Zhang et al/ Chemistry Journal (2012), Vol. 02, Issue 05, pp.

174-178 ISSN 2049-954X

Available online at www.scientific-journals.co.uk
174


Research Paper

Study on Military Polyurethane Adhesive

Changming Zhang
1
*, Zhanggen Huang
1
, Jun Ping Li
2
and Xiao Juan Lu
2


1
State Key Lab. of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2
Shangxi northern Hung Yen Chemical Industrial Co., Taiyuan 030001, China
Tel.: +86-351-4043727; Fax: +86-351-4043727
*E-Mail: zhangcm@sxicc.ac.cn


Abstract

A military polyurethane adhesive, containing two components, was developed. Through a series of studies, the appropriate
preparation conditions and corresponding determination methods were established. The important characteristics, like
include the content of isocyanate, hydroxyl value and bond strength, of component A, component B and JA-1 glue
comprehensively were determined. The results show that the developed products have fine performance and showing good
repeatability in analysis. The storage problem of JA-1 glue was also investigated. The JA-1 glue was laid aside for 6
months; the variation rules between the isocyanate content and the bonding strength were experimented. The final result is
that for smallest change of bond strength, the most optimum of isocyanate content are from 7.5 to 8.0 (W%).

Keywords: Polyurethane Adhesives, Isocyanate Content, Bonding Strength

1. Introduction

Some natural or synthetic substances are collectively
referred as adhesives, in which they are able to allow two
or more homogeneous or heterogeneous materials
connected together and after curing, they should have
sufficient degree of strength. Many types of glue, for
example, the early use of more phenol resin and the
modern popular polyurethane adhesive, all are typical
representatives of glue (Sword, n.d.).

As early as 1940, the German first discovered triphenyl
methane- 4, 4', 4'-diisocyanate adhesives and successfully
used them in tank crawler of World War II. In 1953, the
United States developed a polyurethane adhesive, in which
castor oil and poly-ether polyols were used as raw
materials and in 1984, the pollution problem of using
adhesive was solved (Di, n.d.).

The polyurethane adhesive (PA) is compound consist of
amino formic acid ester group (-NHCOO-) or iso- cyanide
ester group (-NCO) in its molecule (Sword, n.d.).

In 1956, China developed triphenyl methane
triisocyanateand then toluene diisocyanate (TDI) which
ultimately resulted in the two-component solvent-based
polyurethane adhesive. Since 1980s, in China many
advanced production lines and products were successively
imported from abroad. Due to high cost of import of large
quantities of polyurethane adhesive, the indigenous
development of polyurethane adhesive was greatly
promoted and hence developed (Yu, 1991; Hengzi & Qing,
1994 and Di, 2005).

Due to the presence of many high polar and chemical
reactive bases like isocyanate-base (NCO) and urethane
base(-NHCOO) in polyurethane adhesive, it would have
excellent chemical adhesion characteristic to materials
containing active hydrogen. At the same time, due the
presence of the hydrogen bond between the adhesive and
material bonded, the cohesion of macromolecular is
increased resulting the firmness in the degree of adhesion
(Sword, n.d.).

Polyurethane adhesive has also excellent shear strength,
impact resistance and excellent flexibility characteristics. It
Zhang et al/ Chemistry Journal (2012), Vol. 02, Issue 05, pp. 174-178 ISSN 2049-954X

Available online at www.scientific-journals.co.uk
175
is almost suitable for all kinds of materials to need bonding
(Yu, 1991 and Sword, n.d.).

The application of polyurethane adhesive is very
extensively spread in many industries like automotive,
timber (Yu, 1991 and Hengzi & Qing, 1994), footwear,
packaging, construction (Ming et al, 2011), printing ink,
bookbinding, railway, aerospace equipment and protection
of cultural relics, health care and so on (Yu, 1991; and
Hengzi et al ,1994).

