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Amino acid modifiers in

guayule rubber compounds

Colleen McMahan

Research Chemist Lead Scientist, Domestic Natural Rubber United States Department of Agriculture

Agricultural Research Service

Western Regional Research Laboratory Albany, CA USA

United States Department of Agriculture Agricultural Research Service Western Regional Research Laboratory Albany, CA USA
United States Department of Agriculture Agricultural Research Service Western Regional Research Laboratory Albany, CA USA
United States Department of Agriculture Agricultural Research Service Western Regional Research Laboratory Albany, CA USA

USDA-ARS Objective

To develop commercially-viable natural rubber-producing crops suitable for

cultivation in the temperate climate of the United States.

cultivation in the temperate climate of the United States. g u a y u l e

guayule

temperate climate of the United States. g u a y u l e cis 1,4-polyisoprene guayule

cis 1,4-polyisoprene

the United States. g u a y u l e cis 1,4-polyisoprene guayule natural rubber Keys

guayule natural rubber

Keys to sustainability

Tools of genetics, biotechnology ++ utilization of rubber and co-products

guayule natural rubber Keys to sustainability Tools of genetics, biotechnology ++ utilization of rubber and co-products

Opportunity for American and European farmers

Natural rubber the 4 th most valuable agricultural import in the USA (2011) Markets for alternative natural rubber are driving demand US guayule growing region estimated at over 1,000,000 acres

natural rubber are driving demand US guayule growing region estimated at over 1,000,000 acres 79 faostat.fao.org
79
79

faostat.fao.org

Is guayule natural rubber a replacement for Hevea natural rubber? 1. Guayule rubber has lower

Is guayule natural rubber a replacement for Hevea natural rubber?

1. Guayule rubber has lower protein content and is free from Type I latex allergens (Siler et al.

1996, Hamilton and Cornish 2010).

2. Guayule rubber is less thermally stable (Schloman et al 1996a, Keller et al. 1981).

3. Guayule rubber cures more slowly (Schloman

et al. 1996b, Cornish et al. 2008).

4. Guayule rubber has very low gel content (McMahan et al. 2007).

5. Guayule rubber induces SIC more slowly (Shimomura et al. 1982).

 

Plasticity Retention Index: Guayule/Hevea blends

 

70

60

60
60
60

50

PRI

40

30

 

20

10

 

0

 

0

20

40

60

80

100

 

% Guayule

 
   

Green tensile properties

 
 

5

HEVEA PI SBR GUAYULE
HEVEA
PI
SBR
GUAYULE

4

Stress (MPa)

3

2

 

1

 

0

 

0

500

1000

1500

2000

 

Strain (%)

The difference between Hevea and guayule rubber is not the rubber,

it’s the non-rubber constituents: proteins, amino acids, etc.

Onizawa, Curable Rubber Compositions with Amino Acids (1981)

amino acids as vulcanization accelerators, in some cases obviating the need for activators (ZnO).

Othman et al. (1993)

Addition of certain types of amino acids increased compound modulus.

Abad et al. (2002)

improved tensile strength retention attributed to in radiation-cured NR compounds to antioxidant properties of cysteine, alanine and asparagine.

Schloman et al. (2005)

surfactant and washing treatment of Hevea latex reduced the extent of vulcanization in correlation to removal of allergenic proteins.

Tuampoemsab and Sakdapipanich (2007)

improved PRI for deproteinized natural rubber after addition of a Hevea latex extract attributed the result to proteins as natural antioxidants in NR proteins

Amnuaypornsri et al. (2008)

Superior properties of NR are not directly caused by proteins and phospholipids but their interactions with rubber chain ends to form the network structure.

Strain-induced crystallization (SIC) of Hevea rubber (Toki 2014).

Removal of proteins reduce material strength and SIC.

crystallization (SIC) of Hevea rubber (Toki 2014). – Removal of proteins reduce material strength and SIC.

