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(1 9) Qjl) European Patent Office
Office euroDeen des brevets (11) EP 0 852 235 A2

(12) E U R O P E A N PATENT A P P L I C A T I O N

(43) Date of publication: (51) Int. CI.6: C08B 31/00, C08B 3 1 / 1 2 ,

08.07.1998 Bulletin 1998/28 C08B 35/00, C09K 7 / 0 2
(21) Application number: 97122801.0

(22) Date of filing : 23.1 2.1 997

(84) Designated Contracting States: (72) Inventor: Bernu, Cory J.

AT BE CH DE DK ES Fl FR GB GR IE IT LI LU MC Farmington, MN 55024 (US)
NL PT SE
Designated Extension States: (74) Representative:
AL LT LV MK RO SI Patentanwalte
Hauck, Graalfs, Wehnert,
(30) Priority: 03.01.1997 US 778555 Doring, Siemons
Neuer Wall 41
(71) Applicant: 20354 Hamburg (DE)
Chemstar Products Company
Minneapolis, MN 55406-3203 (US)

(54) High temperature stable modified starch polymers and well drilling fluids employing s a m e

(57) A modified starch polymer derived from an

unmodified starch having an amylopectin content of at
least 80% by weight. The starch is modified by
crosslinking with epichlorohydrin, the amount of
epichlorohydrin crosslinking being equivalent to that
which is obtained when a crosslinking reaction is sub-
jected to a Brabender viscosity which reaches a maxi-
mum value and then is reduced with further crosslinking
from its maximum to a value which is no more than 50%
of the maximum value, and is carboxymethylated with a
degree of substitution of at least 0.1 carboxymethyl
groups per anhydroglucose unit. Fermentation stability
is obtained when the degree of carboxymethyl substitu-
tion is about 0.4 or more. The modified starch polymer
may also be hydroxypropylated. The modified starch
polymers provide improved high temperature fluid loss
performance when incorporated into well drilling fluids.
They may also be used in other applications for which
cellulosic polymers have heretofore been employed
because of their better high temperature tolerance com-
pared to conventional starch polymers.

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 EP 0 852 235 A2

Description

Field of the Invention

5 This invention relates to modified starches used in well drilling fluids and to well drilling fluids produced therefrom.

Background of the Invention

US 4,652,384 describes the use of starches in well drilling fluids as follows:

10
"In drilling wells, a mud-like fluid is pumped into the hole to clean and cool the drill bit and to flush to the surface the
rock cuttings that are torn loose by the drill bit. The drilling fluid must have certain physical characteristics. The most
important of these is the viscosity and the water holding or retaining characteristics of the fluid.
"The use of starch in well drilling fluid is well known. It is also well known that conventional starches tend to break
15 down at elevated temperatures for extended periods of time. Specifically, conventional starch tends to break down
or burn up at temperatures of 225° F. or higher when subject to that temperature for longer than four hours. High
temperatures for extended periods of time are often encountered in deeper wells during the drilling process. The
breakdown of conventional starch results in an increase in the consumption of the conventional starch needed in
the mud.
20 "There is a need in the well drilling industry for a starch which can operate for extended periods of time at elevated
temperatures."

