Thermodynamic Data of Copolymer Solutions Part 6 pptx

ENTHALPY CHANGES FOR BINARY COPOLYMERSOLUTIONS 5.1... T/K = 298.15 Comments: the table provides the ratio of ∆dilH12/∆nA, i.e., the enthalpy change caused by diluting the primary solutio

5 ENTHALPY CHANGES FOR BINARY COPOLYMER

SOLUTIONS

5.1 Enthalpies of mixing or intermediary enthalpies of dilution,

and copolymer partial enthalpies of mixing (at infinite dilution),

or copolymer (first) integral enthalpies of solution

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Characterization:

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

Experimental enthalpy data:

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T/K = 298.15

∆solHB ∞ = 0.0 J/(g copolymer)

Comments: the final concentration is about 2 g copolymer/132 g solvent

T/K = 298.15

∆solHB ∞ = 5.82 J/(g copolymer)

Comments: the final concentration is about 0.55 g copolymer/100 g solution

T/K = 298.15

∆solHB∞ = −1.88 J/(g copolymer)

Comments: the final concentration is about 3 g copolymer/132 g solvent

T/K = 298.15

∆solHB∞ = −7.0 J/(g copolymer)

Comments: the final concentration is about 0.85 g copolymer/100 g solution

T/K = 298.15

∆solHB∞ = −2.93 J/(g copolymer)

Comments: the final concentration is about 3 g copolymer/88 g solvent

Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

solvent (A): N,N-dimethylformamide C 3 H 7 NO 68-12-2

T/K = 323.15

∆solHB∞ = −31.8 J/(g copolymer)

Comments: additional information is given for varying isoprene contents between 2 and 22 mol% in the

copolymer in Fig 1 of the original source 76PET

Acrylonitrile/vinyl chloride copolymer

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Characterization:

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

solvent (A): N,N-dimethylformamide C 3 H 7 NO 68-12-2

copolymer (B): AN-VC/29w 59ZEL solvent (A): N,N-dimethylformamide C 3 H 7 NO 68-12-2

Comments: the final concentration is about 1 g copolymer/165 g solvent

solvent (A): N,N-dimethylformamide C 3 H 7 NO 68-12-2

Acrylonitrile/vinylidene chloride copolymer

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Characterization:

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

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Experimental enthalpy data:

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T/K = 298.15 ∆solHB ∞ = −28.03 J/g copolymer

T/K = 298.15 ∆solHB ∞ = −19.25 J/g copolymer (fibre drawn 156%)

T/K = 298.15 ∆solHB∞ = −15.92 J/g copolymer (fibre drawn 300%)

T/K = 298.15 ∆solHB∞ = −14.23 J/g copolymer (fibre drawn 400%)

_ Copolymers from bisphenol A-isophthaloyl chloride and terephthaloyl chloride _

Average chemical composition of the copolymers, acronyms and references:

Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

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Experimental enthalpy data:

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solvent (A): N,N-dimethylacetamide C 4 H 9 NO 127-19-5

T/K = 298.15

∆solHB ∞ = −56.5 J/(g copolymer)

Comments: amorphous sample

solvent (A): 1,1,2,2-tetrachloroethane C 2 H 2 Cl 4 79-34-5

T/K = 298.15

∆solHB∞ = 72.5 J/(g copolymer)

Comments: amorphous sample

solvent (A): 1,1,2,2-tetrachloroethane C 2 H 2 Cl 4 79-34-5

Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

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Comments: solvent mixture concentration 70 wt% C8H10 / 30 wt% C8H18

Butyl methacrylate/isobutyl methacrylate copolymer

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Characterization:

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

Butyl methacrylate/methyl methacrylate copolymer

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Characterization:

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

Characterization:

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

solvent (A): 1,2-dichloroethane C 2 H 4 Cl 2 107-06-2

T/K = 303.15

∆solHB∞ = −6900 J/(base mol copolymer)

