PBT poly(butylene terephthalate)

PBT poly(butylene terephthalate) PARAMETER

UNIT

VALUE

REFERENCES

GENERAL Common name

-

poly(butylene terephthalate)

ACS name

-

poly(oxy-1,4-butanediyloxycarbonyl-1,4-phenylenecarbonyl) (24968-12-5); 1,4-benzenedicarboxylic acid, polymer with 1,4-butanediol (26062-94-2)

Acronym

-

PBT

CAS number

-

24968-12-5; 26062-94-2

Linear formula

OC

COO(CH2)4O

n

HISTORY Person to discover

-

Chipman, G R; Henk, M G; De Boer, J A; Blaha, E W

Date

-

1977

Details

-

reaction of terephthalic acid and butane diol using tetravalent tin catalyst having the organo-to-tin linkage

Chipman, G R; Henk, M G; De Boer, J A; Blaha, E W, US Patent 4,014,858, Standard Oil, Mar. 29, 1977.

SYNTHESIS Monomer(s) structure

HOCH2CH2CH2CH2OH HOOC

COOH

Monomer(s) CAS number(s)

-

107-88-0; 100-21-0

Monomer(s) molecular weight(s)

dalton, g/ mol, amu

90.121; 166.13

Monomer ratio

-

1:1.84

Temperature of polymerization

o

Catalyst

-

tetravalent tin

Number average molecular weight, Mn

dalton, g/ mol, amu

5,600-20,400

Mass average molecular weight, Mw

dalton, g/ mol, amu

26,000-125,000

Polydispersity, Mw/Mn

-

2.0

STRUCTURE

-

Crystallinity

%

33-36; 18-22 (single-bubble lm); 20-47 (double-bubble lm and biaxially stretched lm)

Cell type (lattice)

-

triclinic (DE)

Cell dimensions

nm

a:b:c=0.483:0.594:1.159

Unit cell angles

degree

DEJ=99.7:115.2:110.8

Number of chains per unit cell

-

1

Crystallite size

nm

1.16 (length; D); 1.3 (length, E)

Polymorphs

-

DE

Chain conformation

-

GTG (D); TTT (E)

302

C

220

HANDBOOK OF POLYMERS / Copyrights 2012; ChemTec Publishing

Forouhashad, M; Saligheh, O; Arasteh, R, Farsani, R E, J. Macromol. Sci. B, 49, 833-42, 2010; Song, K; White, J L, Polym. Eng. Sci., 38, 3, 505-15, 1998.

Konishi, T; Miyamoto, Y, Macromolecules, 43, 375-83, 2010.

PBT poly(butylene terephthalate) PARAMETER

UNIT

VALUE

REFERENCES

Rapid crystallization temperature

o

n=2.35-2.60

Al-Mulla, A; Mathew, J; Shanks, R, J. Polym. Sci. B, 45, 1344-53, 2007.

C

COMMERCIAL POLYMERS Some manufacturers

-

BASF, DuPont; Mitsubishi Chemical; Sabic

Trade names

-

Ultradur B; Crastin; Jupilon; Valox

Density at 20oC

g cm-3

1.24-1.34; 1.404 (crystalline; D form); 1.283 (E form); 1.37 (10% glass ber, GF); 1.45-1.47 (20% GF); 1.53-1.55 (30% GF); 1.73 (50% GF)

Bulk density at 20oC

g cm-3

0.60-0.90

Color

-

white

PHYSICAL PROPERTIES

Odor

Shibaya, M; Ohkubo, N; Ishihara, H; Yamashita, K; Yoshihara, N; Nonomura, C, Antec, 1658-62, 2003.

slight o

Refractive index, 20 C

o

C

220-230; 220-250 (10-50% glass ber)

Softening point

o

C

50 (amorphous fraction), 220 (crystalline fraction)

Decomposition temperature

o

C

Thermal expansion coefcient, -40 to 160oC

o

Thermal conductivity, melt

W m-1 K-1

Glass transition temperature

o

C

288 -1

0.9E-4 to 8.1E-5; 0.2-1.2E-4 (10-50% glass ber) 0.25-0.27; 0.23-0.36 (10-50% glass ber); 0.18 (melt, 10-50% glass ber) 31-60; 46 (DSC)

C -1

-1

1,500; 1,400-1,700 (10-50% glass ber); 1,990 (melt, 10-50% glass ber)