In US 4,652,384 a crosslinked starch, for well drilling fluids is disclosed. This starch is preferably cornstarch crosslinked
with phosphorous oxychloride. One example of this reference uses phosphorous oxychloride crosslinked waxy corn
25 starch. It is contended by this reference that the starch can function satisfactorily up to 32 hours at temperatures above
250°F. According to Table I of this reference, however, substantial performance degradation occurs within 24 hours in
an API Fluid Loss test utilizing a starch product prepared in accordance with the teachings of this reference at a 275°F
test temperature.
US 4,822,500 describes well drilling fluids including a saturated brine, a salt soluble in water but not in the brine,
30 "xanthomonas" (xanthan) gum and an epichlorohydrin crosslinked hydroxypropylated starch component. The combina-
tion of starch and gum provides improved high temperature performance relative to drilling fluids employing either of the
gum or the starch components alone and to drilling fluids employing the gum component in combination with a number
of other waxy starch derivatives, including waxy corn starch crosslinked with phosphorous oxychloride and hydroxypro-
pylated.
35 US 4,422,947 describes a well drilling fluid containing a crosslinked potato starch together with other additives. The
reference does not report high temperature duration of fluid loss properties of the fluid.
US 4,123,366 describes a well drilling fluid made from sea water which includes both sodium carboxymethyl starch
and sodium carboxymethyl cellulose as fluid loss additives.
In addition to starches, cellulosic or synthetic polymers have been used as fluid loss control additives in well drilling
40 fluids. Exemplary references disclosing such polymers include US 4,600,515, US 4,652,623 and US 4,988,450. While
some such polymers may provide better high temperature characteristics than the starches and modified starches pre-
viously employed in well drilling fluids, they are generally more expensive. Consequently there is a need for starches
which have improved duration of fluid loss control at high temperatures.
Additional information regarding drilling, fluid compositions and the use of starches therein can be found in J. Bour-
45 chardt, "Chemicals Used in Oil-Field Operations," Chapter 2 of Oil Field Chemistry, pp 3-54, American Chemical Soci-
ety (1989).
In the Derwent WPI database, abstract accession number 85-048247/08 (2/85), it is reported that RO 84742
describes an ion exchange resin prepared from amylopectin crosslinked with epichlorohydrin and reacted with mono-
chloroacetic acid in weight ratio up to 10:1 . There is no suggestion of using this starch or any modification thereof in a
so well drilling fluid.

SUMMARY OF THE INVENTION

The invention is a novel starch which provides remarkably improved high temperature fluid loss performance when
55 incorporated into well drilling fluids. Another aspect of the invention is an improved starch-containing well drilling fluid
in which the starch component is a modified starch as described herein. A still further aspect of the invention is a well
drilling process which employs such a drilling fluid containing the novel starch of the invention.
The novel modified starch of the invention is derived from an unmodified starch or blend of starches having an amy-

2
 EP 0 852 235 A2

lopectin content of at least 80% by weight. The modified starch polymer is crosslinked with epichlorohydrin, the amount
of epichlorohydrin crosslinking being equivalent to that which is obtained when a crosslinking reaction is subjected to a
Brabender viscosity which reaches a maximum value and then is reduced with further crosslinking from its maximum
to a value which is no more than 50% of the maximum value, and is carboxymethylated, suitably with a degree of sub-
5 stitution of at least 0. 1 carboxymethyl groups per anhydroglucose unit. In some embodiments of the invention the mod-
ified starch polymer of the invention is also hydroxypropylated.
In addition to drilling fluids, the starches of the invention are useful in other drilling field applications which utilize
higher cost polymers to obtain higher temperature tolerances, especially applications which currently employ cellulosic
polymers.
10
DETAILED DESCRIPTION OF THE INVENTION

