary Blends of Terephthalate or Isophthalate polyesters
containing EG, CHDM and TMCD
US9273206B2
EXPIRY 2033/07/21
 Field of Invention

The invention relates to the field of TPA or Isophthalate based polyesters , to blends of
terephthate or isophthalate based polyesters containing EG, CHDM with terephthalate or
isophthalate based polyesters containing TMCD and CHDM
 Background
• Polyester Blends are used inorder to develop new materials that take the advantage of the properties of the
specific components in the blend

• PETG copolyester in blends improve properties like lowers viscosity for extrusion processing , increasing adhesion
for lamination processing and altering the heat distortion temperature.

• But PETG is immiscible with PCTT and have different refractive indices and exihibith unacceptable haze

• There is a need in the art for polyester blends containing PETG and PCTT that exhibit an acceptable level of haze.
• PCTG (TPA , CHDM and EG) copolyester that is miscible in binary combinations with PETG and PCTT can act like a

compatabilizer between PCTT and PETG at ternary loading levels to improve properties such as significantly lowering haze

• Ternary blends of PCTT-PETG-PCTG are characterized for low haze 0.5 - 5 %

Polyester Blend Composition :

 Polyester (PCTT) :
• Diacid component consisting 95 mol % of TPA , IPA or mixture
• Diol component consisting 15 - 45 mol % of TMCD and 55 - 85 mol % of CHDM

 Polyester (PETG) :
• Diacid component consisting 95 mol % of TPA , IPA or mixture
• Diol component consisting 25 - 55 mol % of CHDM and 45 - 75 mol % of EG

 Polyester (PCTG) :
• Diacid component consisting 95 mol % of TPA , IPA or mixture
• Diol component consisting 55 - 85 mol % of CHDM and 15 - 45 mol % of EG

 CHDM and TMCD mole ratio of cis/trans : 60/40 to 40/60

• The haze of this blend ≤ 5 % (0.010 inch thickness)

• (-0.02276 * X) + (-0.02273* Y) + (-0.01537*Z) + (0.003789*X*Y) + (6.52*10 -5) + (5.7*10-5*Y*Z) + (-6.7*10-5*Y*Z) ≤ 0.41 - 1 A
• (0.005331 * X) + (0.005345* Y) + (0.00507*Z) + (0.002287*X*Y) + (-4.9*10 -5*X*Z) + (-5.3*10-5*Y*Z) + (-3.1*10-5*X*Y*Z) ≤ 1.22 - 1 B

• (-0.02276 * X) + (-0.02273* Y) + (-0.01537*Z) + (0.003789*X*Y) + (6.52*10 -5) + (5.7*10-5*Y*Z) + (-6.7*10-5*Y*Z) ≤ 0 - 2 A

• (0.005331 * X) + (0.005345* Y) + (0.00507*Z) + (0.002287*X*Y) + (-4.9*10 -5*X*Z) + (-5.3*10-5*Y*Z) + (-3.1*10-5*X*Y*Z) ≤ 1 - 2B

• (-0.02276 * X) + (-0.02273* Y) + (-0.01537*Z) + (0.003789*X*Y) + (6.52*10 -5) + (5.7*10-5*Y*Z) + (-6.7*10-5*Y*Z) ≤ 0.7 - 3 A

• (0.005331 * X) + (0.005345* Y) + (0.00507*Z) + (0.002287*X*Y) + (-4.9*10 -5*X*Z) + (-5.3*10-5*Y*Z) + (-3.1*10-5*X*Y*Z) ≤ 0.7 - 3 B

Where ; X , Y , Z are the weight percent of the polyester PCTT , PETG , PCTG in the polyester blend

The polyester blend satisfying the above Eqn have a haze value ≤ 1.5 % , ≤ 1 % ≤ 0.5 %
1A , 2A , 3A are for low IV and 1B , 2B , 3B for high IV polyesters
Blend Composition :
• 40 - 90 Wt % of PCTT (TPA , IPA , TMCD ,CHDM)
• 1 - 20 Wt % of PETG (TPA , IPA , CHDM , EG)
• 10 - 50 Wt % of PCTG (TPA , IPA , CHDM , EG)

Where the Wt % are based on the total amount of PCTT , PETG , PCTG in the blend and sum of it is 100

The IV of these blends : 0.45 - 1.2 dL/g measured at 250C at 0.5g/100 ml in 60/40 phenol-tetrachloroethane

• The polyester in the blend of the invention comprise dicarboxylic acid residue , diol residue, and optionally branching
monomer residues.

