CA1306570C - Pitch control aid in paper making - Google Patents
Pitch control aid in paper makingInfo
- Publication number
- CA1306570C CA1306570C CA000526936A CA526936A CA1306570C CA 1306570 C CA1306570 C CA 1306570C CA 000526936 A CA000526936 A CA 000526936A CA 526936 A CA526936 A CA 526936A CA 1306570 C CA1306570 C CA 1306570C
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- Canada
- Prior art keywords
- polymer
- component
- pulp
- amine
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
- D21C9/086—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching with organic compounds or compositions comprising organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Medicines Containing Plant Substances (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Liquid Crystal Substances (AREA)
- Valve Device For Special Equipments (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Epoxy Resins (AREA)
- Farming Of Fish And Shellfish (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
ABSTRACT
A method for the control of pitch in an aqueous system used in pulp or paper making is disclosed which comprises adding to the system, or to the pulp making or paper making machinery, a water soluble polymer derived from (a) an epihalohydrin, a diepoxide or a precursor of an epihalohydrin or diepoxide, (b) an alkyl amine having a functionality with respect to an epihalohydrin of 2 and (c) an amine which has a functionality with respect to an epihalohydrin greater than 2 and which does not possess any carbonyl groups.
A method for the control of pitch in an aqueous system used in pulp or paper making is disclosed which comprises adding to the system, or to the pulp making or paper making machinery, a water soluble polymer derived from (a) an epihalohydrin, a diepoxide or a precursor of an epihalohydrin or diepoxide, (b) an alkyl amine having a functionality with respect to an epihalohydrin of 2 and (c) an amine which has a functionality with respect to an epihalohydrin greater than 2 and which does not possess any carbonyl groups.
Description
`-- ~3~65~i10 `~
n ~
This invention relates to the control of pitch in the manufacture of pulp and paper.
It is well known that "pitch" can accumulate in paper making and also in the manu~acture of pulp, causing significant problems. ~Pitch" is the term used to describe the sticky materials which appear in paper maklng; these originate from the wood from which the paper is made.
However, nowadays when more recycled paper is used, ~pitch"
is now used as a general term for all material soluble in organic solvents but not soluble in water, for example the ink or adhesive present ~n recycled paper. The pitch can accumulate at various points in the system. For example, it can block the felt and thus hinder drainage of the paper web. In addition, it can adhere to the wires or drying cylinders causing it to pick holes in the paper. Deposits may also build up at any earlier stage in the papermaking process. When these deposits break loose they may form a defect in the paper such as a spot or a hole. Such defects may even create a weakness in the paper sufficient to induce a breakage in the paper during the production resulting in unappreciated production down-time.
Many mater$als have been used in an attempt to eliminate these problems. Such materials include inorganic treatments such as talc and anionic dispersants. However, conventional dispersants can be ineffective ~n a closed system as there can be a build-up of "pitch". In such - ~31~6~70 systems the pitch particles have to be removed from the water system in a controlled way without being allowed to accumulate on the felt or rolls or, for example, the pipe work used in the paper making machinery. These products have also been found to give a limited effect and there is a need for further improved treatments.
It has now been found, according to the present invention, that certain water soluble poly-quaternary amines are particularly effective for this purpose. Accordingly, the present invention provides a method for the control of pitch in an aqueous system used in pulp or paper making which comprises adding to the system, or to the pulp making or papermaking machinery, a water soluble polyquaternary branched polymer derived from (a) an epihalohydrin, a diepoxide or a precursor of an epihalohydrin or diepoxide, (b) an alkyl amine having a functionality with respect to an epihalohydrin of 2 and (c) an amine having functionality which has a functionality with respect to an epihalohydrin of greater than 2 and which does not possess any carbonyl groups under one or more of the following conditions: i) the polymer is added to the pulp making or papermaking machinery, ii) the pulp is of recycled paper containing adhesive, and, iii) components (a) and (b) are reacted to form a coupling agent which is then reacted wi~h component (c).
