Advances in Blocked Isocyanates and Curatives, and Their Use in

Polyurethanes

Zhenya Zhu, Thomas R. Doyle and Ronald O. Rosenberg

Crompton Corporation, Middlebury, CT 06749, USA

ABSTRACT
Recent developments in blocked isocyanate prepolymers and curatives are
presented. The blocked isocyanate prepolymers are derived from urethane prepolymers
that contain low levels of residual monomer. These starting prepolymers are produced
using Crompton Corporations advanced Low Free manufacturing technology. The
selection and optimization of the prepolymers and curatives are discussed. This includes
data on novel blocked prepolymers produced from TDI, MDI, or PPDI and blocking
agents. These new blocked prepolymers feature easy processing that allows the
formulator a broad choice of diamines for chain extension. The derived materials give
excellent dynamic and mechanical properties. Field successes of these novel
polyurethane blocked systems are given to illustrate their high performance in the
demanding applications of binders, coatings and elastomers.

Crompton Corporation also offers blocked curatives based on the coordination

complex (MDA)3*NaCl (MDA = 4,4-methylenedianiline). Standard products are sold as
dispersions in dioctyl phthalate (DOP). Due to growing health concerns surrounding
DOP, Crompton Corporation has developed a DOP free product, Caytur 21-DIDP. DIDP
is diisodecyl phthalate. The properties of Caytur 21 and Caytur 21-DIDP are discussed.

I.

INTRODUCTION
Blocked isocyanates and curatives are commonly used in coatings, binders,

adhesives and elastomers. Blocked isocyanates and curatives are substances in which all
active isocyanate groups or active hydrogen-containing groups have been reacted with a
blocking agent. Therefore, they are deactivated. At elevated temperature, dissociation
takes place and removes the blocking agent to release the reactive groups. Then these
isocyanate or hydrogen containing groups will participate in the process of chain
extension or crosslinking.
Advantages of the blocking technology include the following.
-

Blocked isocyanate-containing compounds are storage-stable.

One component systems are possible.

Fast-curing diamines may be used as chain extenders.

Isocyanate groups are highly reactive to many other compounds, including

atmospheric moisture. Blocking the isocyanate allows protracted storage of prepolymers
in the presence of moisture and active chain extending agents.
Since the blocked prepolymer may be mixed with chain extender and the mixture
remains stable at ambient temperature, the ease with which these urethanes can be
handled and applied is a great asset. Continuous metering and mixing of prepolymer and
curative is unnecessary. Large masterbatches can be prepared. Ratio error in charging the
prepolymers, curing agents, and optional other components is reduced and labor costs are
reduced considerably.

As long as the mixture is below the deblocking temperature, it is stable even

with fast-curing amines. Once the temperature rises to above about 100oC, deblocking
takes place immediately and the curing completes quickly. Thus, even the aliphatic
amines may be used with prolonged work life. This is particular important for coating

and binding applications. Controlled work life is essential in order to apply the blocked
prepolymer/curative to a treated surface or matrix.

In the same manner, the amino group of a curative may be blocked to give
controlled working life in mixtures with isocyanate-terminated prepolymers.

Crompton offers numerous blocked prepolymers and curatives to the urethane

industry. Products cover blocked prepolymers with a broad range of total %NCO, and
both ether and ester backbones. Most blocked prepolymers offered by Crompton employ
methyl ethyl ketoxime (MEKO) as the blocking agent.

Recently, Crompton has introduced blocked prepolymers from Adiprene LF

prepolymers with low content of free diisocyanate monomer (TDI, MDI, or PPDI). This
approach brings several advantages:

Low prepolymer viscosity.

Low prepolymer melting temperature. Free MDI or PPDI molecules form

high-melting adducts with MEKO. Removing the free PPDI or MDI before
MEKO is added prevents these adducts from forming.

Use of new amine curatives, especially for MDI and PPDI. These isocyanates
are faster-reacting than TDI too reactive for some amine curatives. The long
working life of the blocked systems permits these amines to be used. Durable
elastomers are achieved in a range of hardness, modulus, and dynamic
properties.