Hevea structure model: Amnuaypornsri et al. (2008)

Hevea structure model: Amnuaypornsri et al. (2008)

Guayule natural rubber

establishing technological fit for use

Recently, significant new industrial investment has taken place for guayule production in the southwestern U.S. due to price instability for petroleum-based and imported rubber and to demand for biobased products.

Sustainable reintroduction of guayule rubber in the industrial supply chain would

benefit from a clearer understanding of the similarities and differences between rubbers

from the two plant sources.

The availability of low protein guayule NR enables an alternative model to compare

the impact of non-rubber constituent biological compounds’ interaction with a polymer

of natural rubber stereochemistry.

Here. low-protein guayule natural rubber (GNR) was blended with a series of amino acids varying in chemical structure to study the impact of specific interactions (e.g.

hydrogen bonds, disulfide bonds, and hydrophobic interactions) that may be formed in

the blends.

interactions (e.g. hydrogen bonds, disulfide bonds, and hydrophobic interactions) that may be formed in the blends.

Materials

L-Proline 98.5+%

SAFC Supply Solutions, MO, USA

L-Glutamine FCC grade PhytoTechology Laboratories, KS, USA

L-Cysteine HCl 99.94% NutraBio, NJ, USA

Glycine 98% ACROS Organics, NJ, USA

trans-4-Hydroxy-L-Proline

≥ 99%

Sigma-Aldrich Co., MO, USA

≥ 99% Sigma-Aldrich Co., MO, USA Guayule natural rubber latex Yulex Corporation, USA

Guayule natural rubber latex Yulex Corporation, USA

Hevea natural rubber latex

Centex LATZ

Centrotrade, USA

Fresh Hevea latex

Instituto Agronômico de Campinas

São Paulo, Brazil

Centex LATZ Centrotrade, USA Fresh Hevea latex Instituto Agronômico de Campinas São Paulo, Brazil

Amino acids in blends

trans-hydroxy-

L-proline

C 5 H 9 NO 3

Amino acid

Formula

Glycine

C

2 H 5 NO 2

L-Glutamine

C

5 H 10 N 2 O 3

L- Proline

C

5 H 9 NO 2

L-Cysteine

C

3 H 7 NO 2 S

Structure

H 9 NO 2 L-Cysteine C 3 H 7 NO 2 S Structure Molecular weight, Da
H 9 NO 2 L-Cysteine C 3 H 7 NO 2 S Structure Molecular weight, Da
H 9 NO 2 L-Cysteine C 3 H 7 NO 2 S Structure Molecular weight, Da
H 9 NO 2 L-Cysteine C 3 H 7 NO 2 S Structure Molecular weight, Da
H 9 NO 2 L-Cysteine C 3 H 7 NO 2 S Structure Molecular weight, Da

Molecular weight, Da

75.07

146.15

115.13

121.16

131.13

Hydrophobicity

index

0.501

0.251

0.711

0.68

0.527

Hydrophobicity index from Black and Mouldt (Analytical Biochemistry, 1991) based on arginine =0 and phenylalanine =1; higher number means more hydrophobic.

Mouldt (Analytical Biochemistry, 1991) based on arginine =0 and phenylalanine =1; higher number means more hydrophobic.

Latex blends preparation

Latex blends preparation Blends were RT stirred 48-72 hours then air-dried prior to use.
Latex blends preparation Blends were RT stirred 48-72 hours then air-dried prior to use.
Latex blends preparation Blends were RT stirred 48-72 hours then air-dried prior to use.

Blends were RT stirred 48-72 hours then air-dried prior to use.