Well drilling fluid is also referred to as mud, drilling mud, drill fluid, drilling fluid, oil well fluid and oil well drilling fluid
in the industry and these terms should be understood as interchangeable throughout this application. It will be under-
15 stood that these terms refer to a fluid which is pumped into a well during the drilling operation. The well itself may be for
gas, oil or any other purpose where a well drilling fluid is used.
Depending on their source, starches may contain both amylose and amylopectin molecules, or they may contain
substantially all amylopectin or substantially all amylose. Typical sources of starch are wheat, potato, rice, corn and
roots containing a high starch content. Waxy starches, which are virtually all amylopectin molecules, especially waxy
20 corn starch, are preferred. Blends of waxy starches with minor amounts of amylose-containing starch may also be
employed. The starch, whether a single type or a blend, which is used in preparing the modified starches of the inven-
tion should have a content of amylopectin of at least 80%, i.e., it has a maximum amylose content of 20%. More pref-
erably the amylopectin content is at least 85%, and most preferably at least 95%.
The starch is crosslinked with epichlorohydrin, suitably in a basic aqueous starch suspension, or slurry, at a tem-
25 perature and for a period of time such that the Brabender viscosity of the suspension exceeds the maximum viscosity
which can be obtained in the starch suspension and then drops to about 50% or less of the maximum viscosity, as
determined experimentally. Typically the slurry will contain at least 25% by weight of starch granules. The maximum
Brabender viscosity is reached at a very low crosslinking density and then drops with further crosslinking, as the
crosslinked system becomes increasingly dense. The viscosity will vary by the amount of crosslinking and the test con-
30 ditions, i.e., temperature, concentrations, etc. Preferably, the crosslinking is continued until the viscosity decreases to a
value in the range of from about 35 % to 5% of the maximum viscosity. When the desired viscosity is reached, the
crosslinking reaction is terminated.
The epichlorohydrin crosslinked starch may optionally then be reacted with propylene oxide to form a hydroxypropyl
ether. The reaction of propylene oxide and starch is base catalyzed. Aqueous slurry reactions are generally catalyzed
35 by 0.5 to 1% sodium hydroxide based on the dry weight of starch. Sodium sulfate or sodium chloride may be added to
keep the starch from swelling during reaction with the propylene oxide. Reaction temperatures are generally in the
range of about 38° to about 55° C. Propylene oxide levels generally range from about 1% to about 10% based on the
dry weight of the starch. Propylene oxide-starch reactions take approximately 24 hours to complete under the condi-
tions described and are about 60% efficient with respect to the propylene oxide. It is preferred that the epichlorohydrin
40 crosslinked hydroxypropylated starch contain from about 0.5% to about 20% reacted propylene oxide based on the dry
weight ("moisture free basis" or "MBS") of starch.
Other methods of preparing epichlorohydrin crosslinked starches and hydroxypropyl starch ethers are well known
in the art and can be employed in the manufacture of the starches of the invention.
The modified starches of the invention must also be carboxymethylated. This is suitably accomplished after
45 crosslinking and, if employed, after the hydroxypropylation reaction. Carboxymethylation is accomplished by reacting
the starch with chloroacetic acid or its sodium salt. Such reactions are well known. The degree of substitution (ds) in
the inventive starches is at least 0.1 , more desirably at least 0.3, and preferably at least 0.40 carboxymethyl groups per
anhydroglucose unit in the starch polymer. Polymers with a ds of about 0.4 or higher are especially preferred because
they are stable against fermentation, however, this degree of substitution is much higher than can conventionally be
so achieved in a slurry reactor. Therefore for this reaction the starch slurry is desirably transferred to a paste or "autoclave"
reactor. Alternatively a higher water dilution or a solvent may be employed to allow for reaction to the high degree of
substitution preferably employed in the inventive starches.
Suitably the reacted starch is then drum-dried and milled to obtain a dry product. The milled dry product can then
be incorporated into the oil well drilling fluid at the drill site.
55 At the oil well drilling site, the starch of the present invention will typically be incorporated into the mud when the
consumption of the conventional starch becomes excessive. The mud is prepared in a conventional manner with the
addition of the starch of the present invention. In general, oil well mud is prepared by combining clay, brine and starch.
Any type of brine or clay may be employed with the starch of the present invention. The proportions of the starch, clay

