NEW APPROACH FOR DEVELOPING EPOXY-AMINE ADDUCT CURATIVE WITH MODIFIED EPOXY RESINS Vipin Shukla *, D.K.

Singh, M. Singh and Ravi Shukla Jaydeep Polycon (P) Ltd. Panki Industrial Area, Site-4, D-37,38 Kanpur (India) Key words : Solid epoxy resin, DAPA, PGE, adduct, modified epoxy resins, curing. ABSTRACT Pure aliphatic amines (i.e. triethylenetetramine, diethylenetriamine etc.) are not recommended as hardener in surface coating formulations, as they give blooming, handling problem and toxic hazards, but epoxy-amine adduct is used very conveniently without any type of toxic hazards. Similar adducts are prepared using a variety of amines to provide adduct that will permit a range of cure rates and potlives and provide very good impact strength and flexibility. I am also trying to prepare epoxy-amine adduct but with new approach and also studies its curing behaviour with different modified epoxy resins.

To whom all correspondence should addressed. E-mail : vipin_1222@rediffmail.com vipin_shukla@sify.com Tel : +91-512-2201515, 2692564 & 2674452

INTRODUCTION The hardeners fall broadly into many type of such as polyamines, polyamides, acid anhydrides, aminos, phenolics, thermosetting acrylics, catalytic chemicals etc. The choice of hardener for particular type of an epoxy resin depends on :

the handling properties required such as viscosity, potlife, exotherm and todicity; the physical, chemical, mechanical and electrical properties required; the cure, post-cure time and temperature requirements; the cost of the hardener.1,2 Other factors are involved in selecting amines besides reaction rates.

Many amines are toxic while they are easily handled safely in a chemical plant, toxic hazards can arise if inexperienced, careless or uninformed personnel mix and apply two package epoxy coating incorporating certain amines. In general, toxic hazards are reduced by increasing molecular As molecular weight increases,

weight and reducing water solubility.

volatility decreases, which reduce the chances of inhaling dangerous amount of amine. Also, as water solubility decreases and molecular weight

increases, permeability through body membranes such as skin decreases, generally reducing toxic hazards.

Other disadvantages of utilizing low molecular weight, highly functional amines are their low equivalent weight and viscosities. The

equivalent of pure DETA is 21. If DETA is used with the epoxy resin having an equivalent weight of about 500. The stoichiometric weight ratio of the two components would be about 25:1. This disparate amount of two components would increase the difficulty of obtaining proper mixing and would also result in a high risk of significant error in mixing stoichiometric amount in two-pack system.3,4 One approach to designing amine crosslinkers with higher equivalent weight and lower toxic hazard is to make so-called amine adducts. Amine adducts are prepared by reacting excess primary amines with epoxy resin even at room temperature (R.T.). Each hydrogen atom attached to nitrogen opens upon an epoxy ring. Thus primary amine is first converted to The reaction between liquid

secondary amine and secondary hydroxyl.

epoxy resin and an aliphatic polyamine is shown below:

O 2 H2N
R N

O
C O CH2 CH CH2

+ CH2 CH CH2 O R.T.

Alkylene Polyamine polyamide

H H2 N R N CH2 O CH

Epoxy resin
O H CH2 N R N

CH2 O

O CH2 CH

Epoxy-Amine Adduct Reaction : Formation of standard epoxy-amine adduct adduct

These type of adduct react faster than the free amines because of the increase in hydroxyl groups and also reduce or eliminate blush formation because the primary amine hydrogens are pre-reacted with epoxide groups. Epoxy-amine adduct is used very conveniently for manufacture of chemical resistant paints, having very good impact strength and flexibility. The protection of structural steel work and processing

equipments, chemical plants, oil refineries and food factories are examples of the user of these coatings in corrosive atmosphere. These coatings will withstand wine, beer, cider, molasses, alkalies, detergents and crude and refined oil products. Due to the excellent alkali resistance of these coatings, paint for concrete, cement, plaster surface are formulated from these system also. They are employed as protective coatings for paper book covers, fatty food wrappings, and as finish for bar table tops, floors and other wooden surfaces.5,6 EXPERIMENTAL Material used : JNR-GP-502 [DGEBA] : Jaydeep Polycon (P) Ltd. Kanpur JNR-BG-701 JNR-BG-708 : : do do -

