Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymer of an ethylenically unsaturated reactant with a...
Reexamination Certificate
2000-12-21
2003-02-25
Cain, Edward J. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymer of an ethylenically unsaturated reactant with a...
Reexamination Certificate
active
06525169
ABSTRACT:
BACKGROUND OF THE INVENTION
In the production of paper from aqueous papermaking furnish (stock)—depending on the various employed materials, i.e. pulps (pulps from virgin fibre, broke and/or reclaimed paper) and wet end additives, equipment and process conditions—the stock may contain a certain amount of dissolved components and suspended very fine to microscopic size components, which will normally not be retained completely in the paper web, but will be present in the white water, in which the suspended particles are visible as turbidity.
In the preparation of stock for papermaking the following operations are usually involved: 1) pulping, 2) beating and refining, 3) addition of wet end chemicals and 4) metering and blending.
In 1) [pulping] the various fibrous materials (virgin fibre, broke, reclaimed papers) are dispersed in water by means of suitable dispersing devices (pulpers, deflakers).
By 2) [beating or refining] the fibres are physically modified (by removing of primary fibre wall, bruising, swelling, hydration, etc. . . . ) in such a way as to be suitable for the desired paper production.
Operations 1) and 2) may, if desired, be combined with each other.
Before conveying the stock to the papermaking machine of the assembly, any wet end chemicals are admixed [operation 3)].
If desired, before addition of 3), different kinds of papermaking materials are metered and blended [operation 4)]. Machine broke or reclaimed paper (the latter is suitably also deinked) are preferably repulped separately and then metered and blended with another pulp.
A paper furnish stock often contains pre-refined virgin fibres blended with broke, or for recycled paper, deinked reclaimed fibres optionally blended with broke.
The various components of the white water resulting from drainage, may derive mainly from the following stages: from stages 1) and/or 2) there may result e.g. lignin sulphonates, lignin degradation products, wood extractives, cellulose derivatives (e.g. hemicellulose). From stages 3) and 4) and in particular from the use of optionally coated broke or reclaimed paper there may result components derived from fillers (e.g. white pigments, dispersants, wetting agents, etc. . . . ), from other additives (e.g. modified starches, carboxymethylcellulose, sizing agents, dispersants, dyes, fluorescent whitening agents, coating binders, wetting agents, sodium silicates, biocides, deinking soaps, etc. . . . ) and from the employed water (e.g. humic acids and water hardness salts).
The kind and proportion of such contaminants (dissolved components and fine to microscopic suspended components) in the backwater may vary broadly. Their amounts are particularly relevant in stocks from broke or reclaimed paper and where white water is recycled in the system. These backwater components represent an encumbrance of the backwater in particular with a view to its purification, and furthermore—especially where white water is recycled in the system—the presence of the above mostly anionic contaminants may lead to production problems, e.g. to sheet breaks or loss of sheet quality (e.g. holes and non-uniformity), and may impair the activity of cationic additives (such as flocculants, drainage assistants, retention aids, wet strength resins, synthetic sizing agents, cationic dyes, etc. . . . ) by forming inactive complexes with the anionic contaminants.
It is thus desirable to find a means for reducing the quantity of such backwater components and for enhancing the activity of any cationic wet end additives. In EP-A 0810322 there are described certain polyaminoethers, obtained by reaction of polyethyleneglycol, epichlorohydrin and certain primary diamines with alkaline crosslinking, which are indicated in the specification as being suitable as retention and drainage agents, fixatives and flocculants; the problem to which the there described invention refers relies however only in the retention and drainage efficiency in paper production and an improvement over the state of the art is mentioned only in relation to drainage and retention.
From EP-A-810322, WO-A-95/15996, U.S. Pat. Nos. 4,056,510 and 4,281,199 there are known certain polymers from reaction products of polyol/epichlorohydrin adducts with polyamines, which are essentially non-quaternary, and may be used in various phases of paper production, also as additives to the pulp.
SUMMARY OF THE INVENTION
It has now surprisingly been found that the below defined polycationic, polyquaternary polymers (P) of high cationic density are of outstanding efficiency in particular as fixatives in the production of paper.
The invention relates to the polycationic polymers (P) defined below, their production and use, and aqueous compositions thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention thus provides a polycationic polyquaternary product (P) obtainable by reaction of
(A) an oligohydroxyalkane of molecular weight ≧92 in which the the alkane backbone is optionally interrupted by one or more ether bridges, or a mixture of two or more thereof, or a mixture one or more thereof with a C
2-3
-alkanediol,
with (B) epichlorohydrin,
in the ratio of at least 1 mole of epichlorohydrin for every molequivalent of oligohydroxycompound of molecular weight ≧92 plus 1-4 moles of epichlorohydrin for every molequivalent of C
2-3
-alkanediol, to give a chloro-terminated adduct (E), and quaternizing, optionally cross-linking, reaction of (E) with
(C) at least one aliphatic mono or oligoamine containing on average not more than one nitrogen-bound hydrogen per nitrogen atom.
As oligohydroxyalkanes of molecular weight ≧92 there may be employed known compounds, in particular low molecular oligohydroxyalkanes with 3 to 6 hydroxy groups or polyalkyleneglycols. Preferably (A) is selected from
(A
1
) an oligohydroxyalkane of the formula
X—(OH)
x1
(Ia),
in which
X signifies the x1-valent radical of a C
3-6
-alkane
and x1 signifies a number from 3 to the number of carbon atoms in X, or a mixture of oligohydroxyalkanes of formula (Ia), or a mixture one or more oligohydroxyalkanes of formula (Ia) with a C
2-3
-alkanediol,
and (A
2
) a polyalkylene glycol of the average formula
HO-(Alkylene-O)
x2
—H (Ib),
wherein
Alkylene signifies C
2-4
-alkylene
and x2 signifies a number from 2 to 40.
As amines (C) there may be employed known aliphatic mono- or oligoamines in which at least some of the amino nitrogens are substituted with an aliphatic substituent that does not interfere with the reaction, preferably low molecular alkyl or hydroxyalkyl. (C) is preferably selected from
(C
1
) at least one aminocompound of formula
wherein
Y signifies C
2-3
-alkylene,
y signifies a number from 0 to 3,
R
1
signifies C
1-3
-alkyl or C
2-3
-hydroxyalkyl
and R
2
signifies C
1-3
-alkyl or C
2-3
-hydroxyalkyl, if y is 1 to 3, or hydrogen, if y is 0,
(C
2
) a tertiary amine of formula
N(R
1
)
3
(III)
and (C
3
) at least one diamine of formula
wherein
R
3
signifies hydrogen, C
1-3
-alkyl or C
2-3
-hydroxyalkyl
and w signifies a number from 2 to 6.
The process for the production of (P) is thus characterized in that (A) is reacted with (B) in the above indicated ratio of (B) to (A), to give a chloro-terminated adduct (E), and (E) is reacted with (C) to give a polyquaternary product.
The reaction components and their molar ratios are chosen so that a polyquaternary product, i.e. a product with at least two quaternary ammonium groups per molecule, is formed, preferably so that a product of polymeric character is formed, i.e. a product that contains repeating units derived from (A), in particular cross-linked products, or/and in which (A) is of polymeric character in particular a polyalkyleneglycol preferably corresponding to (A
2
).
According to a preferred feature the invention thus provides polycationic, polyquaternary polymers (P
1
) obtainable by reaction of
(A
1
) an oligohydroxyalkane of the formula
X—(OH)
x1
(Ia),
in which
X signifies the x1-valent radical of a C
Cain Edward J.
Clariant Finance (BVI) Limited
Silverman Richard P.
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