US 20060000570A1

(19) United States

(12) Patent Application Publication (10) Pub. N0.2 US 2006/0000570 A1
Song et al. (43) Pub. Date: Jan. 5, 2006
(54) AMPHOTERIC CATIONIC POLYMERS FOR (22) Filed: Jun. 22, 2005
CONTROLLING DEPOSITION OF PITCH
AND STICKIES IN PAPERMAKING Related US. Application Data

(76) Inventors: Zhiqiang Song, NeWtoWn, CT (US); (60) Provisional application No. 60/585,184, ?led on Jul.
Philip A. Ford, Suffolk, VA (US); 2, 2004. Provisional application No. 60/662,755, ?led
Vincent F. Roy, St-Augustin de on Mar. 17, 2005.
Desrnaures (CA); SWindell A.
Grimsley, Chesapeake, VA (US); Publication Classi?cation
Kenneth W. Satcher, Southaven, MS
(US); Matthew A. Blazey, Suffolk, VA (51) Int. Cl.
(US); Robert Pelbois, Quebec City D21H 21/02 (2006.01)
(CA) D21H 17/45 (2006.01)
(52) US. Cl. .................... .. 162/199; 162/1646; 162/183;
Correspondence Address: 162/1816; 162/1681; 162/1683
CIBA SPECIALTY CHEMICALS
CORPORATION (57) ABSTRACT
PATENT DEPARTMENT
540 WHITE PLAINS RD The present invention relates to a method and composition
P O BOX 2005 for controlling pitch and stickies deposit in a pulp and
TARRYTOWN, NY 10591-9005 (US) paperrnaking process using arnphoteric copolyrners of dial
lyldirnethylarnrnoniurn chloride (DADMAC) With acrylic
(21) Appl. No.: 11/158,845 acid and/or acrylarnide and optionally a siliceous material.
US 2006/0000570 A1
AMPHOTERIC CATIONIC POLYMERS FOR
CONTROLLING DEPOSITION OF PITCH AND
STICKIES IN PAPERMAKING
[0001] This application claims the bene?t of Provisional
Application No. 60/585,184, ?led Jul. 2, 2004 and Provi
sional Application No. 60/662,755, ?led Mar. 17, 2005.
[0002] The present invention relates to a method for
controlling pitch and stickies deposition in a pulp and
papermaking process using amphoteric copolymers formed
from the monomers diallyldimethylammonium chloride
(DADMAC), acrylic acid and optionally acrylamide. The
method may optionally further comprise the addition of a
siliceous material. The pitch and stickies are found in
mechanical pulps, recycled ?ber, coated broke, White Water
and the like. The invention also encompasses a composition
for pitch and stickies control in papermaking comprising the
amphoteric copolymer and optionally, a siliceous material.
BACKGROUND OF THE INVENTION
[0003] The present invention is directed to the use of
amphoteric copolymers or terpolymers of diallyldimethy
lammonium chloride (DADMAC) With acrylic acid and
optionally acrylamide for controlling and preventing depo
sition of pitch and stickies in papermaking. The amphoteric
copolymer may otionally, further comprise a siliceous mate
rial.
[0004] The siliceous material may be any of the materials
selected from the group consisting of silica based particles,
silica microgels, colloidal silica, silica sols, silica gels,
polysilicates, cationic silica, aluminosilicates, polyalumino
silicates, borosilicates, polyborosilicates, Zeolites and sWell
ing clays. This siliceous material may be in the form of an
anionic microparticulate material. When the siliceous mate
rial is a sWelling clay it may typically be a bentonite type
clay.
[0005] Cationic polymers have been used extensively in
paper making as ?occulants for improving retention and
drainage and as coagulants or ?xatives to control anionic
trash and deposition of pitch and stickies. Among the most
important and extensively used cationic polymers for
deposit control are the quaternary ammonium polymers of
diallyidialkyl ammonium compounds (e.g., DADMAC) and
copolymers of epichlorohydrin and dimethylamine knoWn
as polyamines. Homopolymers of DADMAC and
polyamines With high cationic charge density are good for
neutraliZing anionic trash but have limited success for
controlling pitch and stickies deposition. There is still a need
for polymer compositions Which Will prevent pitch and
stickies deposition.
[0006] Pitch and stickies are interfering substances in the
Wet end of papermaking that can affect both the machine
runnability and paper quality. The term “pitch” used here
refers to a colloidal dispersion of Wood-derived hydrophobic
particles released from the ?bers during a pulping process
and is also called Wood pitch. Wood pitch includes fatty
acids, resin acids, their insoluble salts, and esters of fatty
acids With glycerol, sterols, and other fats and Waxes. The
hydrophobic components of pitch, particularly triglycerides,
are considered one of the major factors determining Whether
the presence of such pitch Will lead to deposit problems.
Deposit-forming pitch often contains signi?cantly high
amounts of triglyciderides.
Jan. 5, 2006
[0007] The term “stickies” used herein refers to sticky
materials and interfering substances that arise from compo
nents of recycled ?bers, such as adhesives and coatings.
Stickies can come from coated broke, recycled Waste paper
for board making and de-inked pulp (DIP). The stickies from
coated broke is sometimes called White pitch. Deposition of
pitch and stickies often leads to defects in the ?nished
product and paper machine doWntime causing lost pro?ts for
the mill. These problems become more signi?cant When
paper mills “close up” their process Water systems for
conservation and environmental reasons. Unless the pitch
and stickies are continuously removed from the system in a
controlled manner, these interfering substances Will accu
mulate and eventually lead to deposition and runnability
problems. Technology in place today is based on ?xing the
pitch or stickies to the ?bers before they have a chance to
agglomerate, or alternatively coating the pitch or stickies
With a polymer that makes them non-tacky and therefore
unable to agglomerate.
[0008] Three chemical methods are commonly used by
paper mills to control pitch and stickies deposit:
[0009] 1) detacki?cation
[0010] 2) stabiliZation
[0011] 3) ?xation.
These methods are, hoWever, not commonly used together
since they may con?ict With each other. In detacki?cation, a
chemical is used to build a boundary layer of Water around
the pitch and stickies to decrease depositability. Detacki?
cation can be achieved by addition of pitch adsorbents such
as talc and bentonite. HoWever, pitch adsorbents such as talc
can end up contributing to the pitch deposit problem if the
talc/pitch particles are unable to be retained in the paper
sheet With surfactants and Water-soluble polymers. In sta
biliZation, surfactants and dispersants are used to chemically
enhance colloidal stability and alloW pitch and stickies to
pass through the process Without agglomerating or deposit
ing.
[0012] In ?xation, polymers are used to ?x pitch and
stickies to the ?ber and remove them from the White Water
system. The interfering substances in papermaking systems
are usually anionic in nature and are sometimes referred to
as anionic trash or cationic demand. Anionic trash consists
of colloidal (pitch and stickies) and dissolved materials that
adversely affect the paper making in a variety of Ways
through deposit formation or interference With chemical
additives. Removal of anionic trash by reducing cationic
demand With a cationic polymer is a Way of deposit control
through ?xation. The advantage of using cationic polymeric
coagulants for pitch and stickies control is that the pitch and
stickies are removed from the system in the form of micro
scopic particles dispersed among the ?bers in the ?nished
paper product.
[0013] Cationic polymers are normally used as ?xatives to
control pitch and stickies through ?xation. Nonionic poly
mers discussed in PCT Application No. 200188264 such as
polyvinyl alcohol and copolymers such as polyacrylamide
vinyl acetate have been developed and used for stickies
control through detacki?cation. US. Pat. No. 6,051,160
discloses hydrophobically modi?ed anionic polymers such