Comments: the final concentration is about 0.1 wt%

A graph is given in the original source for ∆solHB ∞

for the binary mixture of 1,2-dichloroethane withdichloroacetic acid

copolymer (B): CBL-PHA/50x 70GIA solvent (A): 1,2-dichloroethane C 2 H 4 Cl 2 107-06-2

T/K = 303.15

∆solHB ∞ = −6500 J/(base mol copolymer)

Comments: the final concentration is about 0.1 wt%

A graph is given in the original source for ∆solHB ∞ for the binary mixture of 1,2-dichloroethane withdichloroacetic acid

solvent (A): 1,2-dichloroethane C 2 H 4 Cl 2 107-06-2

T/K = 303.15

∆solHB∞ = −5860 J/(base mol copolymer)

Comments: the final concentration is about 0.1 wt%

A graph is given in the original source for ∆solHB∞ for the binary mixture of 1,2-dichloroethane withdichloroacetic acid

33 mol% ethylene E-P/33x 79PH1

33 mol% ethylene E-P/33x 79PH2

63 mol% ethylene E-P/63x 79PH1

63 mol% ethylene E-P/63x 79PH2

75 mol% ethylene E-P/75x 79PH1

75 mol% ethylene E-P/75x 79PH2

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

copolymer (B): E-P/63x 79PH1, 79PH2 solvent (A): trans-decahydronaphthalene C10 H 18 493-02-7

copolymer (B): E-P/63x 79PH1, 79PH2 solvent (A): 2,2,4,4-tetramethylpentane C 9 H 20 1070-87-7

Ethylene/vinyl acetate copolymer

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

Poly(ethylene b-poly(propylene

oxide)-b-poly(ethylene oxide) triblock copolymer

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

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EO-b-PO/58w 1700

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Experimental enthalpy data:

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copolymer (B): EO-PO-EO/83x 85COR, 95KIL

Isobutyl methacrylate/methyl methacrylate copolymer

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Characterization:

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

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Experimental enthalpy data:

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Styrene/butyl methacrylate copolymer

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Characterization:

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

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Experimental enthalpy data:

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T/K = 298.15

∆dilH12/(J/mol) 0.564 0.778 0.860 1.056 1.390 1.748

Comments: the table provides the ratio of ∆dilH12/∆nA, i.e., the enthalpy change caused by diluting the

primary solution by 1 mol solvent, where ϕB

(1) denotes the volume fraction of the copolymer

in the starting solution and ϕB(2) denotes the volume fraction after the dilution process

T/K = 298.15

Comments: the table provides the ratio of ∆dilH12/∆nA, i.e., the enthalpy change caused by diluting the

primary solution by 1 mol solvent, where ϕB(1) denotes the volume fraction of the copolymer

in the starting solution and ϕB

(2) denotes the volume fraction after the dilution process

Comments: the table provides the ratio of ∆dilH12/∆nA, i.e., the enthalpy change caused by diluting the

primary solution by 1 mol solvent, where ϕB

(1) denotes the volume fraction of the copolymer

in the starting solution and ϕB(2) denotes the volume fraction after the dilution process

copolymer (B): S-BMA/85w 87KYO

Comments: the table provides the ratio of ∆dilH12/∆nA, i.e., the enthalpy change caused by diluting the

primary solution by 1 mol solvent, where ϕB(1) denotes the volume fraction of the copolymer

in the starting solution and ϕB(2) denotes the volume fraction after the dilution process

Vinyl acetate/vinyl alcohol copolymer

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

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Experimental enthalpy data:

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Comments: ∆dilh12 is the extensive quantity obtained for a given total volume change from V (1) to V (2),

where ϕB(1) denotes the volume fraction of the copolymer in the starting solution and ϕB(2) indenotes the volume fraction after the dilution process

copolymer (B): VA-VAL/04x(1) 55OYA

T/K = 303.15

∆solHB ∞ = −41.3 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3 solvent

T/K = 303.15

∆solHB ∞ = −48.6 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3 solvent

T/K = 303.15

∆solHB∞ = −54.6 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3 solvent

T/K = 303.15

∆solHB∞ = −46.8 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3 solvent

Comments: ∆dilh12 is the extensive quantity obtained for a given total volume change from V (1) to V (2),

where ϕB(1) denotes the volume fraction of the copolymer in the starting solution and ϕB(2) indenotes the volume fraction after the dilution process

copolymer (B): VA-VAL/15x(1) 55OYA

T/K = 303.15

∆solHB ∞ = −60.2 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3 solvent

T/K = 303.15

∆solHB ∞ = −64.7 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3 solvent

Comments: ∆dilh12 is the extensive quantity obtained for a given total volume change from V (1) to V (2),

where ϕB(1) denotes the volume fraction of the copolymer in the starting solution and ϕB(2) indenotes the volume fraction after the dilution process

Comments: ∆dilh12 is the extensive quantity obtained for a given total volume change from V (1) to V (2),

where ϕB(1) denotes the volume fraction of the copolymer in the starting solution and ϕB(2) indenotes the volume fraction after the dilution process

copolymer (B): VA-VAL/20x 55OYA

T/K = 303.15

∆solHB ∞ = −66.4 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3

solvent

T/K = 303.15

∆solHB ∞ = −60.1 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3 solvent

T/K = 303.15

∆solHB ∞ = −64.0 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3 solvent

T/K = 303.15

∆solHB ∞ = −53.2 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3 solvent

T/K = 303.15

∆solHB∞ = −60.4 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3 solvent

copolymer (B): VA-VAL/35x 55OYA

T/K = 303.15

∆solHB ∞ = −44.4 J/(g copolymer)

Comments: the final concentration is < 2 g copolymer/200 cm3

solvent

T/K = 298.15

∆solHB∞ = 1.67 J/(g copolymer)

Comments: the solvent mixture concentration is equal to the comonomer contents,

i.e., 9.0 wt% ethyl acetate/91.0 wt% ethanol

T/K = 298.15

∆solHB∞ = 6.3 J/(g copolymer)

T/K = 298.15

∆solHB∞ = 0.84 J/(g copolymer)

Comments: the solvent mixture concentration is equal to the comonomer contents,

i.e., 44.0 wt% ethyl acetate/56.0 wt% ethanol

T/K = 298.15

∆solHB∞ = 4.6 J/(g copolymer)

copolymer (B): VA-VAL/57w 58TA2

T/K = 298.15

∆solHB∞ = 0.84 J/(g copolymer)

Comments: the solvent mixture concentration is equal to the comonomer contents,

i.e., 57.0 wt% ethyl acetate/43.0 wt% ethanol

T/K = 298.15

∆solHB∞ = 0.0 J/(g copolymer)

T/K = 298.15

∆solHB ∞ = 0.0 J/(g copolymer)

Comments: the solvent mixture concentration is equal to the comonomer contents,

i.e., 67.0 wt% ethyl acetate/33.0 wt% ethanol

T/K = 298.15

∆solHB ∞ = −1.26 J/(g copolymer)

T/K = 298.15

∆solHB ∞ = 0.0 J/(g copolymer)

Comments: the solvent mixture concentration is equal to the comonomer contents,

i.e., 68.6 wt% ethyl acetate/31.4 wt% ethanol

Vinyl acetate/vinyl chloride copolymer

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Characterization:

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

Vinyl chloride/vinylidene chloride copolymer

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Characterization:

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Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

5.2 Partial molar enthalpies of mixing at infinite dilution of solvents and enthalpies of solution of gases/vapors of solvents in molten copolymers from inverse gas-liquid chromatography (IGC)

Copolymer (B) Mn/ Mw/ Mη/ Further information

g/mol g/mol g/mol

solvent (A) T-range/ ∆solHA(vap) ∞

/ solvent (A) T-range/ ∆solHA(vap) ∞

/

K kJ/mol K kJ/mol

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benzene 333.15-393.15 −31.80 n-octane 333.15-393.15 −30.23n-heptane 333.15-393.15 −25.94 toluene 333.15-393.15 −35.30n-nonane 333.15-393.15 −35.62

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