• Equal proportion of diacid (100 mole percent) and diol residues (100 mole percent) which react in equal proportion 1:1 or
1:1.05-2 such that total moles of repeating units is 100 mole percent.
 Modifying Dicarboxylic acids :
The diacid component of the blend can containup to 5 mol % of modifying dicarboxylic acids
Aromatic/cycloaliphatic dicarboxylic acids ; 8-16 carbon atoms
Acyclic dicarboxylic acids ; 2-16 carbon atoms

Eg : Malonic Acid , Succinic acid , glutaric acid , 1,3-cyclohexanedicarboxylic acid , adipic acid , oxalic acid etc

 Modifying Diols :
The diol component of the blend can contain up to 5 mol % of modifying dicarboxylic acids
Eg : Propylene glycol , 1,3 propane diol, 2,4-dimethyl-2-ethylhexane-1,3 diol , diethylene glycol , 1,4 butane diol etc

 Branching Agent :
0.01-10 Wt %
Polyfunctional acids (3-6 carboxy groups) , anhydrides , polyols (3-6 hydroxyl groups)
Eg : trimelltic acid, trimesic acid , pyromelltic anhydride , trimethylolethane etc

 Catalyst :
Alkoxy titanium compounds , Alkali metal hydroxides , Alkali tin compounds , metal oxides
Toner :
To impart neutral hue and brighteness to polyester Eg : Red , Blue

Chain Extenders :
Added at the end of the polymerisation
Eg : Epoxylated novolacs , phenoxy resins (0.1 - 10 Wt %)

Fillers


Impact modifiers


UV Absorbers


Non Polyester Polymers :
Polyamides , Polyethers , Polyacrylates , Polycarbonates etc (50 Wt %)
 Polymerisation Process :

• Operation : Continuous / Semi-continuous / Batch

• Reactors : Stirred tank / Continuous / Slurry / tubular / Extrusion reactors
• Reaction : Melt phase polycondensation and Solid phase polycondensation

 Step 1 : Esterfication of Diol and Dicarboxylic acid at 180 - 280 0C , 7-1379 kPa for 0.5 to 8 hrs to obtain low Mw products (DP
1.5-10)

 Step 2 : Polycondensation of esterfied product at 230 - 350 0C , 53 - 0.013 kPa under high vaccum for 0.1 - 6 hrs until required
DP and IV

• The reaction kinetics of both stages can be increased in the presence of catalyst like Ti , Mn, Zn , Co , P (5 - 100 ppm)

• Phosphorous are incorporated as dibutyl phenyl phosphate, triphenyl phosphate , tributyl phosphate etc

• Phosphrous compounds improves the colour of polyesters during polymerisation.

 Blend Fabrication :

• Melt Blending : Blending the polymers at 200 - 300 0C in an extruder /injection moulding/two roll mill.
The blend is cooled and pelletised and used for further processing (Calendering , Blow moulding etc)

• Solution Blending : Dissolving the polyester in methylene chloride and hexafluoroisopropanol 70:30 mixing the solution followed by
separation via precipitation / evaporation of the solvent

 Processing Methods :

• Extrusion
• Calendering
• Injection Moulding
• Compression
• Profile Extrusion
• Melt Spinning
 Properties :
• Improved Clarity
• Improved Toughness
• Excellent Transparency
• Low haze (good miscibility)
• Good fabrication characteristics

