AN ACCELERATOR FREE

PEROXIDE VULCANIZATION
TECHNIQUE

Presented by
Under the guidance of ANOOP K M (8609)
Dr. A S ABDUL RASHEED FOUZIYA K (8650)
CLINTON THOMSON (8614)
INTRODUCTION

 An accelerator-free curing method has been developed for use with many
existing lattices
 Lattices used are natural rubber (NR), enzymatically deproteinized NR,
guayule NR, synthetic polyisoprene (IR), polychloroprene (CR), and others
 This vulcanization technique can be used for implantable and indwelling
medical devices, non-embryotoxic gloves for embryo transfer, catheter
balloons, sheaths, etc.
 Dip molded rubber films manufactured via this technique are generally highly
biocompatible, and free of the common allergenic agents responsible for Type
IV latex allergies.
 In addition, traditional dip molded products such as condoms and medical
gloves can be improved with the incorporation of this technique
OBJECTIVE

 Production of ultra-thin(.042-.045mm) dip molded products

 Avoid allergic problems due to traditional vulcanization technique
 Analyze the properties of the products produced by using this technique
 For making the production cost effective
 To compare vulcanizing ability of different peroxides
TRADITIONAL TECHNIQUE

 Vulcanization is the process of crosslinking rubber molecules to transform

them from a mainly viscous state to an elastic state by forming a three
dimensional network.
 Sulphur is being used as the most popular vulcanizing agent. Although rubber
can be cured by sulphur alone, the process is very slow and the properties
obtained are not ideal.
 Today sulphur is used in conjunction with one or more accelerators.
 The three dimensional structure produced by crosslink during vulcanization
restricts the free mobility of the long polymeric molecules.
 The crosslinks have the effect of preventing the polymer chains moving bodily
past each other when an external force is applied to the matrix.
 COMPOUNDING INGREDIENTS

Sl. No. Name of the chemical Functions

1. Sulphur Vulcanizing Agent
2. Zinc Oxide Vulcanizing Activator
Setsit S5 / Pilcure S 5 / Noc celer TP / SDBC
3. Vulcanizing Accelerators
(Activated dithiocarbamates)
4. Lowinox CPL / Wingstay-L (Phenolic derivatives) Antioxidants
Ammonium caseinate / Pot. Oleate / Pot. Laurate /
5. Stabilizing agents
KOH
6. 1% Ammonia Solution Stabilizing agent
7. Tamol / Darvan 1 / Darvan 2 Dispersion agents
To impart color to
8. Color pigments
condoms
PEROXIDE VULCANIZATION

 Peroxide vulcanization of latex was a simple process ,here peroxide with

activator is used for vulcanizing dry rubber instead of sulphur
 Hydro-peroxide vulcanized lattices can produce films with physical properties
similar to those of sulphur vulcanized latex films
 The basic mechanism of peroxide prevulcanization involves O — O cleavage
of the peroxide producing alkoxy radicals
 When polymers are crosslinked by peroxides, carbon to carbon bonds are
formed between individual polymer chains.
 The C-C bond is stronger and more thermally stable than the S-S bond
 The higher strength of the covalent C-C bond network means that peroxide
curing is the preferred crosslinking method to obtain optimum thermal
stability.
 COMPOUNDING

COMPOUNDING 1
NATURAL RUBBER LATEX (2672gm)
FRUCTOSE (20%-136gm)
TERT BUTYL HYDROPEROXIDE (68.1%-16.86gm)
POTASSIUM LAURATE (20%-20gm)
WATER(358.4 ml)
COMPOUNDING 2
NATURAL RUBBER LATEX (1336gm)
CUMENE HYDRO-PEROXIDE (10gm)
HYDROXYLAMINE HYDROCHLORIDE (60gm)
POTASSIUM LAURATE (20%-10gm)
WATER (149.2ml) & AMMONIA (25%-30ml)
 FLOW DIAGRAM OF ACCELERATOR-
FREE PEROXIDE CURING METHOD
ADVANTAGES

