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Rubber Division

The 153rd Rubber Division ACS Technical Meeting (Indianapolis, Indiana, May 5-8, 1998) featured a 12-topic symposium, which focused on numerous key issues facing the rubber industry.

One of the most popular topics was the use of alternate vulcan- ization systems versus sulfur cure. This topic selection reflected the recent growth and interest in peroxide-cure vulcanization, which is due to the high-temperature demands of today’s compounds.

Ten other technical papers were presented throughout the day to a packed, standing-room- only audience. Based on this success, a follow-up to this per- oxide-cure-focused symposium

a follow-up to this per- oxide-cure-focused symposium Oaklands Corporate Center 502 Thomas Jones Way Exton, PA
a follow-up to this per- oxide-cure-focused symposium Oaklands Corporate Center 502 Thomas Jones Way Exton, PA

Oaklands Corporate Center 502 Thomas Jones Way Exton, PA 19341 Phone 610-363-4100

Toll Free

Fax 610-363-4140

800-SARTOMER

ACS Technical Meeting

Free Fax 610-363-4140 800-SARTOMER ACS Technical Meeting has been tentatively slated for the 158th Rubber Division

has been tentatively slated for the 158th Rubber Division ACS Technical Meeting and Mini-Expo (scheduled to be held in Cincinnati, Ohio at the Cincinnati Convention Center from October 17-20, 2000).

If you would like more infor- mation about the meeting and exhibition or if you are interested in submitting a contribution, please contact:

ACS Rubber Division

Phone

(330) 972-7814

Fax

(330) 972-5269

Web Site

www.rubber.org

Fax (330) 972-5269 Web Site www.rubber.org SARTOMER CURE concepts Volume IV Inside •

SARTOMER

CURE
CURE

CURE

CURE
CURE
CURE

concepts

Volume IV

Inside

Peroxide-Coagent vs. Sulfur-Accelerator Cure

Methacrylate Coagents for Improved Hot Tear Strength

Fiber/Fabric to Rubber Adhesion

New Reactive Dispersions for Rubber Applications

Basic Principles of Peroxide- Coagent Curing of Elastomers

New Technical Resources

for Rubber Applications • Basic Principles of Peroxide- Coagent Curing of Elastomers • New Technical Resources
for Rubber Applications • Basic Principles of Peroxide- Coagent Curing of Elastomers • New Technical Resources
Peroxide-Coagent vs. Sulfur-Accelerator Cure Table 1 Introduction Adding reactive coagents (such as methacrylate and

Peroxide-Coagent

vs. Sulfur-Accelerator Cure

Table 1

Introduction

Adding reactive coagents (such as methacrylate and acrylate monomers) to peroxide-cure systems delivers notable improvements. Enhancements in compression set and heat resistance (relative to sulfur- cure products) have expanded the use of peroxide-coagent systems in stringent end-use applications, such as automotive under-the-hood applications.

Comparing Cure-System Features

Table 1 lists specific perfor- mance benefits of peroxide- coagent crosslinking over sulfur vulcanization.

them due to perceptions of higher cost. However, more recent focus on the total cost of manufacturing reveals a different picture.

Peroxide-coagent systems are simple, usually requiring a single peroxide and a single coagent to achieve the desired properties. Sulfur-cure applica- tions, in contrast, may require three, four, or even five expen- sive accelerators to overcome deficiencies in the cure systems. Once the costs associated with comparable or improved performance are examined, the peroxide-coagent systems are favored.

The Role of the Coagent

COMPARATIVE FEATURES

Peroxide-Coagent Crosslinking

Sulfur Vulcanization

Excellent compression set

Good tear strength

Superior heat stability

Often bad smell, staining,

Exceptional aging stability

and blooming

Excellent scorch safety

Unsaturated rubbers only

Simple compounding

Sometimes scorchy

Safe handling

Many ingredients needed

Nitroso-amine free

Reversion on overvulcanization

Good tear strength

Good surface cure

Functions with:

elastomer blends

(un)saturated rubbers

Is a coagent really needed? The answer to

this question is, "yes."