1306St~O ~
-2a-A special feature Oe the products u~ed in the present invention is that they may combine with dissolved anionlc material originating from the wood from which the pulp and paper is produced, providing a method of removing these anionic materials thereby lowering the concentration of such materials in the process water. Water soluble anionic materials are released from the wood during pulp manufacture. These components interfere with paper -.~., 13065~70 production negatively in several ways: they decrease the efficiency of many products used in the papermaking process to alter the character of the paper. Examples of such additives include sizes, wet and dry strength agents and dyes. Anionic dissolved materials also reduce the efficiency of retention agents. They limit the extent to which the water system can beclosed and they may also lower the quality of the paper such as its strength. Reference is made to TAPPI papermakers Conference 1979 p49-66 which further discusses, the significance of anionic dissolved materials.
Component (a) is preferably an epihalohydrin, especially epichlorohydrin or epibromohydrin, but dihalohydrins, preferably dichlorohydrins or dibromohydrins, having three to twenty, especially three to ten, carbon atoms per molecule may also be used. Typical dihalohydrins which may be used include the following:
CH ClCHClCH OH
n ~
This invention relates to the control of pitch in the manufacture of pulp and paper.
It is well known that "pitch" can accumulate in paper making and also in the manu~acture of pulp, causing significant problems. ~Pitch" is the term used to describe the sticky materials which appear in paper maklng; these originate from the wood from which the paper is made.
However, nowadays when more recycled paper is used, ~pitch"
is now used as a general term for all material soluble in organic solvents but not soluble in water, for example the ink or adhesive present ~n recycled paper. The pitch can accumulate at various points in the system. For example, it can block the felt and thus hinder drainage of the paper web. In addition, it can adhere to the wires or drying cylinders causing it to pick holes in the paper. Deposits may also build up at any earlier stage in the papermaking process. When these deposits break loose they may form a defect in the paper such as a spot or a hole. Such defects may even create a weakness in the paper sufficient to induce a breakage in the paper during the production resulting in unappreciated production down-time.
Many mater$als have been used in an attempt to eliminate these problems. Such materials include inorganic treatments such as talc and anionic dispersants. However, conventional dispersants can be ineffective ~n a closed system as there can be a build-up of "pitch". In such - ~31~6~70 systems the pitch particles have to be removed from the water system in a controlled way without being allowed to accumulate on the felt or rolls or, for example, the pipe work used in the paper making machinery. These products have also been found to give a limited effect and there is a need for further improved treatments.
It has now been found, according to the present invention, that certain water soluble poly-quaternary amines are particularly effective for this purpose. Accordingly, the present invention provides a method for the control of pitch in an aqueous system used in pulp or paper making which comprises adding to the system, or to the pulp making or papermaking machinery, a water soluble polyquaternary branched polymer derived from (a) an epihalohydrin, a diepoxide or a precursor of an epihalohydrin or diepoxide, (b) an alkyl amine having a functionality with respect to an epihalohydrin of 2 and (c) an amine having functionality which has a functionality with respect to an epihalohydrin of greater than 2 and which does not possess any carbonyl groups under one or more of the following conditions: i) the polymer is added to the pulp making or papermaking machinery, ii) the pulp is of recycled paper containing adhesive, and, iii) components (a) and (b) are reacted to form a coupling agent which is then reacted wi~h component (c).
1306St~O ~
-2a-A special feature Oe the products u~ed in the present invention is that they may combine with dissolved anionlc material originating from the wood from which the pulp and paper is produced, providing a method of removing these anionic materials thereby lowering the concentration of such materials in the process water. Water soluble anionic materials are released from the wood during pulp manufacture. These components interfere with paper -.~., 13065~70 production negatively in several ways: they decrease the efficiency of many products used in the papermaking process to alter the character of the paper. Examples of such additives include sizes, wet and dry strength agents and dyes. Anionic dissolved materials also reduce the efficiency of retention agents. They limit the extent to which the water system can beclosed and they may also lower the quality of the paper such as its strength. Reference is made to TAPPI papermakers Conference 1979 p49-66 which further discusses, the significance of anionic dissolved materials.