Specic heat capacity

J K kg

Heat of fusion

kJ mol-1

21.2

Maximum service temperature

o

C

200; 210 (10-50% glass ber)

Temperature index (50% tensile strength loss after 20,000 h/5000 h)

o

C

120/140; 120-160 (10-50% glass ber)

Heat deection temperature at 0.45 MPa

o

C

130-165; 215-222 (10-50% glass ber)

Heat deection temperature at 1.8 MPa

o

C

50-65; 168-215 (10-50% glass ber)

Vicat temperature VST/A/50

o

C

Dielectric constant at 100 Hz/1 MHz

-

3.2-3.4/3.2-3.3; 3.6-4.7/3.6-4.5 (10-50% glass ber)

Relative permittivity at 100 Hz

-

3.3-3.8; 3.6-4.1 (10-50% glass ber)

Relative permittivity at 1 MHz

-

3.1-3.3; 3.5-3.8 (10-50% glass ber)

Dissipation factor at 100 Hz

E-4

10-20; 12-38 (10-50% glass ber)

Dissipation factor at 1 MHz

E-4

200-219; 130-200 (10-50% glass ber)

Volume resistivity

ohm-m

1-5E13 to 4E14; 1-4.7E14 (10-50% glass ber)

Surface resistivity

ohm

1E12 to 5E15; 1E13-1E15 (10-50% glass ber)

Electric strength K20/P50, d=0.60.8 mm

kV mm-1

15-140; 16-100 (10-50% glass ber)

Comparative tracking index, CTI, test liquid A

-

475-600; 225-500 (10-50% glass ber)

Comparative tracking index, CTIM, test liquid B

-

375-450; 125-150 (10-50% glass ber)

Coefcient of friction

-

0.3-0.6

175; 205-215 (10-50% glass ber)

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303

PBT poly(butylene terephthalate) PARAMETER

UNIT

Surface free energy

mJ m-2

VALUE

REFERENCES

46.3-47.8

MECHANICAL & RHEOLOGICAL PROPERTIES Tensile strength

MPa

50-57; 90-165 (10-50% glass ber)

Tensile modulus

MPa

2,000-2,600; 4,500-9,800 (10-30% glass ber)

Tensile stress at yield

MPa

47-59; 90-165 (10-50% glass ber)

Tensile creep modulus, 1000 h, elongation 0.5 max

MPa

1,100-1,800; 2,500-11,600 (10-50% glass ber)

Elongation

%

35-300; 1.5-4.5 (10-50% glass ber)

Tensile yield strain

%

3.7-8; 1.7-4.0 (10-50% glass ber)

Flexural strength

MPa

62-85; 140-230 (10-50% glass ber)

Flexural modulus

MPa

2,000-2,400; 5,200-14,900 (15-50% glass ber)

Elastic modulus

MPa

2,200-2,600; 4,500-18,700 (10-50% glass ber) -2

Charpy impact strength, unnotched, 23oC

kJ m

Charpy impact strength, unnotched, -30oC

kJ m-2

38-65 (10-50% glass ber)

Charpy impact strength, notched, 23oC

kJ m-2

4-9; <5 to 11 (10-50% glass ber)

Charpy impact strength, notched, -30oC

kJ m-2

4; 62 (10-50% glass ber)

Izod impact strength, unnotched, 23oC

J m-1

1,600

Izod impact strength, notched, 23oC

J m-1

53

Tenacity (ber) (standard atmosphere)

cN tex-1 (daN mm-2)

25-30

Fourne, F, Synthetic Fibers. Machines and Equipment Manufacture, Properties. Carl Hanser Verlag, 1999.

Tenacity (wet ber, as % of dry strength)

%

95-100

Fourne, F, Synthetic Fibers. Machines and Equipment Manufacture, Properties. Carl Hanser Verlag, 1999.

Fineness of ber (titer)

dtex

3-20

Fourne, F, Synthetic Fibers. Machines and Equipment Manufacture, Properties. Carl Hanser Verlag, 1999.

Length (elemental ber)

mm

38-200, lament

Fourne, F, Synthetic Fibers. Machines and Equipment Manufacture, Properties. Carl Hanser Verlag, 1999.