Latex blends preparation Blends were RT stirred 48-72 hours then air-dried prior to use.
GNR L-Gln 2% L-Gln + GNR
GNR
L-Gln
2% L-Gln +
GNR

Test specimen drying

Test specimen drying
Test specimen drying

Compound formulation

Ingredient

Tradename/Supplier

phr (dry)

Guayule latex

Yulex Corporation

100

Potassium hydroxide solution (10%)

Fisher Scientific

0.5

Sulfated methyl oleate salt surfactant

Darvan SMO (1)

1

Sodium alkyl sulfate/sodium lauryl sulfate surfactant

Darvan WAQ (1)

1

Sulfur dispersion

Bostex 378 (2)

1

Zinc oxide dispersion

Zinc oxide dispersion (1)

1

Dithiocarbamate accelerator

Setsit 5 (1)

0-1

Dithiocarbamate accelerator

Setsit 104 (1)

0-1

Antioxidant

Agerite superlite (1)

0-1

   

107.5

1= RT Vanderbilt, Norwalk, CT

2= Akron Dispersions, Copley, OH

Agerite superlite (1) 0-1     107.5 1= RT Vanderbilt, Norwalk, CT 2= Akron Dispersions, Copley,

Characterization methods

Characteristic

Method

Parameters

Instrumentation

Dynamic viscosity (polymer + blends)

ASTM D6204B+C

Cure parameters (compounds)

* (dynamic complex viscosity)

Cure parameters

Advanced Polymer Analyzer Alpha Technologies, Akron, OH

USA

Plasticity Retention Index

ASTM D3194-04

PRI

Wallace Plastimeter Wallace Instruments,

Redhill, Surrey

UK

% Gel

ASTM D3616-95

% gel (insoluble)

-

Green strength of raw films

Mechanical properties of compounds

ASTM D412-06a Die D

Tensile strength

Instron Tensometer Instron, Norwood MA USA

Protein stability

SDS-PAGE

Gel image

-

Die D Tensile strength Instron Tensometer Instron, Norwood MA USA Protein stability SDS-PAGE Gel image -

Results: Dynamic Viscosity

30

20

10

0

% change in η* @ 100°C, 1.0 Hz

+ Gln 0.2 GNRL Control + + Gly 2.0 Gly 1.0 + Gly 0.2 GNRL
+ Gln 0.2 GNRL Control + + Gly 2.0 Gly 1.0 + Gly 0.2 GNRL
+ Gln 0.2 GNRL Control + + Gly 2.0 Gly 1.0 + Gly 0.2 GNRL
+ Gln 0.2 GNRL Control + + Gly 2.0 Gly 1.0 + Gly 0.2 GNRL
+ Gln 0.2 GNRL Control + + Gly 2.0 Gly 1.0 + Gly 0.2 GNRL
+ Gln 0.2 GNRL Control + + Gly 2.0 Gly 1.0 + Gly 0.2 GNRL
+
Gln 0.2
GNRL Control
+
+
Gly 2.0
Gly 1.0
+
Gly 0.2
GNRL Control

+

Gln 1.0

+ + GNRL Control + OH-Pro 2.0 + OH-Pro 1.0 + OH-Pro 0.2 GNRL Control
+
+
GNRL Control
+
OH-Pro 2.0
+
OH-Pro 1.0
+
OH-Pro 0.2
GNRL Control
+
+
+
Cys 2.0
Cys 1.0
Cys 0.2
GNRL Control
+
Pro 2.0
+
Pro 1.0
+
Pro 0.2
GNRL Control
+
Gln 2.0
Control + + + Cys 2.0 Cys 1.0 Cys 0.2 GNRL Control + Pro 2.0 +
Control + + + Cys 2.0 Cys 1.0 Cys 0.2 GNRL Control + Pro 2.0 +
0.2 GNRL Control + Pro 2.0 + Pro 1.0 + Pro 0.2 GNRL Control + Gln

Gly:Pro:OH-Pro 1.0

Gly:Pro:OH-Pro 2.0

+ Gln 2.0 Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* =
+ Gln 2.0 Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* =
+ Gln 2.0 Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* =
+ Gln 2.0 Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* =
+ Gln 2.0 Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* =
+ Gln 2.0 Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* =
+ Gln 2.0 Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* =
+ Gln 2.0 Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* =
+ Gln 2.0 Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* =
+ Gln 2.0 Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* =

-10

-20

-30

-40

-50

Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest
Gly:Pro:OH-Pro 1.0 Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest

Controls average η* = 2830 Pa-sec lowest value + 2.0% cysteine = 1781 Pa-sec

Gly:Pro:OH-Pro 2.0 -10 -20 -30 -40 -50 Controls average η* = 2830 Pa-sec lowest value +
Results: Plasticity Retention Index % change in PRI 700 600 500 400 300 200 100

Results: Plasticity Retention Index

% change in PRI 700 600 500 400 300 200 100 0 Controls average PRI
% change in PRI
700
600
500
400
300
200
100
0
Controls average PRI = 9.6; highest value for +2.0%
cysteine = 35.8
GNRL Control
+ Gly
+ Gly
1.0
+ 0.2
Gly
GNRL
Control
+ 2.0
Gln
+ Gln
1.0
+ 0.2
Gln
GNRL
Control
+ 2.0
Pro
+ Pro
1.0
+ 0.2
Pro
GNRL
Control
+ 2.0
Cys
Cys
+ GNRL
+ 0.2 +
Cys
2.0
OH-Pro
0.2
OH-Pro
1.0
+
OH-Pro
2.0
GNRL
+ 1.0 + Control Gly:Pro:OH-Pro
Control
+
Gly:Pro:OH-Pro
0.2 1.0 2.0
+
Gly:Pro:OH-Pro

Results: Green strength

HydroxyProline/Guayule Blends

100% Gua

 

Green Strength

 

+ 2.0% OH-Pro

 

0.4

 
   

0.3

0.3

Stress MPa

0.2

0.1

0.0

 

0

400

800

1200

1600

 
 

Strain %

   

Glycine: Proline: HydroxyProline

100% Gua

 

Guayule Blends

 

Green Strength

 

+ 2.0% AA

 

0.4

   

0.3

0.3  
 
 

Stress MPa

0.2

 

0.1

0.0

 

0

400

800

1200

1600

 

Strain %

Proline/Guayule Blends 100% Gua Green Strength + 2.0% Pro 0.5 0.4 0.3 0.2 0.1 0
Proline/Guayule Blends
100% Gua
Green Strength
+ 2.0% Pro
0.5
0.4
0.3
0.2
0.1
0
0
400
800
1200
1600
Stress MPa

Strain %

100% Gua Cysteine/Guayule Blends + 2.0% Cys Green Strength 0.4 0.3 0.2 0.1 0 0
100% Gua
Cysteine/Guayule Blends
+ 2.0% Cys
Green Strength
0.4
0.3
0.2
0.1
0
0
200
400
600
800
1000
1200
Stress MPa

Strain %

Blends + 2.0% Cys Green Strength 0.4 0.3 0.2 0.1 0 0 200 400 600 800

Results: % gel

Results: % gel 100% Guayule 100% Hevea 150 100 50 0 -50 -100 + Gly:Pro:OH-Pro 2.0

100% Guayule

Results: % gel 100% Guayule 100% Hevea 150 100 50 0 -50 -100 + Gly:Pro:OH-Pro 2.0

100% Hevea

150

100

50

0

-50

-100

+ Gly:Pro:OH-Pro 2.0 + Gly:Pro:OH-Pro 1.0 + Gly:Pro:OH-Pro 0.2 GNRL Control + OH-Pro 2.0 +
+
Gly:Pro:OH-Pro 2.0
+
Gly:Pro:OH-Pro 1.0
+
Gly:Pro:OH-Pro 0.2
GNRL Control
+
OH-Pro 2.0
+
OH-Pro 1.0
+
OH-Pro 0.2
GNRL Control
+
Cys 2.0
+
Cys 1.0
+
+
Cys 0.2
GNRL Control
Pro 2.0
+
Pro 1.0
+
Pro 0.2
GNRL Control
+
Gln 2.0
+
Gln 1.0
+
Gln 0.2
GNRL Control
+
+
Gly 2.0
Gly 1.0
+
Gly 0.2
GNRL Control