Sulfur-accelerator

systems yield superior

performance over

peroxide-only cure

systems. However,

adding the "proper" coagent to the peroxide systems will lead to

Exposing the Cost Myth

Despite the performance ad- vantages of peroxide-coagent systems, some compounders are still hesitant to incorporate

results even more superior than those of the sulfur-accelerator systems, as Table 2 reveals.

Coagents modify the tight C-C bond network usually achieved

with peroxide-only curing. The coagents homopolymerize and graft onto the polymer backbones, which yields lower compression set and higher tensile strength, tear strength, elongation, and modulus.

Converting from peroxide- only cure to a peroxide- coagent system also yields a reduced peroxide level.

Conclusion

The peroxide-coagent cure system offers con- siderable flexibility over the sulfur-accelerator system. Many peroxides are available, which dictate cure temperatures from ambient to 200º C. Sartomer offers a broad array of non-nitroso scorch-retarded coagents to complement the avail- able range of peroxides and meet specific perfor- mance requirements (Tables 3A and 3B ).

★★★★ = Excellent ★★★ = Good ★★ = Fair = Some positive effect 0 = No effect = Negative

Comparison of Cure Systems –Typical EPDM Compound

Table 2

 

Sulfur-

Peroxide

Peroxide-

Accelerators

Only

Coagent

Cure Variability

Very good

Moderate

Very good

Reversion Resistance

Moderate

Very good

Very good

Tensile Strength

Good

~15% less

Good

Ultimate Elongation

Good

~30% less

Good

Tear Strength

Good

~30% less

Good

Heat-Aging Resistance

Good

~30% less

Good

Compression Set,

Good

Good

Good

Ambient

Compression Set,

Moderate

Moderate

Very good

>100º C

Cure Property Comparison

Table 3A

Product

Saret ® 516

Saret ® 517

Saret ® 519

Saret ® 521

Saret ® 522

Scorch

★★★

★★

★★

★★★

★★

Cure Time

★★

★★★

★★

Compression

★★

★★★

★★★

★★

★★★

Set

Modulus

★★

★★

★★★

★★

★★★

Tensile

★★

★★

★★

★★

★★★

Elongation

★★

★★

Hardness

★★

★★★

★★★

★★

★★★

Mooney

★★★

★★

★★

★★★

★★

Viscosity

Hot Tear

★★★

★★★

Heat Age

★★★

★★★

★★★

★★★

★★★

Adhesion

 

00000

     

Cure Property Comparison

Table 3B

Product

Saret ® 633

Saret ® 634

Sulfur-Accel.

