Flame-Retardants for Polyamides -...

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Flame-Retardants for Polyamides �

General Application Data on Flame-Retardants for Polyamides 6 and 6,6

� Fire-Safety Polyamides (PA) are the oldest and the most widely used of the five major engineering thermoplastics. They are versatile and easy to modify with fiber reinforcement, filler and elastomers. Their crystallinity and high molecular weight explain their excellent balance of properties: high thermomechanical and stress resistance, low friction, good chemical stability and good electrical insulating behaviour. However, due to moisture absorption they do not have very good dimensional stability. PAs play a very important role in the production of electro-mechanical/electronic, automotive and precision parts. They are used mainly for the production of connectors, micro switches, jacks, transformer cores, relay blocks, fans, trimmers and business equipment components. PAs are often glass reinforced. As their flammability involves a real hazard to users, it has been necessary to significantly improve their fire retardancy. This has been achieved mostly by the use of brominated fire retardants, employing antimony trioxide as a synergist. � ICL IP FRs product line This data sheet provides preliminary guidance for the preparation of Flame retarded grades of PA 6 and 6,6. The type of PA may have a considerable influence on properties such as melt flow, impact, electric properties and heat distortion temperatures. ICL IP offers a broad line of Flame-Retardants (FRs) and tailor-made solutions that provide additional benefits in new market segments and applications.





The following FRs are particularly suitable for FR PA passing class V-0 according to the UL 94 standard:

� FR-803P1 (brominated polystyrene- 67% bromine), owing to its polymeric nature, contributes to high comparative tracking index (CTI) and excellent thermal stability. Its advantages in PA are:

non-blooming high temperature processing stability up to 3100C contributing to excellent color stability

excellent electrical properties

� FR-1025 ( Brominated Polyacrylate - 71% bromine), is a proprietary polymeric flame retardant offered by ICL IP. Its main advantages in PA 6 applications are:

effective flame retardancy non-blooming good temperature stability and long term heat–aging stability

easy processability and high melt flow properties for production of thin wall and/or large parts with short injection molding cycles and high precision. It also finds application in PA 6,6 provided temperature in the melt is maintained strictly below 2900C. This processing condition is easy to achieve taking into account the processing aid effect of FR-1025.

excellent compatibility with fiber reinforcement and polymer matrix not solvent extractable chemical resistance

� F-2400 (highest molecular weight brominated epoxy polymers–53% bromine in ICL-IP BEs product line), are melt blendable and are efficient polymeric FR additives. They have good flame retardancy and are suitable for compounds with high UV stability. They are non-blooming.

� F-3100, recently introduced modified brominated epoxy polymer (53% bromine) has excellent cost performance with well balanced properties in PA.

1 For availability, please contact your local Office or Agent/Distributor.





It has a softening range between 1800C and 2200C and is recommended for applications in glass reinforced PA where it is expected to reduce significantly energy consumption during compounding and pressure during injection molding. Other advantages F-3100 has are low metal adhesion and good melt flow during recycling steps.

� 5531 (52% bromine), a newly developed FR system, is one of a series aimed at providing the market with tailor made solutions for specific and high demanding applications. It is a modified grade of high molecular weight brominated epoxy polymer with built-in antidrip properties offering the following advantages:

Non dripping class V-0 achievable with less FR and higher temperature rating according to the Glow-Wire Ignitability Temperature (GWIT)

Critical addition of antidripping agent is not needed Improvement of the thermal stability during recycling operations Low metal adhesion

Its application is developed jointly case by case with interested customers.

� FR-1410 (decabromodiphenyl ethane - 82% bromine) is recommended for low cost applications with PA 6 and 6,6. It offers good fire retardancy at low. It is not melt blendable during injection molding, so does not allow production of thin wall objects.

� FR-20, magnesium hydroxide with various surface-treatments, has the advantages of low smoke and heat release but due to the high loading required, it adversely affects processing and mechanical properties.

All these FRs have undergone extensive toxicological and environmental testing and have been proven to pose no risk to health and the environment.

Detailed application data sheets of these FRs in PA are available from http://www.iclfr.com website.





� Thermal stability Thermogravimetric analysis of the above-mentioned flame-retardants (Table 1) reflects their good thermal stability, enabling high to fairly high processing temperatures.