3
 EP 0 852 235 A2

and brine used in the mud are well known in the art, as are the methods used to combine them. It may also be possible
to use the starch of the present invention with water and clay in the absence of brine or in a brine environment free of
clay when making a well drilling fluid. It is also possible to employ the starch of the present invention with an initial wet
drilling fluid which does not contain starch. In other words, an operator could start the drilling operation with a well fluid
5 which does not contain starch and still employ the starch of the present invention in drilling that well.
In practice the amount of starch added to the mud will be different for different drilling operations and each operator
will use a particular amount which he believes to be superior. In most applications, the amount of starch employed in
the drilling fluid will not exceed about 4 or 5 pounds per barrel of the drilling fluid.
The well treating fluids of this invention can contain other conventional wellbore additives as desired in conventional
10 amounts. Examples of such additives include oil, viscosifiers such as hydroxyethyl cellulose, carboxymethyl cellulose,
xanthan and other gums, lignosulfonate salts such as calcium or chromium lignosulfonates, emulsifiers, weighting
agents, corrosion inhibitors, calcium carbonate, magnesia, other starch derivatives, and the like, as is well known in the
art. In particular xanthan gum employed in the manner and relative proportions as described in US 4,822,500 may be
utilized in the drilling fluids of the invention.
15 Starch polymers of the present invention may be introduced into the hole in any number of ways known to those
skilled in the art. Starch of the present invention may be combined with brine and clay and then added to mud made
from conventional starch at the drill site prior to pumping it into the drill hole. Or, starch of the present invention may be
added directly to a mud which contains conventional starch and the mud containing both starches can be pumped into
the drill hole.
20 The invention can be used in any drilling fluid application where starches are currently used, including specifically
the applications listed in US 4,822,500 at col. 10, line 60 to col. 11, line 24. Further, many other drilling field applications
which utilize higher cost polymers because of the low temperature tolerance of starches can be readily adapted to
employ the modified starches of the invention, especially such applications which currently employ cellulosic polymers.
The invention is illustrated by the following non-limiting examples.
25
Examples

Starches as indicated below were provided and formulated into model drilling fluids which were tested for fluid loss
properties.
30 All fluids were prepared and tested according to standard API mud preparations guidelines using standard malt
cups and a 5 spindle Hamilton Beach multimixer. The prepared fluids were placed in 316 stainless steel heat age cells.
The cells were clamped into tumble oven set at the desired temperature and hot rolled for the desired time. The cells
were taken out and quenched in a sink filled with cold water. API test methods were then conducted, recording the mis
of fluid lost. The fluids were then replaced in the heat age cells and hot rolled for another cycle. The process was con-
35 tinued until complete degradation of the starch occurred.
The starches used were as follows:

Invention Examples

40 Example A

Epichlorohydrin crosslinked, 0.50 ds carboxymethylated, waxy corn starch. This example illustrates one preferred
method of making the starch of the present invention.
To a slurry containing 4950 grams of waxy corn starch, 85.5 grams of 50% sodium hydroxide is added. The alka-
45 lized slurry is heated to 35° C and 7 mis epichlorohydrin is added to crosslink the slurry. Reaction progress is monitored
using a Brabender Viscograph. The reaction is neutralised to pH 6.89 using 40% sulfuric acid when the viscosity curve
reached 18% of the maximum peak viscosity.
To 12,174 grams of the above crosslinked slurry was added 1986 grams 50% sodium hydroxide and 2625 grams
of sodium monochloroacetate. The contents were heated to 60° C and reacted for 50 minutes followed by neutralization
so to pH 10.51 using 40% sulfuric acid. The product was then drum dried and ground to a powder.

Example B

Epichlorohydrin crosslinked, 0.50 ds carboxymethylated, hydroxypropylated, waxy corn starch. This example illus-
55 trates one preferred method of making the starch of the present invention.
To a slurry containing 16,050 grams of waxy corn starch, 277.4 grams of 50% sodium hydroxide is added. The alka-
lized slurry is heated to 35° C and 12.04 mis epichlorohydrin is added to crosslink the slurry. Reaction progress is mon-
itored using a Brabender Viscograph. The reaction is neutralized to pH 7.25 using 40% sulfuric acid when the viscosity

4
 EP 0 852 235 A2

curve reached 28% of the maximum peak viscosity.

To 10,100 grams of the above crosslinked slurry was added 1664 grams 50% sodium hydroxide, 2199 grams of
sodium monochloroacetate, and 304 mis of propylene oxide. The contents were heated to 50° C and reacted for 50 min-
utes followed by neutralization to pH 10.62 using 40% sulfuric acid. The product was then drum dried and ground to a
5 powder.

