SCHOOL OF MATERIALS AND MINERAL RESOURSES ENGINEERING ENGINEERING CAMPUS UNIVERSITI SAINS MALAYSIA Academic Session 2011/2012 SEMESTER

II EBP 216/2

Polymer Engineering Laboratory (Makmal Kejuruteraan Polimer)

Experiment Number Experiment Title Date of Experiment Date of Submission Name Group Number Lab Report Examiner Instructor

: EXPERIMENT 2 : PHENOL-FORMALDEHYDE (RESOL) PREPARATION : 14 MEI 2012 : 21 MEI 2012 : MINCE LEONG YEN SHEE : GROUP 3 : DR. RAZAINA : Ms. SARA

EBP 216/2 Polymer Engineering Laboratory - Academic Year: 2011/2012 Lab Report Rubric Student Name Matric No. Group Experiment No. Experiment Date Submission Date : : : : : : MINCE LEONG YEN SHEE 109445 3 2 14 MEI 2012 21 MEI 2012
CONTENT Category Brief introduction about the experiment
(choose one type of point from the preceding column)

Points 0 5 7 10

Marking Description No introduction Poor introduction with insufficient references or acknowledgement to sources cited Introduction adequate but unoriginal composition with fair number of references Well written introduction with original composition and reference or acknowledgement to sources cited Total = 10% No objective Objective present Total = 5% No experimental details Incomplete experimental details Complete experimental details Total = 10% Communication of experimental results Interpretation of experimental results Ability of presenting and discussing experimental results in an effective way, i.e. easy to understand Total = 50% Conclusion highlights of results and their significance Total = 10% Ability to relay technical information with relatively simple statement Total = 5% Compliance to standard technical report (e.g. graph & table labeling, content, etc.) and submission date

Categorys total points

Remark

For these first 3 categories, lecturers only have to choose options given in the second column, i.e. 0, 5 or 10 marks.

Objective
(choose one type of point from the preceding column)

0 5 0

Experimental
(choose one type of point from the preceding column)

5 10 15 15

Results and Discussion

(stated in the preceding column is the total points for this category)

From this category onwards lecturers are given freedom to mark but according to weightage given in the second column for each row , For example; Marks for the: 1st row = 13/15 2nd row = 11/15 3rd row = 16/20 Total marks for R&D category would be 40/50

20 Conclusion
(stated in the preceding column is the total points for this category)

10

Language
(stated in the preceding column is the total points for this category)

Format and punctuality

(stated in the preceding column is the total points for this category)

Lecturers can use the supplementary marking rubric to give marks to these categories and synchronize them according to weightage given in the second column

10

Total = 10% Total (100%) CONTENT

Experiment 2 PHENOL-FORMALDEHYDE (RESOL) PREPARATION

Abstract Phenolic resins are a family of polymers and oligomers composed of a wide range of structures based on the various reaction products of phenols with formaldehyde. In this experiment, we synthesized phenol-formaldehyde resin and investigated its curing properties. To be able to do that, we have to observe the changes in every stage that occur throughout the experiment. Its changes of physical appearance such as its colour changes as well as its stickiness (viscosity) throughout different stage was observed and analyzed. Other than that, we also checked the solubility of the product in alcohol to indicate the non-occurrence of crosslink in the product. Generally, the product dissolved in alcohol at initial stage but as time move on, the cross-linkage formed in the product causing the immiscible of resin in the solvent. Keywords: oligomer, phenol-formaldehyde resin, curing, crosslink

1.0 Introduction Resins are polymers made by repeatedly linking discrete molecules (monomers) together to form chains or networks. Phenolic resins are oligomers (polymers with a few repeating units) synthesized by repeatedly linking phenolic (hydroxy-aromatic) monomers with aldehyde chemicals. Phenolformaldehyde (PF) resins are thermosetting polymers, which are widely used in many fields. One such application is as wood adhesives for the manufacture of wood-based composites, including plywood, oriented strand board (OSB), and fiberboard. [1] The oligomers from alkaline polycondensation between phenol and formaldehyde (PF) are excellent adhesive resins for wood lamination (plywood, oriented strandboard, veneer lumber). [2] Phenol-formaldehyde or phenolic resins are typically cross-linkable polymeric resins made from phenol and aldehydes, usually pure phenol and formaldehyde. Catalysis is required to synthesize the polymer. When base is used, the materials are known as