JNR-BG-710 JC 43 [Catalyst] JC 40 [Catalyst] PGE [Phenyl glycidylether] Bisphenol-A

: : : : :

do do do do

C.J. Shah and Co., Mumbai do -

Dimethylamino propylamine [DAPA] : Dibutylphthlate [DBP] Solvent-61 : :

Vikas Agrotech., M.P. Jaydeep Polycon (P) Ltd. Kanpur

Method : Synthesis of high molecular weight epoxy resin Liquid epoxy resin (JNR-GP-502) and JC-43 were taken in a half litre reaction three neck flask equipped with a stirrer, thermometer, condenser and in nitrogen inlet. After adding the reactants, the JC-40 was added at 70C and then temperature was maintained at 155-160C for 1 hour. After this bisphenol-A was charged at 160C under vacuum. The resin formed was checked by calculating epoxide equivalent weight (EEW) after regular intervals of time, until the required EEW (800-850) was acquired. The formulation used for the preparation of above resin in Table-2

Synthesis of epoxy-amine adduct Before the preparation of epoxy-amine adduct, we prepare blend of solid epoxy resin in PGE (40%), then we add this resin in DAPA slowlyslowly and maintain temperature 65-70C, after that we add DBP and solvent-61. After conclusion of the reaction, the product is cooled to 55C. Determination of epoxide equivalent weight (EEW) Epoxide equivalent weight of epoxy resin was determined by hydrogen bromide method.7 Determination of amine value Amine value of epoxy-amine adduct was calculated by

perchlorine/aceticacid method.8 Preparation and characterisation of coatings All the modified epoxy resins cured with epoxy-amine adduct hardener with appropriate quantity and determine the film properties of coatings like potlife, hardcure time, scratch hardness, flexibility, adhesion and chemical resistance. Result and Discussion Table-1 shows some important properties of epoxy resins and PGE. Table-2 shows the formulation and properties of solid epoxy resin.

Table-3 exhibits the formulation and properties of epoxy-amine adduct. Table-4 shows the curing schedule of epoxy resins with epoxy-amine adduct and also showed the potlife and hardcure time for samples S1, S2, S3 & S4 and it is clearly visible from Table-4, sample S1 has least potlife and S3 has large potlife which is due to variation in EEW because greater the EEW, greater will be the potlife of samples. Table-5 shows the chemical properties of cured samples and it appears from the table that samples S1, S2 and S3 remain unaffected against immersion tests conducted for assessing the 10% NaOH solution, ethanol, kerosene, toluol and ethyl acetate, sample S4 also remain unaffected against ethanol, kerosene and toluol but appear very slightly blisters against 10% sodiumhydroxide solution and shows slightly blister against ethylacetate. Table-6 exhibits the physical properties of cured samples and it proves from the table that except sample S4, all other samples pass flexibility test. Scratch hardness of samples S1, S2, S3 and S4 are 2600 gms., 2800 gms., 2200 gms., and 2000 gms. respectively and adhesion, as measured for all cured samples. Sample S2 possess 70 kg/cm2, which was superior to that of the samples S1, S3 and S4 showing adhesion of 65, 55, 50 kg/cm2 respectively.