Although in literature there are many reports about the
development (Yu, 1991; Hengzi & Qing, 1994 and Di,
2005), application (Yu, 1991; Hengzi & Qing, 1994)
synthesis (Kothandarman & Nasah, 1993; Chen et al, 2009
and Ming et al, 2011) and analysis (Ziqing, 1994) of the
polyurethane adhesive, however, these reports are lacking
the information about the military need, high bond strength
of adhesive and comprehensive analysis. To adapt military
industry needs, we undertook the task to develop bonding
agent JA-1 glue, in which military coating and military
industry propellant would be bonded. This adhesive is
composed by two parts i.e. A and B. The A is accruing
agent while B is polyester polyols with hydroxyl group.

Through a series of research, this JA,-gum was developed
successfully. This adhesive has not only high bond
strength; the other test indicators are also quite good. The
storage problem of JA-1 was also studied and got some
meaningful results, which were not reported in literature,
so these will be also summarized systematically to provide
reference.

2. Experimental

2.1. Instruments and Reagents

The instrument used detecting adhesive strength is
Shimadzu universal testing machine, provided by the
Japanese Shimadzu company.

3-nicked bottle/ flask of 200 ml capacity, equipped with a
stirrer, temperature measurement and heating units.

2.1.1. Synthetic Reagents

Polycaprolactone polyol was an industrial grade
reagent with 500 of average molecular weight,
produced by Japans Daicel Chemical Industries
Corporation

Toluene diisocyanate (TDI-100) of industrial grade
reagent was produced by Taiyuan Chemical Plant
(Taiyuan city, China)

Trimethylolpropane (TMP) of industrial grade reagent
was produced by Beijing Xing-Sheng-Da Chemical
Technology Co., Ltd. (Beijing city, China)

Ethyl acetate of analytical grade reagent was produced
by Chemical Experimental Factory of Tianjin
University (Beijing city, China)

Dilaurate dibutyltin of chemically pure reagent was
produced by Tianjin Chemical Reagent Factory
(Tianjin city, China)

2.1.2. Analytical Reagents

Dibutylamine of analytical grade reagent produced by
Beijing Chemical Factory (Beijing city, China)

Toluenesulfonic acid of analytical grade reagent
produced by Tianjin Chemical Reagent Factory
(Tianjin city, China)

Ethyl acetate of analytical grade reagent produced by
Chemical Experimental Factory of Tianjin University
(Tianjin city, China)

Pyridine of analytical grade reagent produced by
Beijing Chemical Factory (Beijing city, China)

2.2. Experimental Operation

2.2.1. The Synthesis of A and B Components

2.2.1.1. Preparation of the A component

Through a series of research, the optimum synthesis
process of part A is given below:

Three empty 3-nicked bottles were kept in oven on
temperature from 120-150
o
C for 30 minutes for the
removal of water and making it completely dry.

To one 3-nicked bottle, 97.38 g of toluene diisocyanate
and solvent ethyl acetate, on a ratio of 5:1, were added,
keeping temperature under 60
o
C. Further, 50 ml molten
dehydrated trimethylolpropane was also slowly drip-
added to the reaction flask with constant stirring. The
content was placed at 60
o
C for 2 hours to carry out the
reaction.

Under 60
o
C, the total amount of 97.38 g of toluene
diisocyanate and solvent ethyl acetate was joined the bottle,
in which their ratio is 5:1.

2.2.1.2. Preparation of the B Component

To another 3-nicked bottle 50.00 gm polycaprolactone
polyols was added. Under vacuum and 120 C the
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Available online at www.scientific-journals.co.uk
176
polycaprolactone polyols was dried for two hours to
remove water.

Polycaprolactone polyols was dried by keeping it at 120 C
and under vacuum for two hours. 15 g of molten
dehydrated trimethylolpropane was slowly added to the
flask with constant stirring. The content was kept at 60 C
for 2 hours to carry out the reaction till its completion.

2.2.2. Adhesive Preparation

2.2.2.1. Ratios of Raw Materials

Components A and B, ethyl acetate and dilaurate dibutyltin
were mixed with 10:1.5:2.2:0.07 ratios, under room
temperature stirred for 1 hour and then kept for 5 hours
without any stirring.