Rockwell hardness

M

72

Ball indention hardness at 358 N/30 S (ISO 2039-1)

MPa

130-139; 155 (10-50% glass ber)

Shrinkage

%

0.9-2.2; 0.1-1.34 (10-50% glass ber)

Brittleness temperature (ASTM D746)

o

Viscosity number

ml g-1

107-160; 90-115 (10-50% glass ber)

Melt viscosity, shear rate=1000 s-1

Pa s

150-600

Melt volume ow rate (ISO 1133, procedure B), 220oC/10 kg

cm3/10 min

9-50; 6-24 (10-50 glass ber)

Melt index, 250oC/2.16 kg

g/10 min

20-50

304

190-290 to NB; 26-67 (10-50% glass ber)

C

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PBT poly(butylene terephthalate) PARAMETER

UNIT

VALUE

Water absorption, equilibrium in water at 23oC

%

0.1-0.5

Moisture absorption, equilibrium 23oC/50% RH

%

0.2-0.25; 0.1-0.2 (10-50% glass ber)

Acid dilute/concentrated

-

good/poor

Alcohols

-

good

Alkalis

-

poor

Aliphatic hydrocarbons

-

good

Aromatic hydrocarbons

-

good

Esters

-

good-fair

Greases & oils

-

very good

Halogenated hydrocarbons

-

poor

Ketones

-

poor

Good solvent

-

m-cresol, o-dichlorobenzene, dichloromethane, phenol/tetrachloroethane, triuoroacetic acid

Non-solvent

-

carbon tetrachloride

REFERENCES

CHEMICAL RESISTANCE

FLAMMABILITY Ignition temperature

o

C

93

Autoignition temperature

o

C

>350

Limiting oxygen index

% O2

22-22.2; 19-20 (10-50% glass ber)

Burning rate (Flame spread rate)

mm min-1

<100

Char at 500oC

%

1.5

Lyon, R E; Walters, R N, J. Anal. Appl. Pyrolysis, 71, 27-46, 2004.

Heat of combustion

J g-1

27,910

Walters, R N; Hacket, S M; Lyon, R E, Fire Mater., 24, 5, 245-52, 2000.

Volatile products of combustion

-

CO, CO2, hydrocarbon fragments, tetrahydrofuran

Dzieciol, M, Intern. J. Environ. Anal. Chem., 89, 8-12, 881-89, 2009.

UL rating

-

94HB; V-0 (with ame retardants)

Spectral sensitivity

nm

290-325

Activation wavelengths

nm

305, 325

Excitation wavelengths

nm

340, 383, 395

Emission wavelengths

nm

440-450

Important initiators and accelerators

-

ferrocene, cobalt octoates and naphthenates, compounds containing aromatic keto-ester groups

Products of degradation

-

radicals, crosslinks, hydroperoxides, hydroxyl and carbonyl groups, CO, CO2

WEATHER STABILITY

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305

PBT poly(butylene terephthalate) PARAMETER

UNIT

VALUE

Stabilizers

-

UVA: 2-hydroxy-4-octyloxybenzophenone; 2-hydroxy4-methoxybenzophenone; 2,4-dihydroxybenzophenone; 2,2’,4,4’-tetrahydroxybenzophenone; 2,2’-dihydroxy4-methoxybenzophenone; 2-(2H-benzotriazol-2-yl)p-cresol; 2-benzotriazol-2-yl-4,6-di-tert-butylphenol; 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol; 2-(2Hbenzotriazole-2-yl)-4-(1,1,3,3-tetraethylbutyl)phenol; 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) phenol; 2,2’-methylenebis(6-(2H-benzotriazol-2-yl)4-1,1,3,3-tetramethylbutyl)phenol; 2-(2H-benzotriazol2-yl)-6-dodecyl-4-methylphenol, branched & linear; 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) phenol; 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazole2-yl)-phenol; 2-(3-sec-butyl-5-tert-butyl-2-hydroxyphenyl) benzotriazole; 2-[4-[(2-hydroxy-3-(2’-ethyl)hexyl)oxy]-2hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol; 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy) phenol; (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate; 1,3-bis-[(2’-cyano-3’,3’-diphenylacryloyl)oxy]-2,2-bis-{[(2’cyano-3’,3’-diphenylacryloyl)oxy]methyl}-propane; propanedioic acid, [(4-methoxyphenyl)-methylene]-dimethyl ester; 2,2’-(1,4-phenylene)bis[4H-3,1-benzoxazin-4-one]; Screener: carbon black, zinc oxide; Acid scavenger: hydrotalcite; HAS: 1,3,5-triazine-2,4,6-triamine, N,N’’’[1,2-ethane-diyl-bis[[[4,6bis[butyl(1,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5triazine-2-yl]imino]-3,1-propanediyl]bis[N’,N’’-dibutyl-N’,N’’bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-; decanedioic acid, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products with 1,1-dimethylethylhydroperoxide and octane; bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate + methyl1,2,2,6,6-pentamethyl-4-piperidyl sebacate; alkenes, C20-24-. alpha.-, polymers with maleic anhydride, reaction products with 2,2,6,6-tetramethyl-4-piperidinamine; 1, 6-hexanediamine, N, N’-bis(2,2,6,6-tetramethyl-4-piperidinyl)-, polymers with 2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine; 1,6-hexanediamine, N,N’-bis(2,2,6,6-tetramethyl-4-piperidinyl)-, polymers with morpholine-2,4,6-trichloro-1,3,5-triazine reaction products, methylated; Phenolic antioxidants: ethylene-bis(oxyethylene)bis(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate); N,N’-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)); 3,3’,3’,5, 5’,5’-hexa-tert-butyl-a,a’,a’(mesitylene-2,4,6-triyl)tri-p-cresol; 1,3,5-tris(3,5-di-tert-butyl4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)- trione; Phosphite: bis-(2,4-di-t-butylphenol) pentaerythritol diphosphite; tris (2,4-di-tert-butylphenyl)phosphite; phosphoric acid, (2,4-di-butyl-6-methylphenyl)ethylester; distearyl pentaerythritol diphosphite; Optical brightener: 2,2’-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole)