Controls average gel = 7.9% (sd 1.6); +2.0% cysteine = 12.3%

Results:

Cure curves for cysteine/guayule blends @ 100°C

Strain [S']

100% Gua

+ 0.2% Cys

+ 1.0% Cys

+ 2.0% Cys

Cysteine and Guayule Compound Blends

Cure Curve w/o Acc + AO

5

0 10 20 30 40 Time [min]
0
10
20
30
40
Time [min]

4

3

2

Cys Cysteine and Guayule Compound Blends Cure Curve w/o Acc + AO 5 0 10 20
Cys Cysteine and Guayule Compound Blends Cure Curve w/o Acc + AO 5 0 10 20

Results:

Cure curves glutamine/guayule blends @ 100°C

100% Gua Glutamine/Guayule Compound Blends + 0.2% Gln Cure Curve w/o Acc + AO +
100% Gua
Glutamine/Guayule Compound Blends
+ 0.2% Gln
Cure Curve w/o Acc + AO
+ 1.0% Gln
+ 2.0% Gln
6
5
4
3
2
1
0
10
20
30
40
Strain [S']

Time [min]

Gln Cure Curve w/o Acc + AO + 1.0% Gln + 2.0% Gln 6 5 4
Gln Cure Curve w/o Acc + AO + 1.0% Gln + 2.0% Gln 6 5 4

Results: Cure curves @ 1.67 Hz, 0.5° arc, ~160°C

100% Gua Glycine/Guayule Compound Blends +0.2% Gly Cure Curve +1.0% Gly +2.0% Gly 5.0 4.0
100% Gua
Glycine/Guayule Compound Blends
+0.2% Gly
Cure Curve
+1.0% Gly
+2.0% Gly
5.0
4.0
3.0
2.0
0
10
20
30
40
Time [min]
100% Gua
HydroxyProline/Guayule
+ 0.2% OH-P ro
Compounded Blends
+1.0% OH-P ro
Cure Curve
+2.0% OH-P ro
5.0
4.0
3.0
2.0
0
10
20
30
40
Time [min]
Strain [S']
Strain [S']
100% Gua Glutamine/Guayule Compound Blends +0.2% Gln +1.0% Gln Cure Curve +2.0% Gln 5.0 4.0
100% Gua
Glutamine/Guayule Compound Blends
+0.2% Gln
+1.0% Gln
Cure Curve
+2.0% Gln
5.0
4.0
3.0
2.0
0
10
20
30
40
Strain [S']

Time [min]

100% Gua Glycine:Proline:Hydroxy-Proline/ +0.2% Gly:P ro :OH-P ro Guayule Compound Blends +1.0% Gly:P ro :OH-P
100% Gua
Glycine:Proline:Hydroxy-Proline/
+0.2% Gly:P ro :OH-P ro
Guayule Compound Blends
+1.0% Gly:P ro :OH-P ro
Cure Curve
5.0
+2.0% Gly:P ro :OH-P ro
4.0
3.0
2.0
0
10
20
30
40
Strain [S']

Time [min]

ro :OH-P ro Cure Curve 5.0 +2.0% Gly:P ro :OH-P ro 4.0 3.0 2.0 0 10

Results: Heat stability of Hevea latex proteins

Control

Control

Control

Control

° C ° C

° C 160

° C 160

° C 160

° C 160

° C ° C

° C ° C

° C ° C

° C 140

° C 140

° C 140

° C 140

Marker

Marker

Marker

Marker

Marker

Marker

100 120

100 120

100 120

100 120

Fresh Hevea latex

Fresh Hevea latex

total proteins

total proteins

Centex Hevea latex

Centex Hevea latex

total proteins

total proteins

latex Fresh Hevea latex total proteins total proteins Centex Hevea latex Centex Hevea latex total proteins
Eaton and Grantham (1915) reported adding heat-coagulable proteins in their original form had only slightly
Eaton and Grantham (1915) reported adding heat-coagulable proteins in their original form had only
slightly improved slow curing crepe, but after putrefaction ‘the same proteins had a marked accelerating
action on vulcanization’.