2.2.2.2. Application of Catalyst Dilaurate Dibutyltin

Organometallic compounds such as dibutyltin dilaurate
with strong catalytic effect toward NCO and -OH base
was used as catalyst. Its dosage amount was about 0.5 % of
prepolymer.

2.2.2.3. Pretreatment of Bonding Surface

To bonding the two surfaces, the following pretreatment
was indispensable. The bonding surface was cleaned and
polished in first place. The surface was smeared with
uniform glue liquid and allowed for 15-20 minutes to dry
up. Another surface was smeared in the same way with
uniform glue liquid to and allowed for 1-2 minutes to dry
up. The two surfaces pretreatment needed to bond then
they were pressurized under 20 MPa for 1 hour, then 0.5
MPa was added to pressure, for 2 hours. Finally they were
placed in an oven at 502 C for 2 hours they were aging
treatment.

2.2.3. The Summarization of Analytical Method and
Corresponding Pretreatment (Chen et al, 2009)

2.2.3.1. The Determination of Isocyanate (-NCO%)

The toluene - dibutylamine method was used in which
diisocyanate was reacted with di-n-butylamine to generate
urea. The excess dibutylamine was titrated with standard
hydrochloride acid solution titration.

2.2.3.2. The Hydroxyl Value Determination

The acetylation method was used with p-toluenesulfonic
acid as catalyst. In medium of ethyl acetate, acetic
anhydride was reacted with hydroxyl acetylation, then
excess amount of acetic anhydride was hydrolyzed by
mixture solvent of pyridine and water, then acetic acid was
produced. The amount of acetic acid was titrated by using
standard sodium hydroxide solution.

2.2.3.3. The Determination of Bond Strength

The GB7124-86 standard "adhesive tensile shear strength
determination method" was the bases to determine the
bond strength.

3. Results and Discussion

3.1. The Basic Characteristics of Product

With the most basic indicators used as standards, the A
component, B component, and JA-1 glue were compared
and results are listed in Table 1.

Table 1. Basic Characteristic of Product

Components A B
Colour Yellow Yellow
Indicator (%) 48-57 -
Solid Content (%) 53 -
Determination Value - Hydroxyl Value 405
Other Indicator -
Hydroxyl Value
40050

It is clear from Table 1 that the apparent and the most
basic indicators of products developed achieve basic
indicators requirements.

The content of isocyanate base (Table 2) and
hydroxyl (Table 3) values of JA-1 adhesive were
determined.

The results of Table 2 clearly show that the indicators with
isocyanate content, as required indicator, JA-1 adhesive
meets almost all requirements of indicator.

The determined results show good reproducibility i.e. the
average of isocyanate content is 7.51% and the determined
deviation range is 0.0% to 3.6% while the average
deviation is 1.9%.

Results of Table 3 indicate that the hydroxyl value range is
383-412, having the average hydroxyl value is 396
and the average standard deviation is only 0.08. With
hydroxyl value indicators as standard, the products from
present study are entirely in line with the required
indicator.

The bond strength is the most important requirement of
military applications. Bond strength of JA-1 adhesive was
carried out by Shimadzu universal testing machine.
Typical results are summarised in Table 4.
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Available online at www.scientific-journals.co.uk
177
Bond strength results show that the JA-1 adhesive
has excellent bonding strength i.e. fully in line with the
required indicator. The 6 indicators of adhesives
including strength, hydroxyl value and the
isocyanate content, etc., show excellent characteristics,
so, the objective of development was achieved
successfully.

3.2. Investigation About JA-1 Storage

During the use of JA-1 glue in military industry, the
adhesive strength of the main parameters used to change
during storage, thats why it was very necessary to
understand this variation. Literature is silent about this
problem. To this end, we carried out some preliminary
study. The variation rules between the isocyanate
content and the bonding strength during 6 months
were experimented. The results obtained are shown in
Figure 1.