Caytur 21 and 31 are blocked diamine curatives offered by Crompton

Corporation. They are primarily used to cure prepolymers based on TDI and polyethers.
The products provide a desirable combination of long working life and fast cures. At
room temperature, Caytur 21 reacts very slowly with the terminal isocyanate groups of
the prepolymer. However, when heated to 100 - 150C, the salt complex decomposes
and free MDA rapidly cures the prepolymer. Caytur 31 is virtually unreactive with

prepolymers at room temperature, and rapidly reacts when heated to 115 - 160C. The
additional stability of Caytur 31 allows it to be used with prepolymers dervived from
MDI and polyether polyols. Caytur 21 is unsuitable for prepolymers based on MDI
polyethers, due to its relatively short pot life.

Caytur 21 has below 2% free unreacted MDA by weight. Caytur 31 has

significantly less: below 0.5%. The especially low level in Caytur 31 accounts for its
longer working life with prepolymers typically indefinitely log at room temperature.

Caytur vulcanizates have excellent physical and dynamic properties similar to

those of elastomers based on the curative MBCA (4,4-methylene-bis-[2-chloroaniline]).
Suitable grades of Adiprene/Vibrathane prepolymers are available to provide a full range
of hardnesses (79A to 62D). Caytur can be processed by standard techniques, such as:
open casting, transfer, compression or liquid injection molding. Caytur mixtures may
also be cured by microwave irradiation. The products are uniquely suited for applications
such as belt or fabric coatings and adhesives, because of their long controllable working
life.

Caytur 21 and 31 are dispersions of the solid complex (MDA)3*NaCl in liquid

di(2-ethylhexyl) phthalate, which is commonly known as dioctyl phthalate or DOP. Due
to health issues regarding DOP, Crompton Corporation has developed Caytur 21-DIDP.
Caytur 21-DIDP is a dispersion (MDA)3*NaCl in Diisodecyl phthalate. DIDP replaces
DOP.

II.

CHEMISTRY

1. Blocked Isocyanates and Their Urethane Prepolymers

Diisocyanates and polyols are reacted to form NCO endcapped prepolymers. If a
large excess molar amount of the diisocyanate is applied, it suppresses the formation of
high molecular weight oligomers. The resulting prepolymer will have more regular

isocyanate-polyol-isocyanate structure. If the majority amount of excess free

diisocyanate is removed after preparation, the prepolymer will have narrow molecular
weight distribution. This precursor will be used for the next step, the blocking reaction
(see equation 1).

> 2 OCN-R-NCO + 1 HO-(-ether or ester unit-)n-OH

OCONH-R-NCO
NCO endcapped precursor

excess OCN-R-NCO

(eq. 1)

Free excess monomer

(subsequently removed)

The idea of a blocked isocyanate and urethane prepolymer is that a thermally

labile protecting group masks the isocyanate. On heating, the blocked isocyanate
dissociates into the separate blocking agent and isocyanate. Then the activated
isocyanate reacts with chain extender to cure (equation 2).
OCONH-R-NCO
NCO endcapped precursor

HO-N=CCH3(C2H5) OCONH-R-NHCOO-N=CCH3(C2H5)
MEKO blocking agent

blocked prepolymer

heat
OCONH-R-NCO + MEKO
deblocked prepolymer

H2NR
curative

OCONH-R-NHCONHR_
cured elastomer

Diisocyanates discussed in this paper are toluene diisocyanate (TDI), 4,4diphenylmethane diisocyanate (MDI), and p-phenylene diisocyanate (PPDI).

(eq. 2)

Commonly used blocking agents for isocyanate containing prepolymers are:

methylethylketoxime (MEKO); 3,5-dimethylpyrazole (DMP); nonylphenol; and caprolactam (E-CAP).

Chain extenders for blocked prepolymers demonstrated in this paper are 4,4
methylene dianiline (MDA); diethyl toluene diamine (DETDA); 4,4 methylene-bis-2,6
diethyl aniline (MDEA); and meta-xylene diamine (m-XDA).