Peroxide Alone

Scorch

★★

★★★

★★★

★★★★

Cure Time

★★★

★★

★★★

Compression

0

Set

Modulus

★★★

★★

★★★

Tensile

★★★

★★★

★★★

Elongation

★★

★★★

★★★

Hardness

★★★

★★

★★★

Mooney

0

0

Viscosity

Hot Tear

★★

★★★

0

Heat Age

★★★

★★★

★★★

Adhesion

★★★★

★★★

0

Methacrylate Coagents for Improved Hot Tear Strength

High hot tear strength is important to demolding of elastomeric parts. Sartomer evaluated many coagents
High hot tear strength is
important to demolding of
elastomeric parts. Sartomer
evaluated many coagents to
gather comparative hot tear
strength data, yielding the
following conclusions:
The methacrylate crosslinked
network can dissipate the hot
tear stresses and maintain the
integrity of the crosslinked
product. Sulfur cure, on the
other hand, forms long, flexible
network chains, but the bond
is shown for both room
temperature and 150º C tear.
Above about 5 PHR, tear
strength for both temperatures
is constant.
What makes the metallic Saret
634 interesting is that this
coagent duplicates many
of the other good properties
exhibited by sulfur cure
systems, such as flex modulus
and dynamic properties.
strength is insufficient for
• Methacrylate coagents
are better than acrylates
sustaining the tear stress at
Figure 3:
high-temperature conditions.
Hot Tear Strength for EPDM
Cured with Dicumyl Peroxide
• Difunctional is better
than trifunctional
Coagents that produce good
hot tear properties include:
Figure 2 illustrates the effect
of methacrylate versus acrylate
versus functionality in NBR
Cure. The strong effect of
functionality is seen in the
trifunctional Saret ® 517 data,
where tear strength is reduced
below the control despite a
methacrylate backbone. Even
the difunctional acrylate Saret ®
600
25° C
• Hot tear depends on concen-
tration of coagent up to 5
PHR; then it becomes constant
160° C
500
Saret ® 634, zinc
dimethacrylate
400
• Methacrylates are better
than sulfur
Saret ® 521, difunctional
methacrylate
300
• Acrylates are equivalent
to sulfur
Saret ® 516, difunctional
methacrylate
633 has higher tear strength.
Saret 634, difunctional
methacrylate, exhibits the best
tear strength.
200
100
• Peroxide alone is poorer
than sulfur
0
Figure 2:
Sulfur*
Saret 634*
Saret 521*
The above principles are illus-
trated in the following graphs.
Room Temperature Tear Strength*
For NBR Cure
* Cured to 200 psi Modulus
Theory holds that the ideal
network structure for good hot
tear is a long, flexible crosslink
400
370
In Figure 1, the effect of coa-
gent concentration (Saret 634)
350
Conclusion
300
300
270
derived from difunctional coa-
gents. Trifunctional coagents
tend to restrict the chain
mobility when stresses are
Figure 1:
250
210
Saret 634 Concentration vs.
Tear Strength for EPDM Cure
200
150
100
600
applied, increasing the rate
of rupture stress.
50
Saret 634 offers the superior
hot tear strength necessary for
successful demolding of cured
parts. This hot tear strength
performance is superior to
500
0
None
Saret 517
Saret 633
Saret 634
400
*Die C
Coagent (10 PHR)
300
Ambient
200
150º C
100
0
2468
10
12
14
16
18
20
Saret 634, PHR
Tear Strenght, psi
Tear Strength, PSI
Tear Strength, PSI
Tear Strenght, psi Tear Strength, PSI Tear Strength, PSI Difunctional methacrylate coagents are the best choice

Difunctional methacrylate coagents are the best choice for achieving this ideal network. Since methacrylates tend to react slower than acrylates, they form longer homopolymerized chains between crosslinks.

Die C Tear, 20 IPM Hot Tear 150° C, 10 Minutes Cured 320° C, 30 Minutes

The tear strength superiority of the peroxide-dimethacrylate coagent cure system over the sulfur-accelerator system is shown in Figure 3. Both the Saret 634 and Saret 521 are dimethacrylates.

that of sulfur-cured systems. The Saret 634 also provides excellent tensile strength and flexibility. Saret 516 and Saret 521 offer good hot tear strength, as well as reduced Mooney viscosity and com- pression set.

Fiber/Fabric to Rubber Adhesion

Many rubber products, such as rolls, belts, and hoses are reinforced with metallic or synthetic fibers and fabrics for increased tensile strength. Fabric surfaces cover the wear portion of belts for improved abrasion resistance. If these reinforcements bond poorly, the tensile strength of the rubber product is reduced to the strength of the rubber alone and the product will fail. Good adhesion is necessary to allow the fabric to function in this capacity.