Table 1: Thermogravimetric analyzis (TGA-100C/min in air) FR type FR-20 FR-803P FR-1025 FR-1410 F-2400 F-3100 Weight loss, wt % Temperature, 0C

2 370 340 320 322 345 343 5 385 358 330 345 352 352

10 402 374 335 360 357 358 � Processing conditions Typical processing conditions for compounding and molding PA flame retarded with these FRs are as follows: Compounding Compounding in a co-rotating twin-screw extruder (L/D= 32)

Temperature profile, 0C: 30% GFR PA-6 200-220-230-240-260-270-270-275-275 30% GFR PA-66 200-250-270-270-265-265-270-280-285 Screw speed, rpm 350 Throughput, kg/h 15

Injection molding

Temperature profile, 0C: 30% GFR PA-6 260-280-280-275-285 30% GFR PA-66 270-285-290-300-310* Mold temperature, 0C (PA 6 and 6,6)

80 or 90-110 respectively

Pressures, Bar Injection: 1500-1800 - Holding: 900 - Back: 10

Cycle time,sec PA6/PA66 11/20 * For FR-1025: 260-260-280-285-290





� Overview of properties Tables 2 and 3 provide guidelines for selecting an optimal FR for non-reinforced and glass reinforced PA applications passing class V-0.

Table 2: Properties of V-0 non reinforced PA 6 and 6,6*

FR type Properties

FR-803P FR-1025** FR-1410 F-2400 FR-20

Thermal stability �� Melt flow �� FR efficiency � � �� Impact �� Comparative tracking Index (CTI) �� Thermal aging �� Recycling � �� UV/light stability �� Heat distortion temperature (HDT)

� ��

Non-blooming �� Cost efficiency ��

*�� excellent ** Applicable for PA 6

� FR efficiency Tables 4 to 7 give indicative guidance to define formulations able to pass class V-0 or V-2 according to UL94 with the ICL-IP FR poduct line. Usually FR PA class V-0 and flame retarded by BFRs are also expected to pass the Glow-Wire Ignitability Temperature (GWIT) at 7750C in accordance with IEC 695-2-1/3. � Processing-aid The processing-aid effect of FR-1025 and F-3100 is of particular interest in glass reinforced PA as it is beneficial at each processing step:





1. Energy savings during compounding – low value of specific energy consumptions (SEC).

2. Lower pressure during injection molding. When processed in their softening range, FR-1025 and F-3100 contribute to significant improvement in melt flow properties during injection molding (Fig. 1). Enhanced flow is an especially important feature for electronic devices made of glass-reinforced PA and often designed with thin wall dimensions and complicated shapes.

Table 3: Properties of V-0 glass reinforced PA 6 and 6,6*

FR type Properties

FR-803P FR-1025**

FR-1410 F-2400 F-3100

Thermal stability �� Melt flow � �� FR efficiency �� Impact � �� Comparative tracking Index (CTI) �� Thermal aging �� Recycling �� UV/light stability �� Heat distortion temperature(HDT) �� Non-blooming �� Cost efficiency � ��

*��

� Impact properties Figure 2 compares impact properties of the various FRs in 30% glass reinforced PA, class V-0 according to UL 94.

FR-1025 followed by F-3100 contributes to fairly good impact properties in PA when compared with other commonly used FRs. To further improve impact properties of FR grades of PA, it is recommended to add 5 to 10% of a suitable impact modifier, such as maleic-modified ethylene-propylene terpolymer, ethyl- or butyl-acrylate copolymers, but attention must be paid to the consequent increase in viscosity properties.





0

10

20

30

40

50

FR-1025 F-3100 Ref. no FR FR-803P F-2400

Spir

al fl

ow -

inch

Fig.1: Spiral flow of V-0 30 % GFR PA 6 and 6,6

GFR PA 6 GFR PA 6,6

0

20

40

60

80

100

120

140

FR-1025 F-3100 Ref. no FR FR-803P F-2400

Izod

J/m

Fig.2: Izod notched impact of V-0 30 % GFR PA 6 and 6,6

GFR PA 6 GFR PA 6,6





Table 4: Properties of non reinforced flame retarded polyamide 6.