2. Blocked Amine Curatives:

The following equation describes the formation of the Caytur diamine salt
complex:
3 MDA + NaCl (MDA)3*NaCl

The solid crystalline complex is dispersed as small solid particles in a liquid

plasticizer. The dispersion is stabilized using proprietary agents.

III.

EXPERIMENTAL

1. Typical sample preparation of the deblocked/cured elastomers for physical and

dynamic property testing is as follows.

First, samples were prepared by mixing the blocked prepolymer with chain
extender. Depending on the viscosity of the prepolymer, in general it was heated to a
temperature to give viscosity about 10 poise or lower, while the upper limit of the
temperature is 70oC. The solid curatives like MDEA are generally used in a 20-35
weight% solution in propylene glycol monomethyl ether acetate (PGMEA). Then the
curative solution was used at room temperature to mix with blocked prepolymers.

After the prepolymer and curative were well mixed, the mixture was then fully
degassed and poured onto silicone-greased can lids or into molds. The can lids were used
to prepare cured films of thickness of about 0.25 mm. The molds were used to make
thick elastomer parts (more commonly with the blocked Caytur curative). Can lids or
molds were placed in an oven and then deblocked/cured at 130oC for one hour. They
were further kept at 100oC for 16 hours to post cure or evaporate deblocked MEKO agent
and solvent from the films. (MEKO-based blocked prepolymers are typically used to
make thin sections to permit easy removal of the deblocked MEKO.)

Specimens were cut from the samples prepared above and aged at room
temperature for about 4 weeks before submitted for ASTM tests and dynamic property
analysis.

2. The pot-life of Caytur blocked diamine curatives were measured as follows:

Adiprene L 300 (a TDI/PTMEG prepolymer yielding elastomers of about 90

Shore A) and the appropriate amount of Caytur (95 % of theory) were combined
and the timer was started.

The materials were mixed for one minute by hand and placed on the viscometer.
The initial temperature of the mix was 502C.

Viscosity was measured as a function of time using a Brookfield viscometer.

The pot-life is defined as the time it takes the mix to reach 20,000 cP.

IV. RESULTS AND DISCUSSIONS

1. Conventional Blocked Toluene Diisocyanate Prepolymers:

Crompton offers a broad range of conventional TDI based blocked prepolymers.
A series of prepolymers based on polytetramethylene ether glycol (PTMEG) as the
backbone cover the hardness from Shore 72A to Shore 75D after deblocking and chain

extending. Recently, polypropylene glycol (PPG) and polyester backbones were

introduced as lower-cost alternatives.

ADIPRENE BL-16 is a standard TDI/PTMEG type of MEKO blocked prepolymer.

It may be used as a model to describe how the blocked system works.

When deblocked by heat, the regenerated NCO groups in ADIPRENE BL-16 react
with polyols and polyamines, which are used as curatives. Polyols are quite slow in
reacting with this polymer, so the most useful curatives appear to be aromatic diamines
such as methylene dianiline (MDA), diethyl toluene diamine (DETDA), 4,4 methylenebis-2,6 diethyl aniline (MDEA), or 4,4 methylene-bis-orthochloroaniline (MOCA).
However, MOCA cures at a very slow rate compared to other aromatic diamines, which
may not be suitable in coating and binding applications.

Coatings and adhesives can be prepared in a wide viscosity range by diluting

ADIPRENE BL-16 with such solvents as toluene, xylene or ethyl acetate. Table I shows
the viscosity/solids relationship of a blend of BL-16 and MDA in ethyl acetate.

ADIPRENE BL-16 may also be prepared as a one-component formulation. A BL16/MDA mixture remains fluid for more than four weeks when stored at 24oC. It is ready
to use any time after being poured out of the container and being heated.

Properties of the cured coatings are listed in Table II. As a comparison, ADIPRENE
L 167, a non-blocked prepolymer with otherwise similar composition, was cured with
MOCA. BL-16 cured with MDA shows equivalent performance. By contrast, BL-16
cured with m-XDA offers significantly higher tear strength. The extremely high
reactivity of m-XDA has excluded its use in curing conventional prepolymers. Blocking
the isocyanate enables M-XDA to be used.