as a copolymer of styrene and maleic anhydride for used in
pitch deposit control through, most likely, the pitch stabili
Zation mechanism.
US 2006/0000570 A1
[0014] Homopolymers of DADMAC are commonly used
alone or With other components as ?Xatives for anionic trash
control and pitch control.
[0015] Canadian Patent No. 1,194,254 teaches a method
of reducing Wood pitch particles in aqueous pulp With a
polyDADMAC. The patent does not teach use of the poly
DADMAC for stickies containing pulps from recycled sec
ondary ?bers. Papermakers today face the increased use of
recycled secondary ?ber. Unlike virgin ?ber that Was used in
the past, recycled ?bers contain stickies from many sources
such as glue, adhesives and coating binders. The Canadian
patent is also limited to use of DADMAC homopolymer.
US. Pat. No. 5,989,392 teaches use of crosslinked DAD
MAC polymers for controlling anionic trash and pitch
deposition in pulp containing broke. Apulp ?ltrate turbidity
test is used to evaluate polymer performance in pitch depo
sition control therein. Improved ef?ciencies of solution
crosslinked or branched polyDADMACs over conventional
linear polyDADMAC are demonstrated. The crosslinked or
branched polyDADMACs used are prepared using a poly
ole?nic crosslinking monomer such as triallylamine hydro
chloride or methylene bisacrylamide.
[0016] US. Pat. No. 4,964,955 discloses a method of
using an aqueous slurry of polyDADMAC and kaolin clay
for reducing pitch in pulping and papermaking.
[0017] US. Pat. No. 4,913,775 provides a process Wherein
a Water soluble substantially linear cationic polymer is
applied to the paper making stock prior to a shear stage and
then re?occulating by introducinting bentonite after that
shear stage. This process provides enhanced drainage and
also good formation and retention. This process Which is
commercialiZed by Ciba Specialty Chemicals under the
HYDROCOL trade mark has proved successful for more
than a decade. This process hoWever, relates to retention and
drainage, not pitch and sticky deposit control. The bentonite
and cationic polymer are normally added to the thin stock in
the papermaking process.
[0018] US. Pat. No. 4,795,531 describes a method of
making paper in Which a loW molecular Weight cationic
organic polymer is added to the furnish and then a colloidal
silica and a high molecular Weight charged acrylamide
copolymer of molecular Weight of at least 500,000.
[0019] US. Pat. No. 5,256,252 discloses a method for
controlling pitch deposit using enZyme (lipase) With DAD
MAC polymers. This patent is related more to use of enZyme
Which is a necessary component for the method. A ?ltrate
turbidity test is used to evaluate pitch control performance.
[0020] US. Pat. No. 5,230,774 is directed to a process for
controlling pitch deposits by adding a blend of a homopoly
mer of DADMAC and ammonium Zirconium carbonate.
None of the polymers are copolymers of DADMAC.
[0021] US. Pat. No. 5,131,982 teaches use of DADMAC
homopolymers and copolymers for coated broke treatment
to control White pitch. The patent teaches a method of adding
DADMAC polymer to re-pulped coated broke and then
admixing the treated coated broke pulp With other ?ber
sources before forming a paper sheet. Use of DADMAC
polymers for pitch and stickies control for mechanical pulp
and deinked recycled pulp is not taught. The copolymers
claimed are mainly copolymers of DADMAC and acryla
mide With more than 25% of acrylamide.
Jan. 5, 2006
[0022] Amphoteric polymers are polyelectrolytes contain
ing both positive and negative functional groups in the same
polymer molecule. Amphoteric DADMAC polymers are
DADMAC copolymers containing negative, or potentially
negative, functional groups.
[0023] European Application No. 464,993 discloses use of
an amphoteric copolymer of DADMAC and acrylic acid
salts for controlling Wood pitch deposition or natural pitch.
A ?ltrate turbidity test is one of the test methods used to
evaluate pitch deposit control performance. The polymers
disclosed are not claimed for use in deposit control of
stickies and White pitch in recycle pulps and coated broke.
The amphoteric DADMAC terpolymer claimed does not
include polymers containing acrylamide.
[0024] PCT Application No. 200034581 teaches use of
amphoteric terpolymers of DADMAC, acrylamide and
acrylic acid as a retention/drainage/formation aid in a paper
making process. The terpolymers are also taught for con
trolling White pitch for coated broke. The preferred terpoly
mers of DADMAC, acrylamide and acrylic acid claimed for
treating White pitch contain more than 25% of acrylamide
and not more than 50% of DADMAC. A?ltrate turbidity test
is used to determine the polymers White pitch deposit control
performance.
[0025] European Application No. 058622 teaches a
method for reducing or preventing the deposition of Wood
pitch during the papermaking process With an emulsion
copolymer of DADMAC, DADEAC, acrylamide and
acrylic acid. The copolymer contains 45 to 50% acrylamide,
no more than 50 Wt % of DADMAC and at least 2 Wt % of
an uncommon monomer, DADEAC, (diallyldiethylammo
nium chloride) Which is not commercially available today.
No mention is made for use of the copolymer for stickies
control of recycled ?bers.
[0026] US. Pat. No. 4,505,828 teaches use of an inverse
emulsion amphoteric copolymer made from acrylamide,
acrylic acid and dimethylaminoethyl methacrylate in petro
leum recovery by a Water ?ooding process and in paper
making as a drainage aid. Use of a solution amphoteric
terpolymer of DADMAC, acrylamide and acrylic acid is not
taught. The patent is not related to pitch and stickies deposit
control in papermaking.
[0027] US. Pat. No. 3,639,208 discloses the preparation
and composition of certain amphoteric terpolymers of DAD
MAC, acrylamide and acrylic acid obtained by partly hydro
lyZing a copolymer of acrylamide and DADMAC. The
copolymer and its hydrolyZed terpolymer contains less than
70% DADMAC. The terpolymers obtained are used as
retention aids in papermaking. Use of the amphoteric ter
polymer for pitch control is not taught.
[0028] US. Pat. No. 5,837,100 teaches the use of blends
of a dispersion polymer and a coagulant for coated broke
treatment to improve retention and/or drainage. The Water
dispersion polymer is a copolymer of acrylamide and qua
ternary dimethylaminoethyl acrylate. The coagulant is a
copolymer of epichlorohydrin and dimthylamine. Turbidity
reduction testing is used to determine the activity ef?ciency
of the polymers.
[0029] FiXatives With increased pitch and stickies ?xation
poWer are needed. Alum, starches and loW molecular Weight
cationic coagulants conventionally used for deposit control
US 2006/0000570 A1
can neutralize anionic trash and detrimental substances
(pitch and stickies) and form complexes. However, they may
not carry suf?cient charge and/or molecular Weight to ?x
pitch and stickies complexes to the ?ber. If not strongly ?xed
to the ?bers, the complexes Will become concentrated in the
system and Will lead to deposition problems.
[0030] Innovations in ?xatives for runnability improve
ment by the present inventors have led to development of a
number of diallyldimethylammonium chloride (DADMAC)
copolymers With high ?xation poWer for pitch and stickies
control. These DADMAC polymers have signi?cantly
greater poWer to remove detrimental pitch and stickies from
a papermaking Water system than existing commercial ?xa
tive products. When combined With siliceous material, the
polymers are also effective.
[0031] The above revieW shoWs that there is a need for
controlling pitch and stickies deposition in paper making
With effective polymers. The search for polymer composi
tions Which Will prevent pitch and stickies deposition has