"Resol" and, when acids are used, the materials are known as "Novolac." [4] Novolac is one of the phenolic resins made under acidic conditions using excess phenol; the acid catalyzes the reaction of phenol and formaldehyde to form the cross-linkable polymeric resin. It is widely used for the formation of moulded pieces and articles. [5] When the reaction is carried out to high conversion, the result is a highly crosslinked, often black, hard, tough, impervious solid. Under the reaction conditions, phenol is trifunctional and formaldehyde is bifunctional, hence a network forms. The usual procedure is to carry out the reaction in two stages, first to partial conversion so that the material is still processable, and then finishing off the reaction in the mould to form the final, impervious, cross-linked material. [4]

1.1 Theory Phenol formaldehyde for formation of resoles involved 3 stages which are: A Stage (resoles) is an initial step growth polymerization between phenol and formaldehyde. Phenol and excess formaldehyde react to produce a mixture of methylol phenols end groups and very dynamic resins, always advancing toward a cured state. These condense on heating to yield soluble, low molecular weight resoles. The reaction begins when phenol is deprotonated by the base catalyst to form phenoxide. The negative charge is accommodated by resonance forms with the charge on two ortho- positions and the para- position of the ring. These three structures cause phenol to be trifunctional. Next the phenoxide attacks formaldehyde via ortho- or parapositions. The reaction can proceed at the other active position to become mono-, di-, and tri-substituted due to the phenol is a reactive molecule. At further reaction, methylene or ether bridges may produce that resulted from condensation between methylolphenols and available ortho- or para- positions. Higher temperatures favour the formation of methylene bridges.

Figure 1: Formation of phenoxide. [4]

Figure 2: Reaction at the ortho- and para- position.[4]

Figure 3: Structure of "methylol" compounds, mono-, di-, and tri-substituted [4]

Figure 4: Formation of ether bridge (up) and methylene bridge (down).[4] B Stage (resitol) on heating, resoles interact among each other and with other reaction species present in the system producing larger and mildly crosslink resin molecule which known as resitol. This represents the second stage of condensation. The molecule weight of the resin now is larger compare with resoles. Thus resitol is insoluble

in alkali and alcohol, but partially soluble in acetone. Resitol is softened when heated but become plastic when cooled. C Stage (resite) further heating of resitol will turn it into fully cured or crosslink resin known as resite. The C stage resin is totally insoluble and infusible. This stage is a category as the final stage of phenol formaldehyde polymerization. High molecular weight of product is formed due to the formation three-dimensional network.

Figure 5: Highly crosslinked, 3-D network resol structure [4] Characteristics of phenol-formaldehyde resin at various stages Stage A: 1. Soluble in alcohol 2. Low viscosity 3. Sensitive to low temperature changes 4. A light brown liquid 5. Low molecular weight 6. short and linear of Polymer chains 7. Easy to flow Stage B: 1. Insoluble in alcohol

2. Sensitive to high temperature changes 3. Viscosity higher than resoles 4. Rubbery and brown in colour 5. Lower tendency to flow 6. Higher molecular weight compare with resoles 7. Partially cross-linked in the polymer chain Stage C 1. Three-dimensional network 2. Stable at high temperature 3. Hard and tough solid 4. Insoluble in alcohol 5. Reddish-brown in colour 6. High molecular weight

2.0 Objectives To synthesize phenol-formaldehyde resin and to investigate the curing properties of phenol formaldehyde.

3.0 Experimental 3.1 Materials a. Phenol (95%) b. Formalin (37% formaldehyde solution) c. Sodium hydroxide (40M) d. Ethanol (95%) 3.2 Apparatus a. Pyrex reaction vessel b. Beaker c. Glass rod

d. Hot plate stirrer e. Retort stand and clamp f. Spatula g. Glass dropper h. Measuring cylinder i. Fume cupboard j. Thermometer k. Analytical mass balance l. Aluminium foil