Table III illustrates the physical properties of TDI/ether blocked products with a
range of total %NCO. Difference in hardness and modulus meets the application needs
from leather protective coatings to binders for hard abrasive materials.

Table IV and Table V give the comparison of PTMEG (BL-16), PPG and ester types
of materials. While esters offer overall property advantages, they have the deficiencies of
higher viscosity and lower hydrolytic stability. On the other hand, PPG types offer the
lowest cost and viscosity but generally give lower performance. Table V lists details of
the property comparison between different backbones and different chain extenders.

2. Low Free Monomer Precursor Blocked Prepolymers

While conventional TDI blocked prepolymers have achieved a great success in

market place and field trials, Crompton continues to develop novel blocked systems
based on prepolymers with low free diisocyanate monomer content. Representative
examples of MDI and PPDI materials are reviewed below to demonstrate the advantages
and characteristics of blocked systems based on such precursor prepolymers.

Low Free MDI Precursor Blocked Prepolymers

MDI is one of the most commonly used diisocyanates in industrial polyurethane

applications. However, blocked MDI prepolymer and its application are very limited.
Conventional MDI prepolymers generally contain more than 10% free MDI, due to the
similar reactivities of the two NCO groups in the MDI molecule and the resulting need to
use high levels of MDI monomer to suppress oligomer formation. While MDI
prepolymers may have low viscosity and low melt temperature before blocking, the
blocked prepolymers have high viscosity and gel-like appearance. This is from the high
tendency of crystallization of the blocked MDI monomer.

Crompton has recently introduced low free MDI prepolymers. Large excess amounts
of free MDI are removed via distillation after prepolymer is prepared. Such prepolymers

may be used as precursors to react with MEKO. The resulting blocked prepolymers have
very good processing characteristics, such as low viscosity and melting point with
absence of crystalline precipitate.

Moreover, the most widely used curative for conventional MDI prepolymers is 1,4
butanediol (BDO). Most diamines simply react too rapidly with MDI. Unfortunately,
BDO cured MDI polyurethanes are not suitable for some demanding applications.
Blocked MDI prepolymers from low free isocyanate precursors open the opportunity to
use amine curatives for higher end-use properties.

Table VI shows a comparison of the processing characteristics of blocked MDI

prepolymer (Adiprene BLM-500) vs. standard blocked TDI prepolymer (Adiprene BL16). The viscosity of MEKO-blocked low free MDI prepolymer is higher than that of
BL-16. However, it is within the manageable range. Viscosity can be reduced with
solvent, if desired.

Table VII shows a comparison of amine cured blocked MDI prepolymer vs. BL-16
and BDO cured conventional MDI prepolymer. Using MDEA and MDA, MDI gives
much tougher elastomers than TDI. MDI gives harder elastomer than TDI at given
prepolymer NCO content, denoting the efficient structure of the MDI/extender domains.
The amine-cured MDI elastomers are also much tougher than elastomer from
conventional MDI prepolymer and BDO curative.

Elastomers from deblocked/cured MDI prepolymers also provide improved dynamic

performance. The much lower damping at both low and high temperatures is shown in
Figure 1.

As blocked low free MDI prepolymers provide combinations of dynamic and

mechanical properties that are not available from TDI and conventional MDI
prepolymers, they provide opportunities for formulators to explore fit in various
applications.

Low Free PPDI Precursor Blocked Prepolymers

PPDI based polyurethanes are well known as a class of premium engineering

materials. PPDI materials provide the highest level of combined properties that are not
achieved by other commercially available polyurethanes. It has established a record of
performance in demanding elastomeric applications. Now blocked systems extend its
application beyond elastomers, such as coating and binder applications. The nature of the
blocked systems also extend the range of useful amine curatives for PPDI. It makes
curative choice almost unlimited, even the aliphatic amines have controlled work life.
The merits of PPDI materials can be more extensively explored.