met With limited success and is still ongoing. It has noW been
found that an amphoteric DADMAC copolymer With high
DADMAC and acrylic acid units in an amount from
about 0.1 to about 15% based on the Weight of the DAD
MAC copolymer content is very effective in reducing pitch
and stickies. The amphoteric polymers are effective When
used on their oWn and When combined With siliceous
material.
SUMMARY OF THE INVENTION
[0032] A dual functional polymer capable of controlling
deposition through both ?xation and anionic trash reduction
is desirable. The inventive Water-soluble amphoteric poly
mers described herein serve this dual purpose since they
contain anionic and nonionic hydrogen bonding groups in
addition to cationic functionality for ?xation and charge
neutraliZation. The polymers are also effective When com
bined With siliceous material.
[0033] Amphoteric polymers are polyelectrolytes contain
ing both positive and negative functional groups in the same
polymer molecule. Amphoteric DADMAC polymers are
DADMAC copolymers containing negative, or potentially
negative, functional groups.
[0034] One objective of this invention is to provide for
pitch and stickies deposit control in papermaking an ampho
teric polymer of DADMAC containing anionic groups
Which impart variable charge density and hydrophobicity for
the polymer in response to pH change.
[0035] Another objective of this invention is to provide for
pitch and stickies deposit control in papermaking an ampho
teric polymer of DADMAC containing nonionic functional
groups Which can provide additional interactions through
hydrogen bonding in addition to ionic charge interaction.
[0036] Accordingly, the invention encompasses a process
for pitch and stickies deposit control in papermaking com
prising
Jan. 5, 2006
[0037] adding to a paper furnish
[0038] a composition comprising an amphoteric polymer
Wherein X“ is an anion;
[0039] M+ is hydrogen, ammonium, sodium, or potas
sium;
[0040] R is hydrogen or methyl;
[0041] R1 is methyl or ethyl;
[0042] n is from about 70 to about 99.8%,
[0043] m is from about 0.2 to about 30%, and
[0044] p is from 0 to about 30%,
Wherein n+m+p=100% based on the total Weight of the
amphoteric polymer.
[0045] Preferably, X- is Cl‘,
[0046] M+ is Na”,
[0047] n is from about 85 to about 98%,
[0048] m is from about 1 to about 15%, and
[0049] p is from about 1 to about 10% by Weight based on
the total Weight of the amphoteric polymer.
[0050] The amphoteric polymer composition may further
comprise a siliceous material. The method above may fur
ther comprise the step of adding a siliceous material. The
amphoteric polymer may be added before, after or simulta
neously (preferably separately) a siliceous material to the
furnish.
[0051] The ratio of cationic charge to anionic charge or
potentially anionic charge refers to the ratio of the moles of
the cationic monomer divided by the moles of the anionic
monomer or potentially anionic monomer Which form the
amphoteric polymer.
[0052] The present inventors have discovered that a cat
ionic amphoteric DADMAC polymer With a ratio of cationic
charge to anionic charge greater than about 1.2 can be
successfully used to control pitch and stickies deposit by
removing them from the system in the form of microscopic
particles.
[0053] The present invention is directed to application of
a Water-soluble cationic amphoteric polymer for controlling
and preventing deposition of pitch and stickies in paper
making. The method comprises the step of adding the
amphoteric polymer to treat mechanical pulp for controlling
Wood pitch deposits, coated broke for controlling stickies or
With pitch deposit, and recycled pulp for controlling stickies
deposit. The amphoteric polymer may further comprise a
siliceous material.
US 2006/0000570 A1
[0054] The cationic amphoteric polymer is made by radi
cal polymerization of DADMAC With (meth)acrylic acid
and/or acrylamide.
DETAILED DESCRIPTION OF THE
INVENTION
[0055] In the invention, the amphoteric polymer is any
polymer containing both a cationic charge and an anionic
charge. The cationic amphoteric polymer is an amphoteric
polymer With a cationic charge content greater than the
anionic charge. The cationic amphoteric polymer can be a
copolymer of tWo monomers derived from cationic and
anionic monomers or a terpolymer of three monomers
derived from cationic, anionic and nonionic monomers.
[0056] Cationic polymers are commonly used in paper
making to remove anionic trash by charge neutralization.
Anionic trash consists of colloidal (pitch and stickies) and
dissolved materials that adversely affect the papermaking in
a variety of Ways through deposit formation or interference
With chemical additives. Removal of anionic trash by ?xing
the colloidal particles to ?ber and reducing the cationic
demand With a cationic polymer is a Way of pitch and
stickies deposit control. The advantage of using cationic
polymeric coagulants for pitch and stickies control is that the
pitch and stickies are removed from the system in the form
of microscopic particles dispersed among the ?bers in the
?nished paper product.
[0057] The present inventors have discovered that the
?xation of pitch and stickies to paper ?ber and charge
neutralization can be enhanced by the use of amphoteric
copolymers With a mole ratio of cationic charge to anionic
charge greater than about 1.2, preferably greater than about
4 and most preferably greater than about 5. The amphoteric
copolymers are formed by polymerization of diallyldialky
lammonium compounds and (meth)acrylic acid (and/or its
salts) and optionally acrylamide. The preferred diallyl
dialkyl ammonium compounds are diallyldimethylammo
nium chloride (DADMAC).
[0058] For the purposes of the invention, the phrase
(meth)acrylic or (meth)acrylate refers to both the acrylic and
methacrylic or acrylate or methacrylate derivatives.
(1)
Wherein X- is an anion;
[0059] M+ is hydrogen, ammonium, sodium, or potas
sium;
[0060] R is hydrogen or methyl;
[0061] R1 is methyl or ethyl;
[0062] n is from about 70 to about 99.8%;
[0063] m is from about 0.2 to about 30%
Jan. 5, 2006
[0064] and
[0065] p is from 0 to about 30% With n+m+p=100% based
on the total Weight of the amphoteric polymer.
[0066] Preferably, X“ is Cl“;
[0067] M+ is Na";
[0068] n is from about 85 to about 98%;
[0069] m is from about 1 to about 15%
[0070] and
[0071] p is from about 1 to about 10% by based on the total
Weight of the amphoteric polymer.
[0072] The unit n of the above polymer represents a unit
derived from a cationic monomer selected from the group
consisting of diallyidialkylammonium compounds.
[0073] For example, the cationic monomer can be a dial
lyldiethylammonium halide or diallydimethylammonomium
halide.
[0074] The unit m of the above polymer represents a unit
derived from an anionic monomer or potentially anionic
monomer selected from the group consisting of hydrolysed
acrylamide and (meth)acrylic acids and/or salts thereof.
[0075] The potentially anionic monomer can be hydroly
sed acrylamide.
[0076] Alternatively, the anionic monomer may preferably
be (meth)acrylic acid and/or salts thereof.
[0077] The amphoteric DADMAC polymer for use in
accordance With the present invention is preferably one
containing cationic charge in excess of the anionic charge.
The molar ratio of n/m is preferably greater than about 1.2,
more preferably, greater than about 4 and most preferably
greater than about 5.
[0078] The amphoteric DADMAC polymer may have a
Weight average molecular Weight ranging from about 10,000
to about 20,000,000, preferably, from about 100,000 to
about 2,000,000, and more preferably from about 300,000 to
about 2,000,000.
[0079] The amphoteric DADMAC polymer can be used in
dosages that range from about 0.01 to about 20 lbs/ton,