Sartomer offers several adhesion-promoting coagents, which enhance adhesion and other physical properties. These coagents include:

Saret 633

SR-9051

Saret 634

SR-9051

Figure 1 Tee-Pull Strength of Materials

20 A 17.5 A 15 12.5 A 10 7.5 A A 5 A 2.5 C
20
A
17.5
A
15
12.5
A
10
7.5
A
A
5
A
2.5
C
C
RFL
C
C
C
C
0
Copper Aluminum
Steel
Polyester
Polyester
Nylon
Cord
Cord
Braid
Tee-Pull Adhesion
A
= Adhesive Strip with Saret 633
C
= Control (No Saret 633, Peroxide Alone)
Tee-Pull Force, lb

Monofilament/Braided Wire Adhesion

Saret 633 was evaluated in a "Tee-Pull" adhesion test using the following formulation:

Nordel EPDM

100

N762 Black

100

Sunpar 2280

50

Zinc Oxide

5

Stearic Acid

1

Resin D

1

Dicumyl Peroxide 40KE

7.5

Saret 633

10

The Tee-Pull test uses a special mold with a grid of trenches. An elastomer can be laid into this grid and a filament is laid perpendicular to the elastomer. Filling the trench halfway with the elastomer embeds the filament. After curing, the fil- ament and elastomer resemble a cross. The tensile tester is used to strip the elastomer from the filament.

Figure 1 provides data for Saret 633 and several filaments and braid along with the control without the Saret 633.

In each case, Saret 633 signifi-

cantly improves the Tee-Pull adhesion over the control, especially for the metallic

monofilaments, copper, alu-

minum, and steel. Each adhesive failure was cohesive, including the polyester wherein the elastomer remained on the monofilament after the test.

Nylon Braid

A nylon braid was tested with and without RFL treatment against the elastomer contain- ing no Saret 633 and with Saret 633 as shown on the previous page. The untreated braid tested at 0.3 lb force without the Saret 633 and 3.6 lbs with the Saret 633. The RFL-treated braid tested at 1.3 lbs against elastomer without Saret 633. This data indicates that the Saret 633 can be used in peroxide-cured elastomers to improve adhe- sion to metal and synthetic filaments without the use of external adhesion promoters.

Fabric Adhesion

EPDM was bonded to fabric (nylon, polyester warp) with and without Saret 633 using the formulation described above. The RFL-treated fabric was also tested without the Saret 633. Results shown below reveal the superior adhesion characteristic obtained with the Saret 633 when cured against the fabric at 160º C for 20 minutes. The adhesion was measured on a 1/2-inch wide specimen at 1.0 in./min. test speed. The fabric was peeled from the elastomer at an angle of 180º. Failure mode was cohesive with elastomer remaining on the fabric after the peel test.

In a separate, but similar test (Figure 2), data for Saret 634 and SR-9051 are compared with Saret 633.

Figure 2 Saret Comparison Test

20 15 10 5 0 Saret 633 Saret 634 SR-9051 Control Peel Adhesion, lb
20
15
10
5
0
Saret 633
Saret 634
SR-9051
Control
Peel Adhesion, lb

For applications where water sensitivity is an issue, such as a radiator hose, the SR-9051 can be substituted for the Saret 633. Saret 634 is also less sensitive to moisture than Saret 633.

Conclusion

Saret 633 has demonstrated capability to bond EPDM elastomers to various reinforc- ing mediums without the need for adhesive bonding agents on their surfaces. Alternate coagents exhibited good ad- hesive properties, such as Saret 634 when flexibility is needed and SR-9051 when moisture resistance is needed.

Saret 633 also provides good adhesion in other elastomers.

New Reactive Dispersions for Rubber Applications

Curing with zinc salt powders can achieve particularly strong adhesion properties. But the dust associated with these powders has caused problems, which has discouraged their widespread use.

Dispersions of zinc diacrylate (ZDA) with mono, di, and trifunctional monomers now offer an alternative solution. These dispersions have been developed to improve the incorporation of zinc diacry- late into various cure systems and offer improved property performance, as well as the elimination of dust in the application. Three new reactive dispersions are shown below.

various cure systems, such as painting/brushing, spraying, and mixing.