FR Type Ref. no FR FR-803P Br PS

FR-1025 Br Polyacrylate

FR-1410 EBP***

F-2400 High MW BE

FR-20 Mg(OH)2

Composition, weight % Polyamide 6 100 63.6 70.5 75.4 68.6 39 Flame Retardant - 25 20 15.7 23.1 60 Antimony trioxide - 10.4 8.5 7.9 7.3 - Additives (including anti-dripping) - 1 1 1 1 1 Properties Flame retardancy: UL 94 class (1.6 mm) NR V-0 V-0 V-0 V-0 V-0 Spiral flow, Inch. 40.3 37.3 46.2 38.6 37.6 na** Tensile: Maximum strength, MPa 83 45 67 65 73 67 Elongation at break, % 21 9 29 25 12 1 Modulus, MPa 3,400 2,800 3,100 3,300 3,600 4,300 IZOD notched impact, J/m 37 27 64 64 44 15 HDT (1.81MPa), 0C 57 55 57 59 58 113 CTI*, V 600 400 250 200 250 600

* Comparative tracking index ** Not applicable *** Decabromodiphenyl ethane or Ethane-1,2-Bis(pentabromophenyl)





Table 5: Properties of glass reinforced flame retarded polyamide 6.

FR Type Ref. no FR FR-803P Br PS

FR-1025 Br Polyacrylate

FR-1410 EBP***

F-2400 High MW BE

F-3100 MBE

FR-6120 MC

FR-20 Mg(OH)2

Composition, weight % Polyamide 6 68.9 41.9 48.5 50.8 43.6 43 69.4 39 Glass fiber 30 30 30 30 30 30 15 15 Flame Retardant - 19.1 14.3 12 19.2 18.9 15 45 Antimony trioxide - 7.9 6.1 6.1 6.1 6.5 - - Additives (including anti-dripping) 1.1 1.1 1.1 1.1 1.1 1.1 0.6 1 Properties Flame retardancy: UL 94 class (1.6 mm) NR V-0 V-0 V-0 V-0 V-0 V-2 V-0 Spiral flow, Inch. 38 35.5 43.4 45 26 40.7 32.5 na** Tensile: Maximum strength, MPa 162 131 159 156 163 156 113 120 Elongation at break, % 2.9 1.9 2.3 2.4 2.1 2.3 2.8 1.6 Modulus, MPa 9,300 10,800 11,100 11,100 12,000 9,500 6,200 9,000 IZOD notched impact, J/m 90 68 129 106 77 101 46 26 HDT (1.81MPa), 0C 202 199 200 206 200 199 200 173 CTI*, V 475 400 300 200 250 300 400 475

* Comparative tracking index ** Not applicable *** Decabromodiphenyl ethane or Ethane-1,2-Bis(pentabromophenyl)





Table6: Properties of non reinforced flame retarded polyamide 6,6.

FR Type Ref. no FR FR-803P

Br PS FR-1025

Br Polyacrylate F-2400

High MW BE FR-20

Mg(OH)2 Composition, weight % Polyamide 6,6 100 69.7 74.4 70.9 34 Flame Retardant - 22.1 18.6 21.2 65 Antimony trioxide - 7.4 6.2 7.1 - Additives (including anti-dripping) - 0.8 0.8 0.8 1 Properties Flame retardancy: UL 94 class (1.6 mm) NR V-0 V-0 V-0 V-0 Spiral flow, Inch. 38.8 31.8 38.5 28.7 na** Tensile: Maximum strength, MPa 88 72 83 85 45 Elongation at break, % 9.6 4.4 6.3 9.5 <1 Modulus, MPa 4,200 3,400 3,700 3,900 12,000 IZOD notched impact, J/m 37 25 41 35 10 HDT (1.81MPa), 0C 77 80 77 84 163 CTI*, V 600 450 325 325 600

* Comparative tracking index ** Not applicable





Table 7: Properties of glass reinforced flame retarded polyamide 6,6.

FR Type Ref. no FR FR-803P

Br PS FR-1025

Br Polyacrylate F-2400

High MW BE F-3100 MBE

FR-20 Mg(OH)2

Composition, weight % Polyamide 6,6 69.8 44.1 48.7 46.5 43 34 Glass fiber 30 30 30 30 30 15 Flame Retardant - 17.6 14.3 17.3 18.9 50 Antimony trioxide - 7.6 6.3 5.5 6.5 - Additives (including anti-dripping) 0.2 0.7 0.7 0.7 1.6 1 Properties Flame retardancy: UL 94 class (1.6 mm) NR V-0 V-0 V-0 V-0 V-0 Spiral flow, Inch. 35.3 36.7 49.3 29.5 41.2 na** Tensile: Maximum strength, MPa 176 160 171 179 173 96 Elongation at break, % 3 2.3 2.2 2.5 2.1 3.2 Modulus, MPa 9,700 11,500 11,600 10,300 11,400 10,000 IZOD notched impact, J/m 98 90 89 83 98 33 HDT (1.81MPa), 0C 250 244 249 243 244 230 CTI*, V 600 400 275 300 300 600