preferably from about 0.2 to about 10 lbs/ton based on dry
solids.
[0080] Polymerization of the cationic amphoteric polymer
can be carried out by aqueous solution polymerization,
Water-in-oil inverse emulsion polymerization or dispersion
polymerization using a suitable free radical initiator.
Examples of suitable initiators include persulfates such as
ammonium persulfate (APS); peroxides such as hydrogen
peroxide, t-butyl hydroperoxide, and t-butyl peroxy pivalate,
azo initiators such as 2,2‘-azobis(2-amidinopropane) dihy
drochloride, 4,4‘-azobis-4-cyanovaleric acid and 2,2‘-azobi
sisobutyronitrile; and redox initiator systems such as t-butyl
hydroperoxide/Fe(II) and ammonium persulfate/bisul?te.
Aqueous solution polymerization using ammonium persul
fate (APS) is the preferred method for preparing the cationic
amphoteric polymer of the preferred monomers of DAD
MAC, (meth)acrylic acid and acrylamide.
[0081] (Meth)acrylic acid monomer can be used in its acid
form in polymerization. The produced acid polymer solution
US 2006/0000570 A1
can then be neutralized With a suitable base to the desired pH
and counter ions. Alternatively, (meth)acrylic acid monomer
can be partly or completely neutraliZed before polymeriZa
tion. Examples of suitable bases for neutraliZation of (meth
)acrylic acid monomeric units include NaOH, KOH, and
(NH 4)OH.
[0082] It is preferred to carry out the polymerization in the
absence of oxygen. Oxygen can be removed from the
reaction medium by applying vacuum With agitation or by
purging With an inert gas such as nitrogen or argon. The
polymeriZation can then be conducted under a blanket of the
inert gas.
[0083] The siliceous material may be any of the materials
selected from the group consisting of silica based particles,
silica microgels, colloidal silica, silica sols, silica gels,
polysilicates, aluminosilicates, polyaluminosilicates, boro
silicates, polyborosilicates and Zeolites. This siliceous mate
rial may be in the form of an anionic microparticulate
material. Alternatively the siliceous material may be cationic
silica.
[0084] In one more preferred form of the invention the
siliceous material is selected from silicas and polysilicates.
The silica may be any colloidal silica, for instance as
described in US. Pat. No. 4,961,825. The polysilicate may
be a colloidal silicic acid as described in Us. Pat. No.
4,388,150.
[0085] The polysilicates of the invention may be prepared
by acidifying an aqueous solution of an alkali metal silicate.
For instance polysilicic microgels otherWise knoWn as active
silica may be prepared by partial acidi?cation of alkali metal
silicate to about pH 8-9 by use of mineral acids or acid
exchange resins, acid salts and acid gases. It may be desired
to age the freshly formed polysilicic acid in order to alloW
sufficient three dimensional netWork structure to form. Gen
erally the time of ageing is insuf?cient for the polysilicic
acid to gel. Particularly preferred siliceous materials include
polyalumino-silicates. The polyaluminosilicates may be for
instance aluminated polysilicic acid, made by ?rst forming
polysilicic acid microparticles and then post treating With
aluminium salts, for instance as described in US. Pat. No.
5,176,891. Such polyaluminosilicates consist of silicic
microparticles With the aluminium located preferentially at
the surface.
[0086] Alternatively the polyaluminosilicates may be
polyparticulate microgels of surface area in excess of about
1000 m2/g formed by reacting an alkali metal silicate With
acid and Water soluble aluminium salts, for instance as
described in Us. Pat. No. 5,482,693. Typically the polya
luminosilicates may have a mole ratio of aluminazsilica of
betWeen 1:10 and 1:1500.
[0087] Polyaluminosilicates may be formed by acidifying
an aqueous solution of alkali metal silicate to pH 9 or 10
using concentrated sulphuric acid containing 1.5 to 2.0% by
Weight of a Water soluble aluminium salt, for instance
aluminium sulphate. The aqueous solution may be aged
sufficiently for the three dimensional microgel to form.
Typically the polyaluminosilicate is aged for up to about tWo
and a half hours before diluting the aqueous polysilicate to
0.5 Weight % of silica.
[0088] The siliceous material may be a colloidal borosili
cate, for instance as described in WO-A-9916708. The
Jan. 5, 2006
colloidal borosilicate may be prepared by contacting a dilute
aqueous solution of an alkali metal silicate With a cation
exchange resin to produce a silicic acid and then forming a
heel by mixing together a dilute aqueous solution of an alkali
metal borate With an alkali metal hydroxide to form an
aqueous solution containing 0.01 to 30% B203, having a pH
of from 7 to 10.5. In one preferred aspect the siliceous
material is a silica.
[0089] Preferably When the siliceous material is a silica or
silicate type material it has a particle siZe in excess of about
10 nm. More preferably the silica or silicate material has a
particle siZe in the range about 20 to about 250 nm,
especially in the range about 40 to about 100 nm.
[0090] In a more preferred form of the invention the
siliceous material is a sWelling clay. The sWellable clays
may for instance be typically a bentonite type clay. The
preferred clays are sWellable in Water and include clays
Which are naturally Water sWellable or clays Which can be
modi?ed, for instance by ion exchange to render them Water
sWellable. Suitable Water sWellable clays include but are not
limited to clays often referred to as hectorite, smectites,
montmorillonites, nontronites, saponite, sauconite, hor
mites, attapulgites and sepiolites. These clays may be either
naturally occurring or synthetic. An example of a synthetic
hectorite clay Would be LAPONITE available from South
ern Clay Products, Inc., USA. Typical anionic sWelling
clays are described in US. Pat. Nos. 4,753,710 and 4,913,
775.
[0091] Most preferably the clay is a bentonite type clay.
The bentonite may be provided as an alkali metal bentonite.
Bentonites may be natural or synthetic. Naturally occurring
bentonites may be either as alkaline bentonites, such as
sodium bentonite or as the alkaline earth metal salt, usually
the calcium or magnesium salt. Generally the alkaline earth
metal bentonites are activated by treatment With sodium
carbonate or sodium bicarbonate. Activated sWellable ben
tonite clay is often supplied to the paper mill as dry poWder.
Alternatively the bentonite may be provided as a high solids
?oWable slurry of activated bentonite, for example at least
about 15 or about 20% solids, for instance as described in
US. Pat. Nos. 5,223,098, 6,024,790 and 6,045,657.
[0092] The bentonite may be applied to the cellulosic
suspension as an aqueous bentonite slurry. Typically the
bentonite slurry comprises up to 10% by Weight bentonite.
The bentonite slurry Will normally comprise at least 3%
bentonite clay, typically around 5% by Weight bentonite.
When supplied to the paper mill as a high solids ?oWable
slurry usually the slurry is diluted to an appropriate concen
tration. In some instances the high solids ?oWable slurry of
bentonite may be applied directly to the paper making stock.
[0093] The bentonite may be added to the cellulosic
suspension either before or after addition of the amphoteric
polymer of the invention. The bentonite may also be added
simultaneously, (preferably separately), With the amphoteric
polymer.
[0094] Desirably the siliceous material is applied in an
amount of at least about 100 ppm by Weight based on dry
Weight of suspension. Desirably the dose of siliceous mate
rial may be as much as about 10,000 ppm by Weight or
higher. In one preferred aspect of the invention doses of
about 100 to about 500 ppm by Weight have been found to
US 2006/0000570 A1 Jan. 5, 2006