As with MDI, directly blocking PPDI prepolymer having free PPDI monomer
brings the difficulties of crystallization, higher melting point and higher viscosity. With
removal of the excess PPDI monomer from the prepolymer, the residual PPDI level is
less than 0.1%. Therefore, processing issues related to blocked free PPDI are much
reduced. A low level of solvent might be desirable to further reduce the prepolymer
melting point and viscosity. However, this is not a hurdle since the solvent can be
removed along with the MEKO blocking agent during the deblocking/curing stage.
Solvents that may be added include toluene or propylene glycol monomethyl ether
acetate (PGMEA). The amount used is from 15% to 40% by weight based on the
application requirement.

At 20% PGMEA solution (PGMEA:prepolymer = 20:80 by weight), a blocked

PPDI/PTMEG prepolymer (Adiprene BLP-60) has viscosity of 480 cps at 70oC; and
1100 cps at 50oC. It has a total %NCO of 2.75%.

Table VIII compares key properties of the Adiprene prepolymers from blocked
PPDI (BLP-60) and TDI (BL-16). After deblocked/chain extension with MDA, it is
evident that low free PPDI blocked system outperforms BL-16 in tensile strength,

elongation and tear strength. These are indications that PPDI materials are tougher and
will last longer in field applications.

As discussed, low free MDI blocked systems offer enhanced dynamic

performance. PPDI materials show still better performance: modulus retention to higher
temperature, and low damping over a broad temperature range. As shown in Figure 2,
PPDI (BLP-60/MDA) exhibits lower damping at high temperature. Also, as shown in
Figure 3, PPDI holds the modulus well over 200oC. The low damping and high
temperature modulus retention means that heat build up in PPDI materials will be slower
than that of other materials. Such PPDI polymers may run under higher loads without
failure in certain demanding dynamic applications.

PPDI materials expand the market for polyurethane where MDI and TDI based
materials are not feasible. Their relatively higher cost may be justified for those most
demanding applications and work under harsh environments.

3. Blocked Diamines

Table IX compares the properties of Caytur 21 and Caytur 21-DIDP. It shows

that Caytur 21-DIDP offers the same long working life as Caytur 21. The viscosity of
Caytur 21-DIDP is higher than Caytur 21, but is still low enough to permit easy handling.
The higher viscosity of Caytur 21-DIDP may have the advantage of reducing the settling
rate of the solid complex. Table X lists the viscosity of the prepolymer/curative mixture
and its components. The data shows that the viscosity of the mixture is largely controlled
by the viscosity of the prepolymer. This indicates that Caytur 21-DIDP/prepolymer
mixtures can be processed like ones from Caytur 21. The pot life at 50C for Caytur 21
and Caytur 21-DIDP with L 300 are presented in Figure 4. The figure shows that both
Caytur systems have essentially the same viscosity build up.

V. CONCLUSION

Over the years, Crompton has seen growing market demand for blocked
prepolymers and curatives. Field successes of different types of blocked systems include
the coatings to produce ozone and abrasion resistant finishes for molded rubber goods;
fabric coatings for outstanding wear resistance; and ball mill dispersions. In adhesive
applications, the cured film has a high degree of resistance to dry cleaning solvents and
provides a flexible bond fabric-to-fabric and flock-bonding applications. With Caytur
blocked diamines, numerous uses are found in elastomer applications.

Crompton Corporation offers a wide selection of blocked isocyanate prepolymers and

curatives. These blocked systems have demonstrated high performance in coating,
binder, adhesive and elastomer applications. This includes the following:

TDI based blocked systems represent a broad product line with range of NCO
content, hardness and modulus, as well as the polyol backbones PTMEG, PPG
and esters.

Blocked MDI and PPDI prepolymers provide improved mechanical and dynamic
properties over conventional TDI materials. Precursor prepolymers with low
content of free diisocyanate monomer provide blocked prepolymers with much
improved processing characteristics: reduced crystallinity, lower melt
temperature and lower viscosity. Enhanced performance meets the needs of
highly demanding applications.