Component (a) is preferably an epihalohydrin, especially epichlorohydrin or epibromohydrin, but dihalohydrins, preferably dichlorohydrins or dibromohydrins, having three to twenty, especially three to ten, carbon atoms per molecule may also be used. Typical dihalohydrins which may be used include the following:
CH ClCHClCH OH
CH2ClCH2(OH)CH2Cl CH3CHClCHClCH2OH
CH3CHClCH(OH)CH2Cl CH3CH2CHClCHClCH20H
CH3CHClCHClCH(OH)CH3 cH3cH2cHclcH(OH) CH3CH2cH(oH)cHclcH
CH3CHClCH(OH)CHClCH3 13065~0 CH3CCHClCH2Cl OH
j~3 CH2ClfCHClCH3 and OH
CH2 (OH ) C-CHClCH3 As regards component (b) the alkyl amine may be a compound possessing two tertiary amino groups such as N,N,N',N'-tetramethyleneethylenediamine. Details of the preparation of products derived from such component (b1 and component (a) can be fo~nd in UK-A-l 486 396. However, component ~b) is preferably a dialkylamine in which the alkyl groups individually contain one to three atoms.
Dimethylamine is esPecially preferred.
As previously indicated, component (c) is an amine which possesses a functionality greater than two with respect to epihalohydrin and which does not possess any carbonyl groups; it can therefore act as a branching agent.
It has been found that the use of a branched polymer is an important feature in the performance of the polymer to 13~65`~0 prevent deposition of pitch, as the comparative experiments below show. ~ primary amino group is capable of reacting with three molecules of epihalohydrin so that a simple primary amine possesses a functionality of three.
Likewise, a simple secondary amine will possess a functionality of two and a simple tertiary amine a functionality o~ one. Accordingly, component (c) is typically ammonia, a primary amine, a primary alkylene polyamine having four to twenty-five, preferably four to twelve, carbon atoms and at least one, preferably one to six, primary amino groups per molecule including polyglycolamines as well as aromatic and heteroaromatic diamines but not polyamidoamines because they possess carbonyl groups. Preferred materials include ammonia, diethylaminobutylamine, dimethylaminopropylamine and ethylenediamine, the latter two being especially preferred.
If desired, the polymer may also be derived from a further component which generally has the ability to act as a "end-capping" agent. In general, these materials will also be amines or other material having reactivity towards epichlorohydrin and which possess a functionality less than two and which also possess some other functional group or a fatty chain of, say, at least 12 carbon atoms, such as a simple tertiary amine such as a trialkylamine, especially trimethylamine or a hydroxyalkylamine, typically triethanolamine, or a fatty amine such as octadecylamine.
The polymers used in the present invention may be 13V6S~O
prepared by first reacting components (a) and (b) to obtain a "coupling agent" and then reacting this with component (c) and, if desired, the fourth component. Preferred polymers for use in the present invention include those in S which the coupling agent is derived from epichlorohydrin and dimethylàmine, which is subsequently reacted with ethylenediamine and, iE desired, also with trimethylamine, triethanolamine or octadecylamine.
The polymers may also be prepared by reacting a mixture of components (b) and (c) with component (a). The preferred raw materials for such a process are the same as those given above.
In general, the reaction is carried out in an aqueous medium, typically maintaining the reaction temperature at 5 to 125C, preferably 30 to 95C. The equivalent ratio of component (b) to component (c) is suitably 1:0.009 to 1.0 and preferably 1:0.02 to 0.5 while the equivalent ratio of component (a) to components (b) and (c) may vary widely depending on the amount and nature of component (b). Generally, the ratio of component (c) to component (a) and component (b), together should be selected so that the viscosity of the aqueous polymer solutlon is at least 20 Cps at 50~ dry content. Typically, the ratio is from 1:0.22 to 2.5 and preferably 1:0.25 to 1.3. In general, the reaction can be continued until the desired viscosity, and therefore molecular weight, has been achieved although acid can be used to reduce the pH and 1306S~0 thereby terminate the reaction. A pH of 1 to 7.5, especially 2 to 6.5, is generally preferred for the inal solution.
The upper viscosity limit is not critical provided it is consistent with having a workable solution;
the upper limit is normally about 2000 Cps.
Further details regarding the polymers which can be used and their preparation is to be found in, inter alia, UR-A-2 085 433, US-A-3 855 299 and US Patent Re-Issue 28 808 and, for certain polymers, in "Polyelectrolytes for Water and Wastewater Treatment", ed W L K Schwoyer, CRC
Press Inc, pages 26 - 35. A particularly preferred polymer for use in the present invention is formed by reacting ethylenediamine with a precondensate of dimethylamine and epichlorohydrin, and reacting the product with triethanola~ine to form a water-soluble reaction product.
Another preferred product is formed by reacting a mixture of dimethylamine and ethylenediamine or dimethylaminopropylamine with epichlorohdyrin to form a water-soluble reaction product.