Addition of amino acids to guayule latex….

…acted as a plasticizer reducing bulk viscosity up to 40% (glutamine)

…acted as an antioxidant, in all cases (best for cysteine)

…impacted cure depending on the

composition and R-group structure

Without accelerator acceleration (cysteine)

scorch inhibition (glutamine)

With added accelerator ….reduced cure state (most) …moderated reversion

(glutamine)

Glutamine and Guayule Blends ASTM D6204 B -Viscoisty η* at 1.0 Hz 3500 3000 2500
Glutamine and Guayule Blends
ASTM D6204 B -Viscoisty η* at 1.0 Hz
3500
3000
2500
2000
1500
1000
500
0
0.0
0.2
1.0
2.0
% Amino Acid
Glycine and Guayule Blends
Plasticity Retention Index
25
20
15
10
5
0
0.0
0.2
1.0
2.0
% Amino Acid
Cysteine and Guayule Blends
Plasticity Retention Index
40
35
30
25
20
15
10
5
0
0.0
0.2
1.0
2.0
% Amino Acid
PRI
η* (Pa.s)
PRI

Summary: Addition of amino acids to guayule latex

L-Glycine trans-hydroxy-L- L-Proline Amino acid Glycine L-Glutamine L-Proline L-Cysteine proline trans-hydroxy-L-
L-Glycine
trans-hydroxy-L-
L-Proline
Amino acid
Glycine
L-Glutamine
L-Proline
L-Cysteine
proline
trans-hydroxy-L-
proline
Formula
C
C
C
C
3 H 7 NO 2 S
C
-
2 H 5 NO 2
5 H 10 N 2 O 3
5 H 9 NO 2
5 H 9 NO 3
Structure
-
5-12%, systematic
Gel Content
-
-
Up from 4-11%
-
-
increase
Bulk
Lower
Reduced, esp. at
Lower at 2%
Lower at 2%
Lower at 1%
Lower at 2%
Viscosity
systematically
1%
PRI
Improved
Improved ++
Improved
Improved ++
Improved
Improved
Green
-
-
Slight increase
-
Slight increase
Slight increase
Strength
Reversion
Yes
State of cure slight
bump, NO
reversion
Yes
Yes
Yes
Yes
Slight increase Slight increase Strength Reversion Yes State of cure slight bump, NO reversion Yes Yes

Conclusions

Amino acids can be considered biobased modifiers in latex and bale rubber compounds for use as plasticizers, antioxidants, and as vulcanization aids.

L-glutamine, in particular, served as a plasticizer, antioxidant, and anti-

reversion agent in guayule compounds.

There are over 500 known amino acids; additional studies are required to fully assess their technological, economic, and life cycle potential.

Continued studies can also provide further insight as to the mechanisms of non-rubber constituents’ interaction with polymers in Hevea (and other) natural rubber compositions.

mechanisms of non- rubber constituents’ interaction with polymers in Hevea (and other) natural rubber compositions .

Dankeschön!

This work was supported by the United States Department of Agriculture, Agricultural Research Service through a collaboration with the University of Nevada-Reno.

Materials were generously donated by:

Yulex Corporation Instituto Agronômico de Campinas

RT Vanderbilt Company

Centrotrade Akron Dispersions

Agronômico de Campinas RT Vanderbilt Company Centrotrade Akron Dispersions Ms. Dhondup Lhamo Prof. David Shintani
Agronômico de Campinas RT Vanderbilt Company Centrotrade Akron Dispersions Ms. Dhondup Lhamo Prof. David Shintani

Ms. Dhondup Lhamo

Agronômico de Campinas RT Vanderbilt Company Centrotrade Akron Dispersions Ms. Dhondup Lhamo Prof. David Shintani

Prof. David Shintani

Agronômico de Campinas RT Vanderbilt Company Centrotrade Akron Dispersions Ms. Dhondup Lhamo Prof. David Shintani