Table 1 Material Characteristic Properties of Modified PHAs via Different Methods and Their Applications

From: Polyhydroxyalkanoates: opening doors for a sustainable future

Material type

Polymers

Tm (°C)

Tg (°C)

Xc, (%)/Td(°C)

Mechanical properties

Applications

Reference

Polymer blends

PHB/starch

165.4 to 167.9

67.2 to 87.4

Td=200.5 219.7

σmax=4.99 to 19.7 MPa, E: 578 to 1716 MPa, ɛmax=3.5 to 9.8%

Coating materials, cardboard for food package

10

 

PHB/SA

171.0 to 175.9

8.6 to 9.9

ND

ND

ND

11

 

PHBV/PGA-g-starch

ND

ND

ND

σmax=16.8 to 24.3 MPa, E: 458 to 539 MPa, ɛmax=13 to 18%

ND

12

 

PHB/PVAc-g-starch (CSV)

167 to 171

3 to 25

Xc,PHB=32.9 to 66.4 Td=268 to 295

ND

ND

13

 

PHB/EC

175.3 to 177.0

44.6 to 56.1, annealed samples

Xc,PHB=15.4 to 64.3

ND

ND

15

 

PHB/CAB

178.5 to 189.5

6.3 to 12.5

Xc,PHB=40.6 to 53.2

σmax=13.3 to 29.3 MPa, E: 592.4 to 2288.3 MPa, ɛmax=2.2 to 7.3%

ND

16, 79

 

PHB/lignin

152 to 174

7.0 to 43.0

Xc,PHB=21 to 61

G'=3–5 × 104 Pa at ω of 1 to 100 rad s−1

G''=50-1 × 105Pa at ω of 1 to 100 rad s−1

ND

18

 

PHB/soda lignin

ND

8.6 to 39.5

Td=162 to 212

ND

ND

20

 

PHB/PHBHHx

Approximately 152 to 165

Approximately 0.8 to 5.0

ND

E: 500 to 1210 MPa

Scaffolds for tissue engineering with improved biocompatibility

22, 23

 

PHBV/PLA

PLA:150, PHBV: 170

PLA: 53.2 to 57.6

PHBV:~3

ND

G'=20-1.2 × 104Pa at ω of 0.01 to 100 rad s−1, η=500 to 1030 Pas at ω of 1 rad s−1

ND

29

 

MCL-PHA/PLA

50 to 180

PLA: 55.7 to 57.7, PHA: −32.8~−33.5

Xc,PHA=25 to 58

σmax=30 to 50 MPa

J=8.1 × 10−2–26.0 × 10−2 J

Ductile and tough properties for plastics applications

30, 31

 

PHB/PLA

174.6 to 175.1

PHB: 9.6 to 11.0

PLA: 48.3 to 54.9

Xc,PHB=55.0 to 56.3

E: 274 to 366 MPa σmax=6.5 to 8.7

ɛmax=3.7 to 27.7%

ND

32

 

P3/4HB/PLA stereocomplex (SC)

PLA SC: 218

P3/4HB: -12.5

Xc,PLA SC=38.1 to 45.1

σmax=4.2 to 6.6 MPa, E: 30.8 to 46.7 MPa, ɛmax=362.7 to 949.0

Enhanced processabiltiy and enzymatic hydrolysis rates

34

 

PHBHHx/PCL

PHBHHx: 95.4

PCL: 61.1

ND

Xc,PHBHHx=10 to 60

E: 190.9 to 324.6

σy=7.7 to 12.2 MPa, T: 0.3 to 3.6 J cm−3

Improved cell adhesion and proliferation for musculoskeletal tissue engineering

35, 36

 

PHBV/PCL

PCL: 57.0 to 57.5

PHBV: 137 to 152.4

PHBV: 1.3

Xc,PHBV=5 to 40

E: 170 to 1200 MPa

σy=9.0 to 12.5 MPa ɛmax=8.0 to 25%

Hollow fibers and tubular scaffold in tissue engineering

37, 38

Graft copolymer

PHA-g-chitosan

PHA: PHB, PHBV, PHO

PHB: 150 to 173

PHBV: 117 to 131

PHO: 80

Chitosan: 105 to 116

ND

Td=290 to 308

ND

Drug delivery and tissue engineering

39, 40

 

PHOU-g-PEG

ND

ND

ND

σmax=219 to 263 kPa

ɛmax=379 to 621%

Blood contact device, drug delivery

41, 51, 52

 

PHB-g-PMMA

PHB: 171.8 to 176.8

PHB: 2.5 to 6.0

PMMA: 100 to 102

Xc,PHBV: 12 to 27

Eb=3170 to 3300 MPa

Gc=0.7 to 2.3 KJ m−2

Orthopaedic applications.