The polymer is generally added to the aqueous system with the furnish containing the paper pulp but it is possible to add it at different points in the system depending on the precise nature of the problem.
2~ The amount of polymer required will, of course, depend to some extent on the nature of the wood or other material used to prepare the paper pulp. Also, some ~ ~V65~70 polymer once added will tend to recirculate in the system thus requiring a lower addition rate. In general, however, from 0.1 to 20 ppm of polymer by weight based on the aqueous medium is suitable. Pre~erably, the amount is 1 to 10 ppm. This corresponds in the normal cas~ to an addition of lo to 2,000 grams, preferably 100 to 1,000 grams, polymer per tonne fibre. ~owever, in cases where the polymer is required to neutralize anionic dissolvea materials, generally higher amounts are desirable, in the normal case from 1,000 grams to 50,000, especially from 1,500 to 1~,000 grams, per tonne fibre depending on the process by which the fibres are produced (see, for example, Progr. Colloid & Polymer sci. 65, 251-264 (1978) for a discusssion of the amounts of anionic material likely to be present). Fibres produced by a mechanical process generally require a higher addition than fibre prepared by a chemical process. It is, of course, also possible to only partly neutralize the total amount of dissolved anionic materials. In such cases amounts from as little as, say, 10 grams per tonne of paper may be effective.
Sometimes it can be preferred to spray the reaction product used in this invention onto a particular part of the pulp- or paper-making machinery such as the wire or press felts. In such cases, the polymer is preferably pre-diluted with water, generally to a concentration below 10~ by weight and preferably 1 to 5% by weight.
13065'70 In some instances, it will be convenient to add the polymer together with a biocide. Examples of suitable biocides include those in the :Eollowing classes:
(i) a substituted 5- or 6-membered ring heterocyclic compound in which the hetero atom or atoms are one or more of nitrogen, oxygen or sulphur and the substituent is an alkyl group, a keto group or a hydroxyl group or a halogen atom, such compounds include isothiazolones, and in particular, those having the formula:
S - ~ R
CH - N
wherein R represents hydrogen or chlorine. A blend of these two isothiazolones is commercially available, the weight ratio of the chloro-substituted compound to the unsubstituted compound being about 2.66:1;
(ii) a phenol or chlorinated phenol such as pentachlorophenol (iii) an amine or amide including 2,2-dibromo-3-nitrilopropionamide;
(iv) an organic cyanide or thiocyanate, particularly methylene bis(thiocyanates3;
(v) a sulphone including halosulphones, particularly hexachlorodimethylsulphone:
13~6S~
(vi) a straight chain aliphatic aldehyde, particularly glutaraldehyde;
(vii) a triazine, particularly thio and/or amino-substituted alkyl triazines;
(viii) bis bromo acetoxy butene- and ( ix) a dithiocarbamate, especiallY the monomethyl, dimethyl, monoetnyl and diethyl derivatives, typically in the form of sodium salts.
The polymer is generally compatible with the usual pulp and paper making additives including starch, for example potato or corn starch, titanium dioxide, a de-foamer such as a fatty acid alcohol, a size, for example a rosin size based on abietic acid, a neutral size based on alkyl ketene dimer or a succinic acid anhydride based size and a wet strength resin such as, if neutral, an epichlorohydrin polyamide or, if acid, a melamine- or urea-formaldehyde resin.
The precise nature of the pH of the system is unimportant since the e~fectiveness of the polymer is substantially unaffected by changes in pH.
Some of the polymers used in the present invention are commercially available, typically as aqueous solutions containing a concentration of 40 to 50% per cent.
Typically, the compositions used in the present invention will possess from 1 to 70%, especially 10 to 30~, by weight of the polymer.
The following examples ~urther illustrate the ~30f~5~0 present invention.
Into a reaction flask fitted with reflux condenser, mechanical stirrer and thermometer were placed 183.5 g of 32.7% dimethylamine and 270g of water. 76.04 g of 36% hydrochloric acid was added while maintaining a temperature maximum of 35C by cooling. 208.12 g epichlorohydrin was added during 30 minutes. Cooling was applied to keep the temperature not above 4~C. This temperature was maintained for two hours to produce a stock solution of so-called "coupling agent". 176.9 g of the aqueous solution of the coupling agent was, using the same equipment, heated to 60C. 5.94 g of ethylenediamine was added dropwise over a 30 minute period. The temperature was then kept at 60C for one hour. The reaction mixture was heated to 90C and 32.48 g of 30% trimethylamine was added during ten minutes; gnc was then maintained for two hours and the reaction mixture cooled to room temperature.
