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PLASTICS PSEflRSD BY 101 CATALYZED
F OLYMERIZATIOK OF FURFURAL
by
Justin Truman Long
A Dissertation Shbs&tted to the
Graduate Faculty in Partial Fulfillment of
■Hi® Requirements for the Degree of
DOCTOR OF PHILOSOPHY
fcjor SubjectCheiBical Engineering
Approved;
Iowa State College
1950
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UMI Number: DP12466
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TABLE OP O0IT11TS
Pag©
INTRODUCTION 1
REVIEW OP LITSMTUEE 5
MATERIALS AID METHODS , 10
Materials n
Physical Testing 12
Determination of sample sis© ' 22
Preparation of test specimens Pit
Selection of Standard Composition 2o
Method of Procedure 37
BXPSRIMEMTAL RESULTS 38
Other Puran Derivatives as Additives 52
Acetone derivatives of furfural 5k
Urea derivatives of furfural 5©
Iff eet of r©fluxing on diphenylamine
additive . 60
Mgaln as an Additive 6l
Condensing Agents Other Than Hydrochloric Acid 70
Properties of Pinal Composition 76
DISCUSS! OK 81
conclusions 85
stnotisy 86
LITE1ATUSE CITED 88
ACK&OW&&DGMEHTS 91
T 9 6 d f
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LIST OF FIGURES
Figure Pag#
1 Charpy Impact Testing Machine Ik
2 Paige Impact Testing Machine 15
3 Machine for Testing Tensile Strength 16
k Calibration Curve for Flexural Strength
Testing Ischia® 17
$ Distribution of Average Breaking Strengths of
113 Samples Tested for Flexural Strength 21
6 Effect ©a Flexural Strength of Varying Acid
Concentration 29
7 Preliminary Study of Effect on Flexural Strength
■of Concentration of Various Additives 31
8 Effect on Gelation Time of Various Additives 3k
9 Effect of Temperature on Tim® Required for
Gelation 35
10 .Effect of Varying Additive Concentration on
Flexural Strength 46
11 boss ©f Weight on Beating of Furfural Plastic 79
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LIST OF TABLES
Table Fag®
I Flexural Strengths of $2& Specimens of Furfural
Plastic * Comprising 113 Samples of Varying
Composition 20
II Halation of Sample Size to Coefficient of
Variability 23
III Relation of Flexural Strength to Coefficient
of Variability 2fy.
IV Effect of Varying Hatlo ©f Furfural:hydro
chloric Acid 29
V Effect of Varying Hatlo ©f Furfural:Sulfuric
AeId 29
VI Change in Strength with Age of Furfural Plastic
Containing Diphenylamine as Additive 32
VII Comparison of Celling Tim© with Flexural
Strength 36
VIII Effect of iooia Temperature During Celling Period
on Flexural Strength of Furfural Plastic fn©
additiv®) 3?
' IX Ef f ee t ©a Furfural Plastic of Incorporating Six
Per Cent of Various Additives 1^0
X flwnoary of 'lost Promising Additives 1$
XI Effect on Flexural Strength of Varying Concen
tration of Additives !|5
XII Effect m Flexural Strength of Varying Concen
tration of Purfurtn fy?
XIII Effect of Certain Fur an Derivatives as Additives
(Additive concentration three mole per cent) 53
XIV Effect of Varying Acetone Concentration then
Preparing Furfuralaeetone la situ 55
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IjIST OF TABLES (Continued)
Table Page
XV Effect of Varying Pyridine Concentration When
¥reparian Parfuralacetone In situ 56
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XVI Effect of Varying' Pyridine Concentration When ■
Preparing Furfuralurea in situ 58
XVII Effect of Reflux Time in Preparation of
Furftxraluroa Add!tire In situ 59
XVIII Effect of Varying Concentrations of Llgnin
(Indmlin A) as Additive 62
XIX Effect of Varying Kinds of Llgnin as Additive 63
XX Comparison of Effects of Llgnin 0sed Alone and
with Diphenylamine and Urea as Co-additives 65
XXI Effects of Lignin and Six Per Cent Purfurin as
Co-additives 66
XXII Effects of Llgnin and Fifteen Per Cent Furfurin
as Co-additives 6
?
XXIII Estimated law Materials Costs for Casting
Syrups lade with Various Additives 68
XXIf Physical Properties of Plastics Prepared With
Various Condensing Agents 73
XXV Estimated Materials Costs for Hardened Plastic
for Various Costs of Casting Syrup 75
XXVI Loss in Weight of Furfural Plastic at Various
Temperatures 77
XXVII Resistance of Furfural Plastic to Chemical
Reagents 8o
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1
INTRODUCTION
Natural resources are exhaustible. That our nation is at
last becoming conscious of this fact is emphasized by the
comment and discussion in the public press on the recent
Baekeland Medal Address by Dr. Eugene Rochow (1)* Dr. lochow
pointed out the need of turning to replaceable raw materials*
as it is 'impossible to continue forever using up resources
which cannot be replaced, lot many years ago the supply of
iron ore in this country was thought to be without limit* but
today we find ourselves forced to Import this important
material.
Corncobs, cottonseed hulls* peanut hulls* and similar
agricultural residues are replenished -annually. Their
utilization for the production of chemicals will have an
Increasingly greater' importance with the exhaustion of
■petroleum and coal reserves* Thus the problem of the develop
ment of processes and products based on agricultural residues
is of Rowing importance*
Among the chemicals that may be derived from agricultural
residues* non© Is more interesting than furfural. Furfural
was discovered in 1832 by Bobereiner {2). In I8I4.O, Stenhouse
13) reported the preparation of larger quantities of this
substance, and started an investigation of It® propertl#®.
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2
It was in this early paper that the reslnlfication of furfural
with hydrochloric or sulfur1© aelds was first reported.
Steahouse published an extension of this paper (If) in 1850«
In 18I]5, Fownes (5) first proposed the name t!f urf urol ”,
meaning "oil of bran”, because of its source and character,
ffais name was later changed to "fwfural* to indicate its
aldehydie nature.
During the latter part of the nineteenth century and the
first part of the twentieth century* considerable work was
done on the chemical properties of furfural, but the reslni-
fieatloa reactions were avoided* The successful introduction,
of plastics materials in the forms of celluloid and phenol-
formaldehyde products stimulated an interest in other resin-
forming. reactions* Furfural resins were among those investi
gated* but the high price of furfural prevented extensive
interest in its possibilities* The factory-scale production
of furfural starting in 1922 (65* and the subsequent reductions
in price* greatly stimulated research on resins from furfural*
Because of its nature* furfural can fora resins in two.
waysi through the aldehyde group and through the unsaturatlom
of the nucleus* The aldehyde group reacts with the same types
of compounds that give resins with formaldehyde* such as
phenols* amines, urea*, and polyvinyl alcohol*- 'These resins
will not be considered in this dissertation.
The tendency of furfural to reslnify through the unsatura
tion of the furan ring Is pronounced. When freshly distilled,
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