Caytur 21-DIDP is a dispersion of (MDA)3*NaCl in DIDP. It has the same

advantages as Caytur 21 and does not contain DOP.

Acknowledgment. Special thanks to James Chin, a retired senior scientist, who has
pioneered and made major contributions to the development of blocked systems at
Crompton.

Table I. Viscosity of ADIPRENE BL-16/MDA at Different Solvent

Levels

ADIPRENE BL-16
Methylene dianiline
Ethyl acetate, phr

100 parts by weight

26 parts by weight
Viscosity at 23oC, cps (Pa.s)

0
20
40
60
100

90000 (90)
1600 (1.6)
380 (0.38)
150 (0.15)
30 (0.03)

__________________________________________
Table II. Vulcanizate Property Comparison of Blocked and Nonblocked Systems

_______________________________________________
(MEKO-BLOCKED)

(NONBLOCKED)

ADIPRENE BL-16

ADIPRENE L 167

Curative

m-XDA

MDA

MOCA

Physical Properties
Hardness, Shore A/D

----

95/48

95/48

100% Modulus, psi (MPa)

300% Modulus, psi (MPa)
Tensile strength, psi (MPa)
Elongation at break, %

1120(7.7)
2510(17.3)
4420(30.5)
340

1650(11.4)
3600(24.8)
5400(37.2)
455

1800(12.4)
3600(24.8)
5200(35.8)
480

Split tear, pli

200

130

150

Abrasion resistance, Tabor

(H-22 wheel, 1000g load)
Weight loss, g/1000 rev.

----

0.112

0.112

Oil Resistance
Volume Change, %
After 7 days at 50oC in
ASTM Oil No. 3
Reference Fuel B

-------

+ 6.8
+ 25

+ 6.8
+ 25

Table III. Physical Properties of Various Hardness TDI/PTMEG Blocked Products

Adiprene LC-175

Adiprene BL-16

Adiprene BL-46

Total %NCO*
Curative

2.70
MDA

5.50
MDA

6.90
MDA

Hardness

84 Shore A

95 Shore A

75 Shore D

100% Modulus, psi

1090
300% Modulus, psi
----Tensile, psi
3870
Elongation at break, % 770

1650
3600
5400
455

5850
8300
10670
270

Split Tear, pli

130

200

110

* %NCO available to react with curative after deblocking.

Table IV. Comparison of Polyester, PPG and PTMEG Backbones

PTMEG

Advantage

Disadvantage

- general purpose
- used widely

- highest cost

Polyester

- better tear strength;

- better property retention
at high temperature

- higher viscosity of the

blocked prepolymer;
- lower hydrolytic stability

PPG

- lowest cost;
- lower viscosity of the
blocked prepolymer

- lower heat resistance;

- lower physical strength

Table V. Property Comparison of Different Backbones

PTMEG(BL-16)
Total %NCO*
5.50
Viscosity at 50oC,cps
8500

Polyester
5.30
40,000

Curative

MDA DETDA

MDA

100% Modulus,psi
300% Modulus,psi
Tensile, psi
Elongation at break,%

1650
3650
5400
455

1680
3350
7250
410

1610 1560
2980 3100
6250 6670
530
470

1820
3200
4850
420

1530
3000
4500
380

Split Tear, pli

130

160

145

100

90

DETDA

120

PPG
5.50
7000
MDA DETDA

* %NCO available to react with curative after deblocking.

Table VI. Viscosity Comparison of Blocked TDI and Low Free MDI Prepolymers

Temperature, oC

TDI
BL-16

Low Free MDI

BLM-500*

50
60
70

8500 cps
4500
2360

13600 cps
6700
5100

* Adiprene BLM-500 is the blocked low free isocyanate MDI/PTMEG prepolymer.