The following chart shows typical adhesion values obtained when the CD-627 dispersion is "painted" on cold-rolled steel coupons with a peroxide/EPDM compound cured between the overlapped coupons. Some of the peroxide in the EPDM compound migrates into the dispersion, thereby curing it and bonding the EPDM to the metal. The system is cured at 160º C for

20 minutes. Peroxide/EPDM compounds and cure tempera- tures can be varied to suit each application. A control without dispersion gives very

 

Viscosity cp @ 25ºC

Functionality

ZDA%

Properties

CD-626

6,000

One

~30

Adhesion,

 

Low Mooney

Flexibility

CD-627

21,000

Two

~30

Adhesion,

 

Good General

Properties

CD-628

8,000

Three

~30

Adhesion

 

Low Set,

Fast Cure

All three reactive dispersions eliminate the dust normally encountered in the use of zinc diacrylate and provide a "paste" that can be added to

little adhesion of 70 lbs.

For comparison, when a solvent-based adhesive was pre- cured on the metal coupons and the peroxide/EPDM compound was

cured between them again, the system demonstrated good adhesion at 800 lbs. Polar tackifiers can be added to the dispersion to improve green tack.

can be added to the dispersion to improve green tack. Bulletin Peroxide-Cured EPDM CD-627 as a

Bulletin

Peroxide-Cured EPDM CD-627 as a Bonding Adhesive

800

800 700 500 – 800 600 500 400 300 200 100 70 0 Control CD-627
800
700
500 – 800
600
500
400
300
200
100
70
0
Control
CD-627
Solvent Adhesive
Lap Shear Adhesion, LB

One-Inch Overlap, CRS Cure 160° C/20 minutes

Conclusion

Sartomer zinc salt dispersions, such as CD-627, offer a valu- able alternative to curing with the zinc salt powders to gain good dispersions without dust.

Basic Principles of Peroxide-Coagent Curing of Elastomers

Sartomer's latest application bulletin–Basic Principles of Peroxide-Coagent Curing of Elastomers–serves as both a teaching tool and a handy reference for compounders

who want to understand the science of peroxide-coagent cure of elastomers.

The bulletin assists with the selection of an appropriate coagent and peroxide, with

a focus on processibility and performance. Presented in

a clear, question-and-answer

format, it explores the roles of peroxides and coagents in the cure process and their impact on elastomer proper- ties. Performance data shows

the benefits of using Sartomer coagents over alternative products. Finally, product recommen- dations are presented based on processing and performance

dations are presented based on processing and performance Application Bulletin Basic Principles of
Application Bulletin Basic Principles of Peroxide-Coagent Curing of Elastomers
Application
Bulletin
Basic
Principles
of
Peroxide-Coagent
Curing
of Elastomers

requirements.

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Sartomer Company’s web site, www.sartomer.com, provides information about the com- pany and its specialty chemical product lines. It features a complete listing of Sartomer's products, including over 150 different monomers, an exten- sive line of epoxy, urethane and specialty oligomers, UV photoinitiators, hydrocarbon resins, and other specialty chemicals. The site also provides access to technical and application articles pub- lished by Sartomer, company press releases, and information request forms.

company press releases, and information request forms. Along with its tailor-made products, Sartomer offers the

Along with its tailor-made products, Sartomer offers the following resources for fast, chemist-to-chemist communication and technical information retrieval.

Technical Hotline

(800-949-6544)

Sartomer's technical hotline provides immediate answers from technical personnel on the applicability and proper use of Sartomer products.

Fax-On-Demand System

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STIR CD-ROM Version 2.0

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Sartomer Company's new interactive CD-ROM contains technical information on various crosslinking raw materials used in many different applications. The disk includes an indexed collection of tech- nical datasheets for individual products, application bulletins and technical papers.

The STIR 2.0 disk also con- tains an electronic catalog that enables elastomer compounders to interactively explore Sartomer's many product offerings without having to page through a large catalog. Compounders can search for products by functionality,

The information contained in this booklet is believed to be accurate. However, all recom- mendations are made without warranty, since the conditions of use are beyond Sartomer Company’s control. The listed properties are illustrative only and are not product specifica- tions. Sartomer Company disclaims any liability in connection with the use of the information and does not warrant against infringement by reason of the use of its products in combination with other material or in any process.

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