be effective. Alternatively, higher doses of siliceous material about 30 minutes. Then an aqueous solution containing 5.6
may be preferred, for instance about 1000 to about 2000 g of sodium metabisu?te is added over 40 minutes. The
ppm by Weight. reactor is held at 90° C. for another 30 minutes to complete
[0095] Dosages in the paper industry are frequently the polymeriZation (above 99% conversion). The polymer
solution is diluted With suf?cient Water to about 35% solids.
expressed in the units kg/ton based on dry Weight of the This product has a solids content of 35.3 Wt. % With a 25°
furnish. Expressed in these units the amount of siliceous
C. Brook?eld viscosity of 8,800 cps and a 25° C. Brook?eld
material added to the furnish may range from about 0.2 to
about 10 kg/ton; preferably about 1.0 to about 6 kg/ton; most viscosity at 20% solids (20% BV) of about 400 cps. The
20% BV is proportional to molecular Weight of the polymer
preferably about 1.0 to about 4 kg/ton based on the dry
and therefore the data are used to compare the molecular
Weight of the furnish.
Weights of different solution polymers.
[0096] The Weight to Weight ratio of the amphoteric
polymer to siliceous material may range from about 02:10; TABLE 1
preferably 1:1 to 1:4; and most preferably 1:2. For example,
the ?xative or polymer may range from about 0.5 to about Copolvmers of DADMAC acrylic acid and acrylamide
2 kg/ton With the siliceous dosage ranging from about 1 to 2Viscosity, 20% BV at
about 2 kg/ton. Sample M1/M2/M3" Solids cps 25° C., cps
[0097] For deposit control the siliceous material and the lControl 100/0/0 34.6% 7,850 410
polymeric ?xative are preferably added to the thick stock Polymer 1 95/5/0 35.3% 8,800 400
(about 2-4% cellulose concentration) during the papermak Polymer 2 90/10/0 35.3% 8,850 400
Polymer 3 95/5/0 35.4% 15,700 630
ing process. Polymer 4 90/10/0 35.4% 15,560 625
Polymer 5 80/20/0 34.6% 39,800 1500
[0098] The amount of the free radical initiator used in the Polymer 6 60/40/0 34.6% 31,000 1300
polymeriZation process depends on the total monomer con Polymer 7 95/5/0 21.1% 2760 2180
centration and the type of monomers used and may range Polymer 8 92/80 21.5% 2730 1960
from about 0.2 to about 5.0 Wt % of the total monomer Polymer 9 92.5/2.5/5 21.6% 2860 1990
Polymer 10 91/8/1 20.3% 2400 2240
charge to achieve conversion of more than 99% of the total
monomer. 1Homopolymer of DADMAC
2Viscosities of 1000 to 3000 cps, use spindle LV3 at 30 rpm; 3000 to
[0099] The speci?c embodiments of this invention are 8000 cps use spindle LV3 at 12 rpm and 8,000 to 16,000 cp, use spindle
illustrated by the folloWing examples. These examples are LV3 at 6 rpm.
illustrative of this invention and not intended to be limiting. *M1 = DADMAC; M2 = acrylic acid M3 = acrylamide