The Figure 1 shows that during 6 months the adhesive
strength of JA-1 glue decreased with decrease in
isocyanate base content. The curve also clearly indicates
that for lower isocyanate content (W%) of adhesive, their
changes of bond strength were higher than that of high
isocyanate content. Finally, the isocyanate contents of
7.5-8.0 were in optimum range, the corresponding change
rate of adhesive strength was less than 4.13%.
Table 2. The content- Determination Results of Isocyanat Base (W%)

S. No. Content (1) W% Content (2) Average S.D (%) Indicator (%)
1 7.53 7.58 7.55 3.6 7.51.0
2 8.00 8.02 8.01 1.4 7.51.0
3 6.61 6.65 6.63 2.8 7.51.0
4 6.80 6.82 6.81 1.4 7.51.0
5 7.82 7.82 7.82 0.0 7.51.0
6 8.21 8.24 8.22 2.2 7.51.0
Average 7.50 7.52 7.51 1.9 -

Table 3. The Determination Results of Hydroxyl Value (KOH mg/g)

S. No. Content (1) Content (1) Average S.D (%) Indicator
1 399 398 399 0.25 40050
2 383 383 383 0 40050
3 388 389 389 0 40050
4 395 395 395 0 40050
5 400 400 400 0 40050
6 410 412 411 0.24 40050
Average 396 396 396 0.08 -

Table 4. Bond Strength (MPa) Determination

S. No. Bond Strength (1) Bond Strength (2) Bond Strength (3) Average Required Strength
1 4.37 4.38 4.57 4.44 > 3
2 4.62 4.68 4.90 4.73 > 3
3 3.41 3.58 3.49 3.49 > 3
4 3.16 3.28 3.25 3.23 > 3
5 3.85 3.78 3.84 3.82 > 3
6 3.72 3.75 3.70 3.72 > 3
Average 3.86 3.91 3.96 3.91 > 3

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178
5.5 6.0 6.5 7.0 7.5 8.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
B
o
n
d
i
n
g

s
t
r
e
n
g
t
h
Isocyanate base content
C
B
M
P
a
MCO(W%)
B Original
C After 6 months


Figure 1. The Relationship of Isocyanate Base Content and Bonding
Strength

4. Conclusion

A military adhesive polyurethane JA-1 with
two-components was successfully developed. The
appropriate raw materials formulations, the optimum
process conditions and the corresponding tested analysis
methods were established.

Some key indicators including isocyanate content,
hydroxyl value, adhesive property, etc. were also
determined. The measured results confirm that the
performance of product was fine.

The storage problem about JA-1 glue was also investigated.
The samples were laid aside for 6 months, the variation
rules between the isocyanate content and the bonding
strength were experimented, the results show that when
isocyanate contents are in the range of 7.5-8.0 (W%), the
corresponding change rate of adhesive strength would be
less than 4.13%.

This article provides complete and detailed information
about military JA-1 adhesive which have not been reported
in literature.

References

Chen J.C., Huang, H., Zhang, Y., Zhou, Z., and Huang, W.
(2009) Kinetics of synthesis of polyurethane curing agent
from trimethylolpropane and toluene diisocyanate.
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Di, G.A. (n.d.) Polyurethane Adhesive [Internet], Baidu
Encyclopedia. Available from: <http://goo.gl/9zwWx>
[Accessed 10 August 2012].
Di, Z.W. (2005) Polyurethane adhesives research and
development. Electronic Materials and Electronic
Technologies, 1, pp. 26 -30.

Hengzi, C., and Qing, L.Y. (1994) Costume of isocyanate
industry for forty years. Polyurethane Industry, 4, pp.
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Jun, Y.L., and Xiong, S.X. (1994) Application of
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Kothandarman, H., and Nasar, A.S. (1993) The Kinetics of
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Ming, L., Hung, W., and Yong, H. (2011) TDI-TMP
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Ziqing, Z. (1994) On the national standard (GB120094)
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