CONCLUSION This type of epoxy-amine adduct reduces the exotherm, which developed during the synthesis of epoxy-amine adducts. This adduct also reduces the cost as compare to other epoxy-amine adducts. The observation indicate that the use of this curative in coating results improved chemical resistance and physical properties. It was found that the use of this curative had no adverse effect on coating properties. REFERENCES 1. Lee, H. and Neville, K.; Handbook of Epoxy Resins, McGraw Hill Book Company (N.Y.), P. 7-15, (1967). 2. Joshi, P.L.; Epoxy Resins, Paint India, Vol. 40, No. 7, P. 20, (1990). 3. Wicks, Z.W.; Jones, F.N. and Pappas, S.P.; Organic Coatings : Science and Technology. Vol. 1, Wiley Interscience Publication, New York, P. 172, (1992). 4. Panda, H.; Epoxy Resins : A Review (Part-1), Chemical Weekly, 20 November, P. 148, (2000)

5.

Weinmann, D.J.; Dangayach, K. and Smith, C.; AmineFunctional Curatives for Low Temperature cure Epoxy Coating, Journal of Coating Technology, Vol. 60, No. 863, December, P.30, (1996).

6.

Meeus, F.; New developments in ambient cure epoxy resins for high performance industrial coatings, Journal of Oil Colour and Chemist Association, Vol. 73, No.5, P. 187, (1990).

7.

Lee, H. and Neville, K.; Handbook of Epoxy Resin, McGraw Hill Publication (Inc.) New York, Chapter 4, P. 17, (1967).

8.

Patil, S.; Testing of Paints, Current Awareness Service, Mumbai, P. 47, (1993).

ACKNOWLEDGEMENT The author would like to thank Mr. Sandeep Shukla, Managing Director and Mr. Sanjay Shukla, Director for their valuable suggestions and guidance extended to me during the course of study and preparation of the paper.

Table-1 : Properties of epoxy resins and PGE

Grade of epoxy resins JNR-GP-502 JNR-BG-701 JNR-BG-710 JNR-BG-708 PGE Specific gravity @ 25C 1.14 1.12 1.12 1.10 1.14 Viscosity @ 25C (cps) 12000 600 650 500 20 Epoxide equivalent weight (gm/eq.) 200 185 215 220 165

Colour (gardener) G 2G G 2G 3G

Type

Pure DGEBA Modified epoxy resin Modified epoxy resin Modified epoxy resin Reactive diluent

Table-2 : Formulation and properties of solid epoxy resin Ingredients JNR-GP-502 JC-43 JC-40 BPA Properties Specific gravity @ 25C Viscosity (40% solution in high butylcorbital) cps Epoxide equipment weight (gm/eq.) Softening point (C), Duran Hg method Amount 60 gm. 0.09 gm. 0.03 ml 28.8 gm. Values 1.10 550 875 95

Table-3 : Formulation and properties of epoxy-amine adduct curative

Ingredients 40% solution of solid epoxy resin in PGE DAPA DBP Solvent-61 Properties Aspect (visual) Amine value Viscosity @ 25C (cps)

Amount (gm) 82 42.5 7 16 Values Very slightly yellowish 340 10,000

Table-4 : Curing schedule of modified epoxy resins with epoxy-amine adduct Samples JNR-GP-502 JNR-BG-701 JNR-BG-710 JNR-BG-708 Epoxy-amine adduct (phr) Potlife (min.) @ 25C Hardcure (hours) S1 100 30 22 8 S2 100 50 24 12 S2 100 50 25 12 S4 100 50 30 12

Table-5 : Chemical properties of cured samples

Samples S1 S2 S3 S4

10% NaOH solution NE NE NE VSB

Ethanol NE NE NE NE

Kerosene NE NE NE NE

Toluol NE NE NE NE

Ethyl acetate NE NE NE SB

NE= No effect, VSB= very slightly blisters, SB=slightly blister

Table-6 : Physical properties of cured samples Flexibilitya (1/8 mandrel) Pass Pass Pass Fail Scratch hardnessb (grams) 2600 2800 2200 2000 Adhesionc (kg/cm2) 65 70 55 50

Samples S1 S2 S3 S4

a- ASTM-D-522 b- BS-3900 c- ASTM-D-879