EXAMPLES Performance Evaluation

[0102] Commercial products listed in Table 2 are also used
Synthesis of Polymers in the evaluation for comparison.
Example 1 TABLE 2A

Synthesis of Amphoteric DADMAC Polymers 1-10 Existing commercial ?xatives (EFC) products tested
and DADMAC homopolymer Control Product ID Polymer Chemistry
[0100] The procedure for making Polymer 1 is described Alco?x 269 LoW MW DADMAC homopolymer
in this example. Other polymers are made folloWing the Alco?x 110 High MW DADMAC homopolymer
same procedure, but using different monomer ratios, initiator Alco?x 111 High MW DADMAC homopolymer
Alco?x 159 Medium MW polyamine
feeds and temperature to obtain polymers With different Alco?x 160 High MW polyamine
compositions and molecular Weights. Molecular Weights of Alco?x 158 LoW MW polyamine
the polymers are measured using the bulk viscosity or 1Alco?x 161 DADMAC copolymer
Brook?eld viscosity (BV) at 20% polymer solids. A high 2Alco?x 505 DADMAC copolymer
Rai?x 120 Cationic starch
20% BV value indicates a high MW. Properties of the
polymers synthesiZed are shoWn in Table 1. 1Copolymer of 95% DADMAC and 5% acrylamide.
2Copolymer of 50% DADMAC and 50% acrylamide.
[0101] A 1-liter reactor equipped With a condenser, a
thermometer, a nitrogen inlet, and an overhead agitator is
charged With 453.86 g of 66% monomer DADMAC, 15.8 g
[0103] Avacuum drainage ?ltrate turbidity test is used to
of acrylic acid, 59 g of deioniZed Water and 0.15 g of Versene
demonstrate the performance of the amphoteric polymers of
the present invention and commercial ?xatives products and
(Na4EDTA). 35 g of a 25% NaOH solution is added sloWly their ability to ?x pitch, stickies and other contaminants onto
to the reactor at room temperature to neutraliZe the acrylic
?bre and therefore control and prevent these contaminants
acid. The polymeriZation mixture is purged With nitrogen
and heated With agitation to a temperature of 90° C. 36 g of
from deposition during paper making. The detailed test
procedure is shoWn beloW.
a 14.5% ammonium persulfate (APS) aqueous solution Was
sloWly fed to the reactor over 165 minutes. The reaction [0104] 1. About 250 mL of a 3-5% consistency furnish is
temperature is alloWed to increase to above 1000 C. and then measured into a baffled Britt jar. Adequate mixing is
maintained at 100 to 110° C. during the APS feed period. provided With a IKA mixer set to agitate at 1000 rpm.
After the APS feed, the reaction mixture is diluted With [0105] 2a. The required amount of polymer is added to the
deioniZed Water to about 40% solids and held at 90° C. for agitated thick stock and alloWed to mix for 2 minutes.
US 2006/0000570 A1 Jan. 5, 2006

[0106] 2b. Optionally, the required amount of siliceous

material is added to the agitated thick stock and allowed TABLE 3A
to mix for 2 minutes.
100% recycled furnish deinked pulp (DIP)
[0107] 3. The treated thick stock is then ?ltered through a furnish
Whatman 541 ?lter paper (11 cm diameter, coarse— blank turbidity, 578 NTU
retention for particles>20-25 microns) under vacuum.
Dosage, kg/ton 0.2 0.4 0.8
[0108] 4. Vacuum ?ltration continues until the “Wet line” Turbidity, NTU
just disappears or approximately 200 mLs of ?ltrate is
collected. Commercial ?xative (Alco?x 159) 126 73 50
Polymer 3 (5% AA) 99 63 41
Polymer 4 (10% AA) 176 104 49
[0109] 5. Turbidity of the ?ltrate is measured With a Polymer 5 (20% AA) 149 105 51
suitable turbidimeter. Polymer 6 (40% AA) 159 101 50
[0110] 6. Cationic charge demand (CCD) of the ?ltrate is
determined by colloidal titration.
Example 4
[0111] Dosage used is in Weight of active polymer per ton
of pulp solids (dry Weight). Performance on Coated Broke
[0112] The loWer the ?ltrate turbidity, the greater is the [0115] Performance of the DADMAC copolymers of the
pitch and stickies control of the treatment employed and
therefore the better performance of the polymer used. present invention for White pitch control is evaluated on
different types of coated broke. The samples are tested on the
Example 2 folloWing three types of broke.