Results of exposure

-

3-year exposure in Central Europe caused only slight color change; 90% tensile strength is retained after 3,600 h in Xenotest 1200

HMIS: Health, Flammability, Reactivity rating

-

1/1/0; 0/1/0 (HMIS)

Carcinogenic effect

-

TOXICITY

not listed by ACGIH, NIOSH, NTP

TLV, ACGIH

mg m

-3

3 (respirable), 10 (total)

OSHA

mg m-3

5 (respirable), 15 (total)

306

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REFERENCES

Ultradur Brochure KT/K, F204, BASF 2010.

PBT poly(butylene terephthalate) PARAMETER

UNIT

VALUE

Typical processing methods

-

coating, electrospinning, extrusion, extrusion foaming; lm extrusion, injection molding, monolament extrusion, rotational molding

Preprocess drying: temperature/ time/residual moisture

o

C/h/%

80-130/2-8/0.02-0.04

Processing temperature

o

C

235-270 (injection molding); 230-290 (coating); 230-270 (pipe extrusion); 230-270 (extrusion)

Processing pressure

bar

30 (extrusion melt pressure); <100 (extrusion backpressure); 20-150 (injection pressure); 0.3-0.7 (injection molding backpressure)

Residence time

min

<35; 2.5 (max cycle time)

Additives used in nal products

-

Fillers: antimony trioxide, aramid, barium sulfate, boron nitride, calcinated kaolin, carbon black, carbon ber, glass ber, glass spheres, mica, montmorillonite, talc, titanium dioxide, zinc borate; Antistatics: antimony-doped tin oxide, carbon nanotubes, polyaniline, polyisonaphthalene; Antiblocking: calcium carbonate, diatomaceous earth, silicone uid, spherical silicone resin, synthetic silica; Release: calcium stearate, uorine compounds, glycerol bistearate, pentaerythritol ester, silane modied silica, zinc stearate; Slip: spherical silica, silicone oil

Applications

-

automotive (connectors, distributor caps, door knobs, lamp sockets, lightning bezels, mirror housings, windshield wiper arms), brush bristles, composites, automobile lamps, consoles, contact carriers, covers, electrical and electronics (capacitors, connectors, circuit breakers, capacitor housings, encapsulation of transformers, bers, motors, and solenoids, printed circuit boards, relays), housewares, housings, lighting, plumbing, power tools, sporting goods, textiles, tire cords

Outstanding properties

-

dimensional stability, weather resistance, resistance to fuels, impact resistance, electrical insulation properties

-

ASA, epoxy, lCP, PA12, PC, PCL, PET, PHB, PVB, SAN

degree

16.4, 17.7, 21.1, 23.8, and 25.4

REFERENCES

PROCESSING

BLENDS Suitable polymers

ANALYSIS x-ray diffraction peaks

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