3.3 Procedure A resol preparation was done by mixing phenol (10g) with formalin (12ml) in a reacting vessel followed by addition of NaOH (1ml) at 80C for 1 hour with continuous stirring. Any physical change of the reacting polymeric resin was noted. After slight cooling, the upper aqueous layer was decanted. Few drops of the product were dropped in a beaker of ethanol to check its solubility. Its physical appearance and solubility in alcohol were noted (A stage). The rest of the product was poured onto an aluminium foil folded cover. The resin was heated slightly and its physical state was noted by using glass rod. It melted into a rubbery state (B stage) initially and transformed into a hardened and infusible state (C stage) finally. At last stage the solubility of the product was tested by dissolved it in the alcohol solvent again. Precautious Steps: 1. 2. Phenol and formalin are carcinogenic. Avoid inhaling their vapour and wash with Initially, reaction of phenol and formalin is exothermic. Rigorous stirring would

excess water when they come into contact with skin. help preventing for any bursting of the reacting mixture. Thus avoid directing the reaction vessel towards other person. 3. 4. During the weighing of phenol, not only the aqueous shall be taken, the solute When testing the solubility of resin, ethanol must more than sample. should be taken also.

5.

Make sure to direction test tube is point to away from people to avoid splitting of

chemical solution. 4.0 Result and Discussion 40 M of NaOH was provided in laboratory but the material used in this experiment was 100 ml of 5 M NaOH. (Na = 20, O = 16, H = 1)
40 V1 = 5 (100 ) V1 = 12.5ml M 1V1 = M 2V2

Where
M 1 = Initial Concentration
V1 = Initial Volume

M 2 = Final Concentration
V2 = Final Volume

12.5 ml of 40M of NaOH was used to produce 100 ml 5M NaOH.

Procedure Resol preparation

Observation beaker was hot. The an

Indication It is exothermic This shows that there is an The increase in viscosity. reaction.

Product was subjected to 80oC water bath and continuous stirred for 1 hour. The solution was slightly cooled.

were formed.

2 layers

upper aqueous layer was transparent and the lower layer was light brown in colour. layer was formed. Only a small amount of upper

The lower layer was tested with ethanol.

The

The

lower layer was soluble in ethanol

polymer short chain.

chains and

are

simple.

There is no cross-link The lower layer was The colour intensity of the solution turned darker and became sticky resin time and Formati on of obviously air bubble The resin slowly hardened with eventually solidified. 5. The solubility of final product was tested with ethanol. final product Had The was a insoluble in ethanol. smooth surface. Did not contain air bubbles on surface. increased formation cross-linkage slowly The viscosity of the resin upon heating with time and becomes rubbery and then fully hardens. 3-D network of cross-link is formed throughout the resin. The heat provided causes of methylene bridge and

poured onto aluminium foil folded cover and was heated slightly.

Stages of Resol Formation In the initial stage, phenol is dissolved in formalin (37% formaldehyde solution). This is due to the formation of hydroxymethyl phenols which known as resoles. Later the solution added with NaOH which is the base catalyst to deprotonated the phenol monomer to form phenoxide and then attacked by aldehyde molecule forming methylol compounds.(Refer to Figure 1,2&3) When the mixture is being subjected to water bath and continuous stirred in an hour, formation of 2 layers of solution can be observed. The upper layer refers as water solution while the lower part is considers as resoles. Condensation takes place with formation of little amount of water molecule that eliminated as vapour during heating. It is found that the compound is soluble in ethanol

solvent due to the present of low molecular weight of molecule and less percentage of crosslink in the compound. This stage of compound is termed as resol or A stage. The stickiness and viscosity of the resol increases gradually as heat is continuous supplied to the resol. The colour intensity of the resol becomes darken without formation of water molecule. When some of the resol is put on a tissue paper, it sticks on it indicate that its transform in rubbery state. Thus this state is recognized as resitol or B stage. Resite is formed when the resitol is continuous heated. This is the C stage. This transformation of stage happens rapidly from rubbery state to fully harden. At this state the mixture seen to be hardened and turns into reddish-brown colour. The resite resin is insoluble in ethanol solvent due to the formation of 3-D network that causing a high molecular weight of resin.