[0113] The samples tested in this example all have a [0116] 45# Pub Matte, a light-Weight free sheet
relatively loW molecular Weight expressed by the 20% BV
of about 400 cps. Testing is performed on 100% recycled old [0117] 38# DPO, heavy Weight groundWood containing
corrugated container (OCC) furnish from a linerboard mill [0118] 70# DPO, heavy Weight groundWood containing
experiencing serious stickies deposit problem. This example
shoWs that With similar MW, the amphoteric DADMAC [0119] For each dosage of polymer treatment, the turbidity
copolymer Polymer 1 performs better in the turbidity reduc and cationic demand of the ?ltrate is measured. The results
tion than the DADMAC homopolymer control. Results in of the study are shoWn in the Tables 4A, 4B and 4C.
Table 2B for the Control, Polymer 1 and Polymer 2, dem
onstrate that the performance improvement With incorpora TABLE 4A
tion of the AA anionic component is diminished When the M
content is above 10%. 45# Pub Matte: Turbidity of treated furnish
at different dosage lb/ton on dry solids basis
TABLE 2B
Dosage (lb/ton)
100% recycled Old Corrugated Container 0.4 0.8 1.2 1.6 2.4
(OCC) furnish
Polymer 7 2635 511 176 110
blank Turbidity, 379 NTU
Polymer 8 2792 396 194 120
Polymer 9 2558 414 166 68
Dosage, kg/ton 1.0 2.0 5.0
Alco?x 110 2995 825 246 200
Turbidity, NTU Alco?x 269 2011 322 248
Alco?x 159 1258 447 316
Control 1 (homopolymer 0% AA) 57 49 43
Polymer 1 (5% AA) 57 46 39
Polymer 2 (10% AA) 60 54 42
[0120]
Example 3 TABLE 4B

[0114] The samples tested in this example all have a 70# DPO: Turbidity of treated furnish at
different dosage lb/ton on dry solids basis
higher molecular Weight expressed by the 20% BV of above
600 cps. Testing is performed on 100% recycle deinked pulp Dosage (lb ton)
furnish from a paper mill. This example further demon
0.4 0.8 1.2 1.6 2.4
strates that the performance improvement With incorpora
tion of AA anionic component is diminished When the AA Polymer 7 110 57 44 31
content is above 10%. See Table 3A. Acommercial ?xative Polymer 8 141 49 29 35
(Alco?x 159, a medium MW polyamine) commonly used Polymer 9 88 56 31 31
Alco?x 110 170 87 58 46
for deposit control in paper mills is also included in the Alco?x 269 157 130 97
testing. Polymer 3 of the present invention gives signi? Alco?x 159 110 87 72
cantly better performance in turbidity reduction than the
commercial ?xatives.
US 2006/0000570 A1 Jan. 5, 2006

[0121] different molecular Weights, 2 copolymers of DADMAC

and acrylamide With different monomer ratios and molecular
TABLE 4C Weights, 3 polyepiamines With different molecular Weights
and structures, and 1 cationic starch. Of the 9 commercial
38# DPO: Turbidity of treated furnish at ?xatives tested, Alco?x 161, a DADMAC copolymer, per
different dosage lbfton on dry solids basis
formed consistently the best among the commercial prod
Dosage(lb/ton) ucts. Therefore, results of the amphoteric DADMAC
copolymers of the present invention are compared only to
0.4 0.8 1.2 1.6 2.4 those of Alco?x 161 to shoW their performance over existing
Polymer 7 10372 4090 2246 302 commercial ?xative products. As can be seen from Table 6A,
Polymer 8 4894 605 131 56 B and C, the amphoteric DADMAC copolymers of the
Polymer 9 7556 2596 329 122 present invention perform signi?cantly better than the best
Alco?x 110 11368 5192 2172 184
Alco?x 269 2512 247 127
commercial ?xative for all three types of furnishes. An
Alco?x 159 6856 2286 319 improvement of greater than about 20 to about 74% turbidity
removal over Alco?x 161 is observed using the amphoteric
DADMAC copolymers of the present invention.
[0122] The test data on existing commercial ?xative prod
ucts (Alco?x 269, Alco?x 110, and Alco?x 159) are also TABLE 6A
obtained for comparison and shoW the bene?t of using the
Filtrate turbidity of treated furnish With 100% TMP
copolymers of the present invention. The copolymers of the at different dosages (kg/ton on dry solids base).
present invention give performance signi?cantly better than Turbiditv of untreated furni h is 213 NTU.
all the commercial products tested.
Dosage lgg/ton Average % FT reduction
Example 5 0.25 0.5 1.0 2.0 FT, NTU over Alco?x 161

Performance on Deinked Pulp (DIP) Recycled Furnish. Alco?x 161 154 120 80 43 99 0
Polymer 7 126 96 63 27 78 20
[0123] The test data on recycled deinked pulp (DIP) are Polymer 8 116 95 57 23 73 24
obtained to shoW performance of the amphoteric DADMAC Polymer 9 131 91 71 23 58 19
copolymers over existing commercial ?xatives products
Alco?x 161, a coplymer of DADMAC and acrylamide. The
neW DADMAC-based amphoteric polymer samples give [0127]
performance signi?cantly better than the commercial prod
ucts. Improvements of up to about 50% over a commercial TABLE 6B
DADMAC copolymer (Alco?x 161) in average turbidity Filtrate turbidity of treated furnish With 100% DIP at different dosage
reduction are obtained. (kg/ton on dry solids base). Turbidity of untreated furnish is 218 NTU.
[0124] Filtrate turbidity (FT) results in Table 5 shoW DIP Average % FT reduction
furnish treatment With amphoteric DADMAC copolymers Dosage (kg/ton) 0.10 0.2 FT, NTU over Alco?x161
and compare With furnish treated With a commercial DAD
Alco?x 161 100 41 71 0
MAC copolymer (Alco?x 161). Polymer 7 78 28 53 25
[0125] LoWer FT indicates better performance for stickies Polymer 8 62 25 44 38
Polymer 9 79 32 56 21
deposit control.

TABLE 5 [0128]
% FT
reduction TABLE 6C
Dosage lb/ton Average FT, over
Filtrate turbidity of treated furnish With 60% TMP and 40% DIP at
1.0 2.0 3.0 4.0 NTU Alco?x 161 different dosages (kg/ton on dry solids base). Turbidity of untreated
furni h is 164 NTU.
Alco?x 161 131 87 65 49 83 0
Polymer 1 111 64 52 45 68 18.1 Average % FT reduction
Polymer 3 100 55 45 41 60 27.4 Dosage (kg/ton) 0.10 0.2 FT, NTU over Alco?x 161
Polymer 7 98 48 48 34 57 31.3
Polymer 8 71 41 29 23 41 50.6 Alco?x 161 125 103 114 0
Polymer 7 106 77 92 45
Polymer 8 90 64 77 74
Polymer 9 115 85 100 28
Example 6
Performance on TMP, DIP and TMP/DIP Mix Furnish. Example 7
[0126] Amphoteric DADMAC copolymers of the present [0129] Filtrate turbidity (FT) of treated furnish of 100%
invention are evaluated on three types of furnish (TMP, DIP TMP at different dosages (kg/ton on dry solids basis) of
and mix of DIP&TMP) from a paper mill together With nine ?xative and bentonite.
commercial products. Various commercial ?xative products [0130] The turbidity and total ester concentrations (a mea
included in the testing are 3 DADMAC homopolymers With sure of pitch) are determined in the ?ltrate and compared in
US 2006/0000570 A1 Jan. 5, 2006