Table VII. Property Comparison of Conventional MDI, Blocked Low Free

MDI and Blocked TDI
MDI
B 635*

Blocked Low Free MDI

BLM-500**

Blocked TDI
BL-16

Curative

BDO

MDEA

MDA

MDA

Hardness, Shore A

89

95

97

95

100% Modulus, psi

300% Modulus, psi
Tensile, psi
Elongation at break, %

1100
----6110
390

2200
3800
6350
410

2100
2400
4250
600

1650
3600
5400
455

Split Tear, pli

80

145

210

130

* Vibrathane B 635 is a conventional non blocked MDI/PTMEG prepolymer.

** Adiprene BLM-500 is a blocked low free isocyanate MDI/PTMEG prepolymer.

Table VIII. Property Comparison of Chain Extended Blocked PPDI vs.

Blocked TDI
Blocked PPDI
ADIPRENE BLP-60*

Blocked TDI
ADIPRENE BL-16

Curative

MDA

MDA

100% Modulus, psi

300% Modulus, psi

1900
2300

1650
3600

Tensile, psi
Elongation at break, %

6120
650

5400
455

Split Tear, pli

210

130

* ADIPRENE BLP-60 is a blocked low free isocyanate PPDI/PTMEG prepolymer.

Figure 1. BLM-500 vs BL-16; Damping Property Comparison

0.2
0.18

BLM-500/MDA
BL-16/MDA

0.16
0.14

Tan Delta

0.12
0.1
0.08
0.06
0.04
0.02
0
30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220
Temperature, C

Figure 2. BLP-60 vs BLM-500; Damping Property Comparison

0.08

0.07

BLP-60/MDA
BLM-500/MDA

0.06

Tan Delta

0.05

0.04

0.03

0.02

0.01

0
30

40

50

60

70

80

90

100 110 120 130 140 150 160 170 180 190 200 210 220

Temperature C

Figure 3. Storage Modulus Comparison Between PPDI, MDI, and TDI Blocked Systems

1.00E+10

BLP-60/MDA
BLM-500/MDA
BL-16/MDA

G', dyn/cm2

1.00E+09

1.00E+08

1.00E+07

1.00E+06
20

40

60

80

100

120

140

160

Temperature C

180

200

220

240

Table IX. Properties of Caytur 21 and Caytur 21-DIDP

Caytur 21

Caytur 21-DIDP

Dispersant

DOP

DIDP

EW (gr/mole)

217

217

Viscosity @ 30 C (cP)

420

1060

Pot Life (min)

33

35

Table X. Caytur Component and Mixture Viscosity

Material

Viscosity @ 50C (cP)

DOP

17

DIDP

24

Caytur 21

155

Caytur 21-DIDP

300

Adiprene L 300

5,250

Caytur 21 + L 300*

6,800

Caytur 21-DIDP + L 300*

6,000

* Initial viscosity after mixing

Figure 4. Caytur Pot Life Curve (50C)

20000

Viscosity (cP)

18000

Caytur 21

16000

Caytur 21-DIDP

14000
12000
10000
8000
6000
4000
0

10

15

20

25

30

35

Time (min.)

Biography

Zhenya Zhu
Dr. Zhenya Zhu is a Research Scientist for the Adiprene/Vibrathane Department,
Crompton Corporation, USA. One of his major responsibilities is the research and
development of blocked prepolymers. He holds a M.S. in Polymer Science and

Engineering from East China Univ. of Chemical Technology (China) and a Ph.D. in
Polymer Chemistry from Rensselaer Polytechnic Institute (USA).

Thomas R. Doyle
Dr. Thomas R. Doyle is a Staff Scientist for the Adiprene/Vibrathane Department,
Crompton Corporation, USA. One of his responsibilities is the research and development
of blocked curatives. He holds a B.S. in Chemistry from the University of Connecticut
and a Ph.D. in Polymer Chemistry from The Polytechnic University (Brooklyn, New
York).

Ronald O. Rosenberg
Ronald O. Rosenberg is an R&D Section Manager for the Adiprene/Vibrathane business
at Crompton Corporation, U.S.A. He holds an M.S. in Chemical Engineering from Yale
University and an M.B.A. from the University of Connecticut.