Comparison of novolac and resol preparation Resol Novolac

Formation of resoles is a one-stage process. Formation of novolacs is a two-stage process. All ingredients are mixed together at one First mixture between phenol, formaldehyde, time. and acid. Second stage involves the addition of curing agent. Basic catalyst (pH more than 7) is used. Acid catalyst (pH less than 7) is used. For For example: NaOH. Usually but not necessarily, a molar excess of formaldehyde is used to make resol resins. Ratio of phenol to formaldehyde is 1 to 1.5 phenol < formaldehyde. Experience in 3 stages where in : A stage involved formation of resol. B stage involved formation of resitol. C stage involved formation of resite. The base catalyst dephotonate the phenol. example acid catalyst: oxalic, sulphuric acids. A molar excess of phenol to formaldehyde are conditions used to make novolac resins. Ratio of phenol to formaldehyde is 1 to 0.8 phenol > formaldehyde. Experience in 2 stages where: A stage involved formation of novolac. B stage involved formation of resite. The acid catalyst photonate the carbonyl group

of formaldehyde. Formation of phenoxide at initial Formation of methylol derivatives at initial mechanism of reaction.

mechanism of reaction.

Contains methylene bridge (-CH2-) and Contains ether linkage (-CH2-O-CH2-). Methylene bridge is formed by the elimination of the water molecule condition

methylene

linkage

(-CH2-).

Formation of methylene bridges in acidic

Formation of ether linkage

Self-crosslinking (cure the resin without Required methylol groups

crosslinking

agent

such

as

incorporation of a cure agent) due to the hexamethylenetetramine to complete the curing process

*By manipulating the phenolic to aldehyde monomer ratio, pH, catalyst type,
reaction temperature, reaction time, and amount of distillation, a variety of resin structures demonstrating a wide range of properties are possible.

5.0 Conclusion From the experiment, we learned that the synthesis of phenol-formaldehyde undergoes different stages. The phenol-formaldehyde resin in different stage has its own properties and difference. The percentage of crosslinking in the phenol-formaldehyde resin in every stage

varied causing changes in physical and chemical properties such as the solubility in solvent. The ability of transformation of stage of the phenol-formaldehyde resin gives good abrasive properties. In addition, factors like phenolic to aldehyde monomer ratio, pH, catalyst type,
reaction temperature, reaction time, and amount of distillation can give different influence on the mechanism and properties of product.

Thus, with the unique apparent of every stage,

the phenol-formaldehyde is suitable for many conditions in term of application.

6.0 Reference

1. Y. Lei, Q. Wu, K. Lian. (2006). Cure Kinetics of Aqueous PhenolFormaldehyde

Resins Used for Oriented Strandboard Manufacturing: Analytical Technique. Journal of Applied Polymer Science, Vol. 100: pp 16421650. Wiley Periodicals, Inc. 2. Gardziella, A., Pilato, L. A., and Knop, A. (2000). Phenolic Resins: Chemistry, Applications, Standardization, Safety and Ecology. New York: Springer. 3. Peter W. Kopf. (2002). Phenolic Resin. Encyclopedia of Polymer Science and Technology, Vol.7: pp 322-368. John Wiley & Sons, Inc. 4. Chem424 - Synthetic Polymer Chemistry: Phenol-Formaldehyde and Related Polymers http://chem.chem.rochester.edu/~chem424/novolak.htm
5. Xu Junming, Jiang Jianchun and Lv Wei. (2010). PREPARATION OF

NOVOLACS USING PHENOLIC RICH COMPONENTS AS PARTIAL SUBSTITUTE OF PHENOL FROM BIOMASS PYROLYSIS OILS. Chemical Society of Ethiopia, 24(2): pp 251-257.

Appendix

Figure 6: The mixture of phenol formaldehyde before heated

Figure 7: Mixture immersed in water bath

Figure 8: Resol solution (Stage A)

Figure 9: Harden phenol-formaldehyde resin (Stage C)