Example C

50/50 blend of the products of Examples A and B.

10
Comparative Examples

Example D

15 0.50 ds carboxymethylated corn starch.

Example E

Epichlorohydrin crosslinked, 0.50 ds carboxymethylated, corn starch. Viscograph curve was 14% of maximum
20 peak viscosity. (Corn starch counterpart to Example A).

Example F

Epichlorohydrin crosslinked, 0.50 ds carboxymethylated, hydroxypropylated, corn starch (lower crosslink density
25 than Example G).

Example G

Epichlorohydrin crosslinked, 0.50 ds carboxymethylated, hydroxypropylated, corn starch. Viscograph curve was
30 17% of maximum viscosity peak. (Corn starch counterpart to Example B).

Example H

Epichlorohydrin crosslinked, 0.50 ds carboxymethylated, hydroxypropylated, potato starch. Viscograph curve was
35 29% of maximum viscosity peak. (Potato starch counterpart to Example B).

Example I

Epichlorohydrin crosslinked corn starch. Viscograph curve was 28% of the maximum peak viscosity.
40
Example J

Epichlorohydrin crosslinked waxy corn starch. Viscograph curve was 38% of the maximum peak viscosity.

45 Example K

Stager™ 141 a phosphorous oxychloride (POCI3) crosslinked potato starch of US 4,422,947.

Example L
50
A phosphorous oxychloride (POCI3)/ epichlorohydrin crosslinked waxy corn starch.

Example M

55 A phosphorous oxychloride (POCI3) crosslinked, hydroxypropylated corn starch.

5
 EP 0 852 235 A2

Example N

Epichlorohydrin crosslinked, hydroxypropylated corn starch of US 4,822,500.

5 Example O

Stabilose™ LV. This is a commercial 0.50 ds carboxymethylated potato starch product. Without being bound
thereby, it is believed that this product may be epichlorohydrin crosslinked and may be blended with CMC (car-
boxymethylated cellulose).
10
Example P

PAC LV a low viscosity, carboxymethylated cellulose.

15 Example Q

Epichlorohydrin crosslinked, 0.50 ds carboxymethylated, hydroxypropylated, waxy corn starch. Viscograph curve
was 55-65% of maximum viscosity.

20 Example R

Epichlorohydrin crosslinked, 0.50 ds carboxymethylated, hydroxypropylated, waxy potato starch. (Lower crosslink
density than Example G, potato starch counterpart to Example F).

25 Invention Examples

Example S

Epichlorohydrin crosslinked, 0.50 ds carboxymethylated, hydroxypropylated, blend of waxy and regular corn starch.
30 The starches were blended at a ratio of 50% waxy to 50% regular corn. The waxy corn starch was understood to con-
tain 1% amylose whereas the regular corn starch was understood to contain 26% amylose. On this basis, the final blend
provided 13.5% amylose. The Viscograph curve was 26% of maximum viscosity.

Example T
35
Epichlorohydrin crosslinked, 0.50 ds carboxymethylated, hydroxypropylated, blend of waxy and regular corn starch.
The starches were blended at a ratio of 75% waxy to 25% regular corn. The waxy corn starch was understood to con-
tain 1% amylose whereas the regular corn starch was understood to contain 26% amylose. On this basis, the final blend
provided 7.25% amylose content The Viscograph curve was 30% of maximum viscosity.
40
Example U

Epichlorohydrin crosslinked, 0.15 ds carboxymethylated, hydroxypropylated, waxy corn starch. Viscograph curve
was 30% of maximum viscosity.
45
Comparative Examples

Example V

so Epichlorohydrin crosslinked, 0.15 ds carboxymethylated, hydroxypropylated, waxy corn starch. Viscograph curve
was 55-65% of maximum viscosity.

Example W

55 Epichlorohydrin crosslinked, 0.08 ds carboxymethylated, hydroxypropylated, potato starch. Viscograph curve was
55-65% of maximum viscosity.