 It is simple and cost effective

 It is favourable to produce thin film
 It is energy efficient and less cure time
 NR films made via this system have exceptionally low levels of extractable
proteins.
 Products produced via this new curing method can effectively be manufactured
without sulfur, accelerators, activators, and boosters.
 It may be possible to significantly reduce or potentially eliminate Type IV allergens
in a variety of medical devices.
 Tensile set properties are generally more favorable than what can be obtained
with traditional methods.
 This helps to produce pore-free films, which are necessary to prevent the passage
of pathogens, or other unwanted substances, through the wall of the dipped part.
DISADVANTAGES OF EXISTING TECHNIQUE

 Many traditionally compounded and cured latex films will not pass
cytotoxicity tests
 Ultra thin products cannot be produced
 Not possible to eliminate Type VI allergens completely
RESULTS
COMPOUNDING 1
 Tert-butyl hydroperoxide Compounding-
Results of the product compatibility tests within agreeable limits with
the standard values.

LATEX PROPERTIES

Viscosity HST MST pH NH3 % SDT

Compound Cure TS

Day Day Day Day Day Day Day Day Day Day Day Day Day
Day 1 Day 2 Day 7 Day 1 Day 2
1 2 7 1 2 7 7 1 2 7 1 2 7

PPNR 5 hrs 51.5 21.1 21.3 21.5 1102 1073 1050 300 291 260 10.88 10.68 10.44 0.55 0.40 0.35 7.9 7.9 7.7

STD 7 hrs 51.5 21.0 21.5 21.8 753 712 665 378 345 286 11.05 10.98 10.95 0.75 0.71 0.68 7.2 7.2 7.0
 Comparison of BVBP

Before Ageing After Ageing 7 days

Compound 4th day 5th day AVG 4th day 5th day

BV BP NC BV BP NC BV BP BV BP NC BV BP NC

PPNR 20.35 1.21 0/10 21.65 2.03 1/10 21.00 1.62 19.65 1.08 1/10 19.45 1.17 2/10

STD 34.20 1.45 0/10 30.33 1.76 0/10 32.27 1.61 37.66 1.68 0/10 46.50 1.73 0/10
 COMPOUNDING 2
 Cumene hydroperoxide compounding-
Experiments have been conducted and the values compared to the
standard values

LATEX PROPERTIES

Viscosity HST MST pH NH3 % SDT

Compound Cure TS

Day Day Day Day Day Day Day Day Day Day Day Day Day
Day 7 Day 1 Day 7 Day 1 Day 2
1 2 7 1 2 2 7 1 2 7 1 2 7

PPNR 8 hrs 52 21.5 21.3 21.2 954 921 892 295 263 240 10.58 10.21 9.98 0.59 0.51 0.30 7.4 7.7 7.3

STD 7 hrs 51.5 21.0 21.5 21.8 753 712 665 378 345 286 11.05 10.98 10.95 0.75 0.71 0.68 7.2 7.2 7.0
 Comparison of BVBP

Before Ageing After Ageing 7 days

Compound 4th day 5th day AVG 4th day 5th day

BV BP NC BV BP NC BV BP BV BP NC BV BP NC

PPNR 12.03 .3 9/10 13.2 .6 8/10 12.5 .5 11.2 .35 8/10 12.1 .53 9/10

STD 34.20 1.45 0/10 30.33 1.76 0/10 32.27 1.61 37.66 1.68 0/10 46.50 1.73 0/10
INFERENCE

 Compounding with two different types of peroxides have been conducted and
the standard test have been performed on both.

 Compounding with tert-butyl hydroperoxide is more effective comparitively.

REFERENCE
 Bruce K. Rodaway (08/28/73), Prevulcanization of Rubbers by Hydrogen
Peroxide and An Activator, US Patent 3,755,232
 Dipping With Natural Latex, 1995, The Malaysian Rubber Producers=
Association
 Geoffrey Scott, (01/13/59), Curing Natural Rubber Latex with a Peroxide, US
Patent 2,868,859
 Mark W. McGlothlin -Accelerator Free Curing of Dip Molded Latex Films
President Apex Medical Technologies, Inc. San Diego, CA
 Walter S. Ropp (03/14/61), Vulcanization of Latex with Organic
Hydroperoxide, US Patent 2,975,151
THANK YOU