 Applications :
• Sheets
• Films (monolayer and multilayer)
• Fibers
• Tubes
• Preforms
• Containers
• Bottles
 Viscosity of Blends prepared via Melt Blending

Resin Type Resin EG (mol %) CHDM (mol%) TMCD (mol %) Viscosity (dL/g)
PCTT A 0 78 22 0.72
PCTT B 0 78 22 0.63
PETG C 69 31 0 0.75
PETG D 69 31 0 0.59
PCTG E 38 62 0 0.73
PCTG F 19 81 0 0.75
PCTT G 0 72 28 0.67
PCTT H 0 65 35 0.64
PCTG I 50 50 0 0.76
PCTG J 38 62 0 0.63

Example 1 : Polyester prepared from 100 mol % TPA with varying amounds of CHDM , EG and TMCD
 Haze and Refractive Index of blends

Resin A + Resin C
(high IV)

Resin B + Resin D
(low IV)

Resin B + Resin D + Resin E

Resin Type Resin EG (mol %) CHDM (mol%) TMCD (mol %) Viscosity (dL/g)
PCTT A 0 78 22 0.72
PCTT B 0 78 22 0.63
PETG C 69 31 0 0.75
PETG D 69 31 0 0.59
PCTG E 38 62 0 0.73
 Properties of Blends prepared by Extrusion
Example PCTT PCTT PETG PETG PCTG Haze (%) Refractive Tg 1 Tg 2
(wt %) (wt %) (wt %) (wt %) (wt %) Index (0C) (0C)
1 100 0 0 0 0 0.30 N/A
2 95 0 5 0 0 3.30 N/A
3 90 0 10 0 0 6.21 N/A
4 80 0 20 0 0 14.50 N/A
5 0 95 0 5 0 0.94 1.5481 104.95 N/A
6 0 90 0 10 0 2.45 1.5490 82.06 104.45
7 0 85 0 15 0 3.77 1.5497 82.11 104.15
8 0 100 0 0 0 0.18 1.5477 106.82 N/A
9 0 50 0 5 45 0.19 1.5535 88.29 100.93
10 0 50 0 15 35 0.43 1.5532 85.72 101.41
11 0 60 0 10 30 0.42 1.5523 85.32 99.84
12 0 60 0 15 25 1.44 1.5524 84.86 100.20
13 0 70 0 5 25 0.36 1.5513 97.60 N/A
14 0 70 0 10 20 0.48 1.5511 84.38 100.85
15 0 80 0 5 15 0.36 1.5502 99.98 N/A
• Miscibility in the context of polymer blends refers to blends that have a single phase structure witha single Tg
• Blends with more than one Tg but having low haze are considred to be miscible.

• When a binary combination of two polymers forms an immiscible blend adding a third polymer which is atleat partially
miscible in the binary combination with each of the other two materials separately will form a blend with some miscibility

Miscibility can be increased by :

• Decreasing the resin inherent viscosity

• Changing the resin chemistry to make more chemically similar
• Increasing the temperature/residence time /catalytic system when the materials are melt blended to promote higher
transesterfication
Polyesters from Terephthalic Acid , TMCD
and EG
US005955565A
Expired - 2017-12-23
 Field of
Invention

This invention relates to co-polyesters from TPA , TMCD , and EG that have a

combination of high impact strength , high hardness and high heat resistance
 Dicarboxylic acid :
• TPA/DMT (80 - 100 mol %)
• Aromatic dicarboxylic/ester having 20 Carbon atoms (≤ 20 mol %) Eg : Isophthalic acid , 4,4’-biphenyl dicarboxylic acid

• Aliphatic dicarboxylic acid/ester having 16 Carbon atoms (≤ 10 mol %) Eg: malonic , succinic , glutaric acid

 Glycol :
• TMCD (25 - 85 mol %) (45-55 mol % trans isomers)
• EG (15 - 75 mol %)
• Diol having 3-16 Carbon atoms (≤ 10 mol %) Eg : 1,2-propane diol, 1,6 hexane diol , polyethylene glycol

o Total mol % of dicarboxylic acid and glycol component 100

 Catalyst :
• Zinc acetate , dibutyltin diacetate, dibutyltin oxide
Process :