43, 44, 49

 

PHBV-g-HEMA

138 to 156

2.3 to 63

Td=297 to 316

ND

Improved cellular interactions with film

46

 

PHBV-g-PVP

140.0 to 158.4

7.7 to 8.6

Xc,PHBV: 35.5 to 45.9

ND

Increased antibacterial activity

47

Block Copolymer

PHOU-b-PCL

60 to 61.5

−57~−60

ND

ND

Facilitating biomolecules conjugation

55

 

PHB-b-PLA-b-PCL

123.4 to 130.2

−23.5~−31.2, 11.2 to 32.8

Xc,PHB: 12.1 to 49.7

ND

Blood contact device

56

 

PHB-r-PCL

PCL: 38.0 to 62.7

PHB: 133.0 to 141.0

−18.3~−62.0

Xc,PHB: 36.6 to 53.8

σmax: 11.0 to 30.5 MPa

ɛmax:=117 to 990%

nd

57

 

P3/4HB-r-PCL

32.3 to 78.4

−21.5~−40.1

Xc,P3/4HB: 3.2 to 20.9, Td=251.6 to 279.5

ND

Wound-healing materials

58

 

P3/4HB-r-P3/4HBa

49.8 to 95.4

−10.8~−48.4

Xc,P3/4HB: 0.5 to 26.8, Td=247.7 to 286.3

ND

Hemostatic materials

59

 

P3/4HB-r-P3/4HB/PHHxHO

44.9 to 75.6

−9.0~−44.6

Xc,P3/4HB: 0.4 to 16.9, Td=241.9 to 264.8

ND

Hemostatic materials

60

 

PHO-r-PHB

61 to 178

−45−4

ND

E: 200 to 1560 MPa

σmax=7.0 to 38 MPa ɛmax=6.3 to 490%

Excellent thermoplastic properties and mechanical properties for medical applications

61

 

PHB-b-PEG

PEG: 47 to 56

PHB: 122 to 152

ND

ND

ND

Self-assemblies for drug delivery

62

 

P(3HV-co-4HB)-b-MPEG

PEG: 53.5

ND

ND

ND

Drug delivery in cancer therapy

63

 

PEG-b-PHB-b-PEG

PEG: 23 to 57

PHB: 140 to 153

ND

Xc,PHB: 53.3 to 73.6 Td=382.9 to 391.0

ND

Supramolecular hydrogel for drug delivery

64, 80

 

PHB-r-PEG

PEG: 31.4 to 61.6

PHB: 82.2 to 148.5

−49~−33

Xc,PHB: 9.3 to 44.5 Td=260.2 to 279.4

E: 21 to 120 MPa, σy: 5.9 to 10.2 MPa, ɛmax: 11-1912%

Biomaterials with programmed degradation rates

66, 67

 

P3/4HB-alt-PEG

32.01 to 53.21

−24.16~−44.26

Td=241.7 to 277.9

ND

Hemocompatible materials

68

 

PHB-r-PEG-r-PPG

ND

ND

Td=227 to 303

η: 0.05 to 0.2 mPa s at 5 °C; 43 to 55 Pa s above 30 °C.

Thermal-responsive hydrogels for protein release and 3D cell culture

69, 70, 71

 

PNIPAAm-b-PHB-b-PNIPAAM

124.3–142.2

ND

Xc,PHB: 7.3 to 42.6 Td=235.9 to 291.9

ND

Temperature-induced smart surface for cell detachment

72, 73, 74

 

PDMAEMA-b-PHB-b-PDMAEMA

ND

ND

Td=230 to 293

ND

Stimuli-responsive drug delivery and gene delivery

75, 76

  1. Abbreviations: CAB, cellulose acetate butyrate; EC, ethyl cellulose; MCL-PHA, medium-chain-length polyhydroxyalkanoates; PGA, polyglycolic acid; PHB, poly(3-hydroxybutyrate); PHBV, poly(3-hydroxybutyrate-co-3-hydroxyvalerate); PLA, Poly(lactic acid); PVAc, poly(vinyl acetate); SA, starch acetate.
  2. σmax: Tensile strength, E: Young’s modulus, ɛmax: Elongation at break, G': Storage modulus, G'': loss modulus, ω: Frequency. J: Total absorbed energy in Charpy impact test, σy: yield stress. T: toughness, Eb: Bending modulus in Charpy impact test. Gc: Critical energy release factor, nd: not determined.
  3. aP3/4HB with different 4HB contents were employed as prepolymers.