6
 EP 0 852 235 A2

Fluid loss results:

System 1

5 A model well drilling fluid using a saturated salt solution containing 1 g NaHC03 and 35 g API Standard Evaluation
Base Clay per 350 g solution. The formulations were prepared and tested for fluid loss properties at 275°F according
to API Specification 13A: Specification for Drilling Fluid Materials, Section 11.5, Saturated Salt Water Test. Test results
are reported in Table 1.
The results depicted in Table 1 show that the modified starches of the invention provide remarkably improved reten-
10 tion of fluid loss properties compared to the prior art and to similarly modified starches of higher amylose content.

Table 1
API Fluid Loss Results (mis)
15 1
Example Heat Aging Time (Hours) at 275°F
0 16 32 48 64 80 96 112
Invention Examples
20 A 56 23 18 12 7 8 37 120
B 22 6 6 8 28 71 124
C 37 8 8 10 10 12 81 116
Comparative Examples
25 . . . . . . . .
D 5 58 93 110
E 19 8 8 25 112
F 6 12 48 82 95
30 G 78 12 16 104
H 22 6 40 107
I 12 8 77
J 17 8 6 9 91
K 5 80 105
L 8 26 86
M 7 17 80
to N 109 13 7 46 113
O 10 88 109
P 4 10 51 82 93
Q 7 6 14 65 90
45
R 8 19 82
Invention Examples
S 13 7 6 19 57 96
50 T 17 7 6 11 38 80
U 88 — 28 16 7 7 30 127
Comparative Examples
V 19 5 7 38 90
55
W 14 5 25 89

7
 EP 0 852 235 A2

System 2

Several of the modified starches described above were also tested for fluid loss properties in another drilling fluid
system employing an API saturated salt mud containing attapulgite, as described in US 4,652,384. The test fluid was
prepared by adding 6300 grams NaCI to 15,750 mis Dl water and then adding 551 .25 grams attapulgite. This compo-
sition was mixed for 1 hour to form a salt gel. The modified starch was added at 5 grams of starch per 350 mis of the
salt gel. Fluid loss properties on aging at 275°F, reported in Table 2, again showed improved heat aging resistance for
the compositions employing starches of the invention.

Table 2
API Fluid Loss Results (mis)
Example Heat Aging Time (Hours) at 275°F
0 16 32 48
Invention Examples
A 63 15 34 107
B 24 9 65 80
Comparative Examples
G 54 14 148
H 29 28 120
K 3 80 141
L 6 68 143
M 7 91 138

System 3

Another test drilling fluid system was prepared by blending 360 g prehydrated gel (10 ppb Gold Seal Bentonite),
0.15 g KOH, 37 g KCI, 65 g Barite and 4 g of a modified starch. Fluid loss properties on aging at 250°F, reported in Table
3, again showed improved heat aging resistance for the compositions employing starches of the invention.

Table 3
API Fluid Loss Results (mis)
Example Heat Aging Time (Hours) at 250°F
0 16 32 48
Invention Examples
A 40 34 30 12
B 22 17 14 13
Comparative Examples
E 30 15 28 129
F 16 34 102
I 61 90
J 50 72 106
N 157 49 85
Q 11 18 44 83

8
 EP 0 852 235 A2

System 4

In still another test fluid system, this one a 4% salt water system as set out in AP1 13A, Section 11.3, using a 285°F
heat aging temperature, the compositions prepared using starches of the invention again showed improved heat aging
5 resistance. Results of these tests are reported in Table 4.

Table 4
API Fluid Loss Results (mis)
Example Heat Aging Time (Hours) at 285°F
0 16 32 48 64 85 109 115 130
Invention Examples
A 24 15 12 10 6 11 17 35 126
B 13 7 6 7 7 17 107
Comparative Examples
F 6 10 26 69
K 5 6 60 83
L 7 5 7 12 12 83
O 8 18 53 83
R 6 12 51 85
Q 7 6 9 18 76

The starch polymers, formulations and test results described above are merely illustrative of the invention and
30 those skilled in the art will recognize that many other variations may be employed within the teachings provided herein.
Such variations are considered to be encompassed within the scope of the invention as set forth in the following claims.