Step 1 : Heating the dicarboxylic acid and glycol in the presence of catalyst ; at 150 - 200 0C for a sufficient time to react
significant portion of distillable glycol

Step 2 : Heating the product of step 1 at 220-3200C for 1-2 hrs

Step 3 : Removal of the unreacted glycols by applying vaccum

• Amount of EG reacted in step 1 is usually around 75-90%

 Properties :

• Heat deflection temperature ≥ 700 C (at 264 psi)

• Rockwell Hardness ≥ 70
• High impact strength ≥ 53.4 J/m
• High Tg
• High heat resistance

Applications :
• fibers
• Films
• Molded articles
• Sheets
 Properties of PET/EG/TMCD Copolyesters
No TMCD (mol %) Ethylene Glycol (mol%) Impact Strength (J/m) Rockwell Hardness L Heat Deflection (0C)
1 0 100 35.2 76 61
2 13 87 41.1 76 66
3 34 66 1.57 84 80
4 50 50 129.8 90 90
5 56 64 369.2 92 79
6 44 36 662.2 94 102
7 69 31 611.4 95 108
8 84 16 137.8 103 118
9 100 0

• Example : Preparation of copolyesters containing 100 mol % TPA , TMCD and EG

• TPA is preferred due to its rigidity of the aromatic ring and straightness due to para substituted carbonyls and also gives polyesters high
impact strength , good extrudability , injectability and machinability.

• Copolyesters outside of the concentration of the present invention 25-85 mol % TMCD and 15-75 mol % EG do not have the combination of
high impact strength , hardness and high heat resistance as compared to the present invention

• Polyesters with less than 15 mole % EG do not have adequate hardness or heat resistance
• Polyesters with more than 75 mole % EG do not have adequate impact strength of Engineering Plastics
• On increasing the EG content the hardness and heat resistance decreases.
 Properties of PET/CHDM Copolyesters
No CHDM (mol %) Ethylene Glycol (mol%) Impact Strength (J/m) Rockwell Hardness L Heat Deflection (0C)
1 0 100 44.9 81 62
2 16 84 55.0 70 60
3 31 69 48.6 63 64
4 44 56 90.8 63 61
5 50 50 921.7 62 66
6 59 41 1531.5 59 64
7 77 23 1542.2 56 64
8 77 23 1580.1 56 67
9 83 17 1170.0 56 65
10 100 0 1000.0 57 67

Example : Polyesters of 100 mol % TPA , EG and CHDM

The results show that polyester of the present invention have superior combination of impact strength , hardness and
heat resistance

On increasing the EG content the impact strength decreases and hardness increases.
 Properties of commercial polyesters
Composition Impact Strength (J/m) Rockwell Hardness L Heat Deflection (0C)
PET 7352 35.8 80 63
PETG 6763 83.8 67 64
PCTG 5445 1532.6 60 67
PCT 1222.9 71 60

o PET 7352 : 100 mole % TPA ,100 mole % EG

o PETG 6763 : 100 mole % TPA , 69 mole % EG , 31 mole % CHDM
o PCTG 5445 : 100 mole % TPA , 42 mole % EG , 58 mole % CHDM
o PCT : 100 mole % TPA , 100 mole % CHDM

• The commercial polyester blends are inferior to the present invention in terms of combination of impact strength ,
hardness and heat resistance
CoPolyster Resin Compositions with Improved Melt flow
Properties
WO2019046061A1
 Field of Invention

This invention relates to copolyesters resin composition that exibit improved flow properties when

in melt form and are therefore particularly useful in injection molding , extrusion , 3D printing and

similar applications
• Linear copolyester polymer (X=0.5-0.9 , Y=1-X , n= 40-100)
• Linear copolyester oligomer (X=0.5-0.9 , Y=1-X, n= 10-40)