Table 7. The testing procedure is essentially the same as that prising an amphoteric polymer represented by the folloWing
preformed for the commercial ?xatives shoWn in Table 2 structure (I)
except a 2% consistency furnish is tested and the residual (I)
ester, triglyceride esters and total ester pitch concentrations
are determined using gas chromatography (GC).
[0131] The GC analysis Was run on a DB-5HT 5m><0.25
mm><0.10 micron column, an Inlet temperature of 300° C.
and an FID Detector temperature of 350° C. The heating
program: Initial temp of 100° C. hold for 1 minute then
increase 15° C./min up to 350° C. and hold for 15 minutes.

TABLE 7
Filtrate turbidity of treated furnish of mechanical
pulp at different dosages (kg/ton on dry solids basis .

Polymer
dosage Residual
(solids Bentonite Centrifuged Ester Triglyceride Ester Pitch
basis) dosage Turbidity Conc. esters Total
Treatment Kg/ton kg/ton NTU (ppm) (ppm) (ppm)
Blank 0 0 564 2.4 1.5 3.9
Alco?x 269 1 0 362 0.6 0.6 1.2
1Polymer 10 1.0 0 455 0.6 0.6 1.2
2bentonite 0 2.0 398 1.3 1.2 2.5
bentonite 1.0 2.0 337 0.2 0.2 0.4
followed by
Polymer 10

1Terpolymer of DADMAC, acrylic acid and acrylamide.

2Bentonite is supplied under the tradename HYDROCOL 2D1 from Ciba Specialty
Chemical Corp. The HYDROCOL 2D1 Was supplied as a 5% aqueous slurry based on
the total Weight of the aqueous slurry.

Example 8 Wherein X“ is an anion;

[0132] Treatment of Coated Broke With Polymer and M+ is hydrogen, ammonium, sodium, or potassium;
Bentonite R is hydrogen or methyl;
[0133] The furnish is primarily bleached TMP. The furnish R1 is methyl or ethyl;
is combined With about 12 to 20% coated broke and diluted
to approximately 3% consistency using White Water from the n is from about 70 to about 99.8 Wt. %, m is from about
mill process. Bentonite Was added ?rst as a 5% aqueous
0.2 to about 30%
slurry at a dosage of 1.5 kg/t then folloWed by polymer 10. and
Table 8 shoWs the improvement in turbidity When the p is from 0 to about 30%,
amphoteric polymer is combined With bentonite.
With n+m+p=100% based on the total Weight of the
TABLE 8 amphoteric polymer.
2. A method according to claim 1,
Tubidity knockdown for coated broke
Wherein X- is Cl‘,
Treatment Turbidity in NTU
M+ is Na”,
Blank 925 n is from about 85 to about 98%,
Alco?x 269 (0.4 kg/ton) 287
Polymer 10 (0.2 kg/ton) 240 m is from about 1 to about 15%,
Polymer 10 (0.8 kg/ton) + 1bentonite (1.5 kg/ton) 130
and p is from 0 to about 10% by Weight.
1Bentonite is supplied under the tradename HYDROCOL 2D1 from Ciba 3. A method according to claim 1 further comprising the
Specialty Chemical Corp. step of adding a siliceous material.
4. Amethod according to claim 3 Wherein the amphoteric
[0134] It should be understood that the above description polymer is added to the paper furnish folloWed by addition
and examples are illustrative of the invention, and are not of the siliceous material.
intended to be limiting. Many variations and modi?cations 5. A method according to claim 3 Wherein the siliceous
are possible Without departing from the scope of this inven material is added to the paper furnish folloWed by addition
tion. of the amphoteric polymer.
6. A method according to claim 3, Wherein the siliceous
1. Amethod of controlling pitch and stickies deposition in material is an anionic microparticulate material.
papermaking Which method comprises the step of adding to 7. A method according to claim 3, Wherein the siliceous
paper furnish prior to sheet formation a composition com material comprises material selected from the group con
US 2006/0000570 A1
sisting of silica based particles, silica microgel, colloidal
silica, silica sols, silica gels, polysilicates, cationic silica,
aluminosilicates, polyaluminosilicates, borosilicates, poly
borosilicates and Zeolites.
8. A process according to claim 3 Wherein the siliceous
material is a sWellable clay.
9. A process according to claim 8 Wherein the sWellable
clay is selected from the group consisting of hectorite,
smectitites, montmorillonites, nontronites, saponite, sauco
nite, hormites, attapulgites, and sepiolites.
10. A method according to claim 2, Wherein m is from
about 1 to about 8%.
11. A method according to claim 1, Wherein p is from
about 1 to about 8%.
12. A method according to claim 1, Wherein the ampho
teric polymer has a molar ratio of n/m of about 1.2 or greater.
13. A method according to claim 12, Wherein the molar
ratio of n/m is about 4 or greater.
14. A method according to claim 1, Wherein
n represents a unit derived from a cationic monomer
selected from the group consisting of diallyldialkylam
monium compounds;
m represents a unit derived from an anionic monomer or
potentially anionic monomer selected from the group
Jan. 5, 2006
consisting of hydrolysed acrylamide, hydrolysed meth
acrylamide, acrylic acid, methacrylic acid and/or salts
of acrylic acid or methacrylic acid.
15. Amethod according to claim 14, Wherein the anionic
monomer is hydrolysed acrylamide.
16. Amethod according to claim 14, Wherein the anionic
monomer is acrylic acid, methacrylic acid and/or salts
thereof.
17. A method according to claim 14, Wherein the cationic
monomer is diallyldiethylammonium halide or diallydim
ethylammonomium halide.
18. A method according to claim 1, Wherein the ampho
teric polymer of formula (I) has a Weight average molecular
Weight ranging from about 10,000 to about 20,000,000.
19. A method according to claim 1, Wherein the paper
furnish contains thermal mechanical pulp, recycled pulp,
coated broke, deinked pulp or mixtures thereof.
20. A composition for pitch and stickies control in paper
making comprising a structure (I) according to claim 1 and
optionally, a siliceous material.