* Comparative tracking index ** Not applicable





� Comparative Tracking Index (CTI) PA flame retarded with FR-20 (magnesium hydroxide) has significantly higher comparative tracking index (CTI) than halogenated FR systems. Among the BFRs, FR-803P2 is the flame retardant of choice when good balance of properties is needed, but specially for imparting outstanding electrical properties to the matrix. FR-803P2 provides high values of CTI, making it unique in electrical and electronic applications, where this property is often a requirement. � Processing thermal stability FR-803P exhibits outstanding thermal processing stability as manifested by the low color change occurring in the event of a sudden stop of the injection molding machine. Comparative testing in glass reinforced PA 6 and PA 6,6 at 2900C and 3000C respectively with 5 minute residence time in the injection molding machine shows that compounds flame retarded with FR-803P have a significantly better color stability at high temperatures than with other brominated FRs recommended for these applications (Figure 3). F-2400 and F-3100 have also fairly good color thermal stabilities for processing temperatures higher than 2900C while FR-1025, as written earlier, should never be processed above 2900C. � Health – Safety - Environmental aspects ICL IP FRs product line has undergone extensive toxicological and environmental testing3, and has been proven to pose no risk to health and the environment. For instance, results of analyses performed by Institut Fresenius Chemische und Biologische Laboratorien GmbH on ICL IP FRs product line itself and under conditions simulating a modern municipal solid waste incinerator for presence of polybrominated dibenzo-para-dioxins/dibenzofurans (PBDD/PBDF), have shown it to

2 For availability, please contact your local Office or Agent/Distributor. 3 Further information available upon request





be in full compliance with the requirements of the global most strict criteria of the German Dioxin Ordinance and EPA TSCA 40 §766.27 Final Rule requirements1. As part of an ongoing Product Stewardship Program and Customer oriented policy, ICL IP is committed to implement further toxicological and environmental tests, should this be needed.

� Applications As a result of their efficient combination of properties, ICL IP's broad line of Flame-Retardants (FRs) is offering a series of tailor-made solutions that provide additional benefits in new market segments and applications. ICL IP's FR product line is recommended for the production of PA electro-mechanical/electronic parts, automotive and other precision parts like switches. Typical examples of application are shown in Figures 4 to 6: connectors in the computer, high voltage switches and automotive industries. In these applications, ICL IP's FR product line exhibits inherent advantages such as processing aid effect for thin injection molding, good thermal stability, good impact and good electrical properties. The polymeric FRs are often preferred if non-blooming properties are needed.

0

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30

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FR-1210 FR-1025 F-3100 F-2400 FR-803P

Col

or c

hang

e D

E

Fig.3: Color change after 5 minutes residence time in a molding machine of V-0 30 % GFR PA 6 and 6,6

GFR PA 6 290°C GFR PA 6,6 300°C





Figure 4: Connector and fan inside a PC Figure 5: High voltage switches

Figure 6: connector in automotive





For further advice and assistance, contact our representatives in your area:

Head Office ICL-IP Ltd. Phone: +972 8 6297 608 Fax: +972 8 6297 846 E-mail: [email protected] North America and Mexico Asia Pacific ICL-IP America Inc. China Phone: +1 877 661 4272 ICL China Fax: +1 314 983 7610 E-mail: [email protected] Phone: +86 21 5386 3322 Fax: +86 21 5386 3336 South America E-mail: [email protected] ICL Brasil Ltda Japan Phone: +55 11 2155 4539 ICL-IP Japan Ltd Fax: +55 11 2155 4507 E-mail: [email protected] Phone: +81 3 6801 8430 Fax: +81 3 6801 6970 Europe E-mail: [email protected] Main Office Asia Pacific ICL-IP Europe B. V. ICL Asia Ltd Phone: +31 20 800 5800 Fax: +31 20 800 5805 Phone: +852 28277761 E-mail: [email protected] Fax: +852 2824 1502 E-mail: [email protected] Italy Other Parts of the World PM Chemicals Italy ICL-IP Sales Office Phone: +39 02 204 87225 Fax: +39 02 204 9449 Phone: +972 8 6297 633 E-mail: [email protected] Fax: +972 8 6297 819 E-mail: [email protected]

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Flame-Retardants for Polyamides -...

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