 Dicarboxylic Acid component :

• TPA/DMT

 Glycol component :
• TMCD (10-50 mol %)
• CHDM (50-90 mol %)

 Process :
• Transesterification :
• Polycondensation :
• The linear polymer or oligomer contains some macrocyclic species (cyclic dimers , trimer species) < 1 % due to side
reactions
• The linear polymers contain certain cyclic groups contributed by monomers cyclo hexyl ring of CHDM ; cyclo butyl
ring of TMCD and benzyl ring of TPA

• Amount of linear copolyester polymer in the composition : 60-99 Wt%

• Amount of linear copolyester oligomer in the composition : 1-40 Wt%

• The composition also contains other additives and ingredients : Reinforcements , mold release agents , fillers ,
surface friction modifiers , light and heat stabilizers, extrusion aids , antistatic agents , toner , tougheners , adhesion
promoters etc.

 The present invention includes :

• Reaction of DMT with the diols ; TMCD and CHDM to form a reaction product stream containing the linear copolyster
polymer and oligomer
• Sourcing the linear copolyester polymer and oligomer
• Mixing the linear copolyester polymer and linear copolyester oligomer to form the polyester resin
 TX1500HF Control TX1500HF w/5wt% Oligomer
Motor Load 85 67
Melt pressure 93 47

Example :A resin (TX1500HF w/5wt% Oligomer) containing a linear copolyester polymer and oligomer and the control
TX1500HF (Triton copolyester by Eastman)

• In the case of TX1500HF w/5wt% Oligomer a 21 % reduction in motor load and 49 % reduction in melt pressure
relative to TX1500HF Control .

• This is indicative of a reduction in melt viscosity (good melt flowability)

 No Sample Mn Mw Mz PD IV
1 TX1500HF Control 9051 17967 27179 1.985 0.61
2 TX1500HF Compounded control 8713 17542 27032 2.013 0.60
3 TXHF w/5wt% Oligomer 8023 17213 26907 2.145 0.59
4 Oligomer 1917 3880 9322 2.024 0.21

• The oligomer has lower molecular weight compared to control materials

• Addition on 5 wt% oligomer to X1500HF polymer broadens the molecular weight distribution by 7 - 8 %
 Properties of the Composition Vs Control

No Sample TS Yield TS Break EL EL Tens Impact Tg

(Mpa) (Mpa) Yield Break Mod (Mpa) (J/m) (0C)
(%) (%)
1 TX1500HF 43.3 50.1 5.6 151.2 1497.0 888 104.5
Control
2 TX1500HF 43.2 44.1 5.5 113.2 1507.0 896.8 104.4
Compounded
control
3 TX1500HF 44.2 42.7 5.3 110.0 1559.0 902.5 102.3
w/5wt%
Oligomer

• The TXHF w/5wt% Oligomer has similar Tensile strength (Yield) , Elongation (Yield) , Tensile Modulus and Impact
Strength to TX1500HF Compounded control

• The Tensile strength at break and Elongation at break are negatively impacted by the oligomer addition

• The Tg of TX1500HF w/5wt% Oligomer is lower than control

 No Sample Oligomer Torque Melt Pressure
(%) (%) (psi)
1 TX1000 Comp Control 0 93 1141
2 TX1000 + 2.5% Oligomer 2.5 90 1050
3 TX100 + 5% Oligomer 5 86 1010
4 TX100 + 10% Oligomer 10 80 905
5 TX100 + 20% Oligomer 20 68 761

• A linear copolyester polymer (Eastman -TX1000) and linear copolyester oligomer were formed

• The given compositions were compounded in a twin screw extruder (260 0C , 150 rpm , feed rate : 25 lbs/hr)

• The composition of the present invention showed a decrease in torque and melt pressure i.e an indicative of the
reduction in melt viscosity and improvement in melt flowability.
Miscible blends of Terephthalate polyesters containing CHDM and
TMCD US20100159176A1
Expired