Claims

35 1. A modified starch polymer, obtained from an unmodified starch or blend of starches having a content of amylopec-
tin of at least 80% by weight, the starch polymer being crosslinked with epichlorohydrin and carboxymethylated, the
amount of epichlorohydrin crosslinking being equivalent to that which is obtained when a crosslinking reaction is
subjected to a Brabender viscosity which reaches a maximum value and then is reduced with further crosslinking
from its maximum to a value which is no more than 50% of the maximum value, and the degree of carboxymethyl
40 substitution being at least 0.1 carboxymethyl groups per anhydroglucose unit.

2. A modified starch polymer as in claim 1 wherein said content of amylopectin is at least 85% by weight and said
degree of carboxymethyl substitution is at least 0.3 carboxymethyl groups per anhydroglucose unit.

45 3. A modified starch polymer as in claim 1 wherein said content of amylopectin is at least 95% by weight.

4. A modified starch polymer as in any of claims 1-3 wherein said degree of carboxymethyl substitution is at least 0.4
carboxymethyl groups per anhydroglucose unit.

so 5. A modified starch polymer as in any of claims 1-4 said polymer being further modified by hydroxypropylation of the
polymer.

6. A modified starch polymer as in claim 5 wherein the starch polymer is hydroxypropylated to an degree which cor-
responds to from about 0.5% to about 20% reacted propylene oxide based on the dry weight of said unmodified
55 starch.

7. A modified starch polymer as in any of claims 1-6 wherein said reduced Brabender viscosity value is no more than
35% of the maximum value.

9
 EP 0 852 235 A2

8. A modified starch polymer as in any of claims 1-7 obtained from an unmodified starch or blend of starches which
is substantially amylose-free.

9. A modified starch polymer as in claim 8 wherein said substantially amylose free starch is waxy corn starch.
5
10. A well drilling fluid formulation comprising a mixture of brine, clay and starch wherein the starch is a modified starch
polymer as in any of claims 1-9.

11. A well drilling fluid as in claim 10 further comprising an xanthan gum.

10
12. A well drilling fluid as in claim 10 further comprising at least one of hydroxyethyl cellulose, carboxymethyl cellulose,
a lignosulfonate salt, an emulsifier, a weighting agent, a corrosion inhibitor, calcium carbonate, magnesia, or
another starch derivative different from said modified starch polymer.

15 13. In a well drilling process comprising the step of providing a drilling fluid comprising a mixture of brine, clay and a
fluid loss polymer to a bore hole, the improvement that at least a portion of the fluid loss polymer is a modified
starch polymer as in any of claims 1-9.

14. A well drilling process as in claim 13 wherein the drilling fluid is subjected to a temperature of about 275°F or higher
20 within said bore hole for a period exceeding 24 hours.

15. A method of preparing a modified starch for well drilling comprising the steps of:

crosslinking an unmodified starch having a content of amylopectin of at least 80% by weight, to a degree cor-
25 responding to a Brabender viscosity which reaches a maximum value and then is reduced with further
crosslinking from its maximum to a value which is no more than 50% of the maximum value, and
carboxymethylating the resulting crosslinked starch polymer to a degree of substitution of at least 0.1 car-
boxymethyl groups per anhydroglucose unit.

30 16. A method as in claim 15 wherein said unmodified starch is waxy corn starch, said degree of carboxymethyl substi-
tution is at least 0.40 carboxymethyl groups per anhydroglucose unit, and said reduced Brabender viscosity is no
more than 35% of said maximum value.

17. A method as in claim 15 further comprising hydroxypropylating the starch polymer to a degree which corresponds
35 to from about 0.5% to about 20% reacted propylene oxide based on the dry weight of unmodified starch.

40

45

50

55

10