This reaction mixture had a total solids content of 40.7%.
using the equipment described in Example 1, 25.35 g of 36% hydrochloric acid was added to a mixture of 68.81 g of 32.7% dimethylamine solution and 121.4 g water. The temperature was kept below 35C by cooling. 83.25 g epichlorohydrin was added at such a rate that temperature was maintained at 40C. This temperature was then kept for one hour. The reaction mixture was heated to 60C and 1306S~0 7.5 9 ethylene diamine was added over 15 minutes while maintaining the temperature at 60c. This temperature was kept for another 30 minutes. The reaction mixture was heated to 90C and 37.25 g triethanolamine was added dropwise over 30 minutes. This temperature was maintained for a further two hours to complete the reaction. The total solids content was 44.6%.
The products prepared in Examples 1 and 2 were evaluated using essentially the method described in 1977 TAPPI paper makers Conference p 23-32 by Ch E ~arley. This method is built on TAPPI Standard Method RC324 which is a recognised method for evaluating depositability of pitch.
The standard pitch solution was prepared as described in the above references. A synthetic pitch emulsion/dispersion was prepared by adding one litre volume of deionised water at 50C to the synthetic pitch to reach a 1200 ppm concentration.
~ solution of calcium chloride was added to reach a hardness of 340 ppm expressed as calcium carbonate. The pH was adjusted to 8Ø To evaluate the products as pitch control agents, the products were added to obtain a concentration of polymer as specified in Table I. The depositability of the pitch was evaluated according to the procedure in the above references. The test duration was always five minutes. The results are presented in Table I
(mg deposited pitch).
13(:~65'7~) TABLE I
PRODUCTCONCENTRATION (PPM) DEPOSITED PITCH (MG) ~lank -- 280 Example 1 2 252 5 Example 1 10 2 Example 2 2 255 Example 2 10 28 An amino~last resin was prepared essentiall~
according to Example III in US Patent 3 582 461 for comparison.
84 g tl mole) of dicyandiamide, 196 (2.4 moles) of 37% by weight inhibited aqueous formaldehyde solution, 126 g tmole) o~ 85% active formic acid were charged into a 1 litre four neck flask equipped with an agitator, thermometer and condenser. The mixture was agitated for 0.5 hours at room temperature. External heat was applied to the reaction mixture and the mixture was heated to 60C
over a 0.5 hour period. The reaction temperature was gradually raised from 60C to the boiling point of the mixture. The exothermic reaction, which occurred when the temperature was raised above 60C, was controlled by intermittent cooling. The boiling point of the reaction mixture was reached after three hours heating. The mixture was boiled for 15 minutes and then cooled rapidly to 55C.
42 g of methanol was added to etherify free methylol groups 13~65'~0 and the mixture was agitated for 2.5 hours and then cooled to 25C. The resulting reaction product was a water soluble dicyandiamide-~ormaldehyde condensate in the form of a clear water soluble syrup containing 40~ by weight solids.
This resin was evaluated according to procedure in Example 3 with the following results.
concentration (ppm) Deposit (mg) Blank 299 2 ~ 93 10 ppm 80 Some other products with potential as pitch control agents were evaluated following the procedure of ~xample 3 with the following results.
15 Product Concentration ~eposit (mq) . . .
Blank - 299 Polyacrylate100 Ppm 212 Cationic starch 100 ppm 94 Paper makers' alum 100 ppm 41 To a mixture of 68.81 g of 32.7% dimethylamine and 121.4 g water was added 25.35 g of 36% hydrochloric 130~;5~(~
acid dropwise over 30 minutes. The temperature of the reaction mixture was not allowed to e~ceed 35C, some cooling was req~ired. 83.25 g of epichlorohydrin was added at such a rate that the temperature of the reaction mixture was maintained at 40C. After the exothermic reaction was completed the solution was maintained at 40C until it became clear (1 hour). After heating to 60C, 7.5 g of ethylenediamine was added quickly over 5 minutes. The reaction mixture was maintained at 65C for a further hour.
The reaction mixture was then cooled to room temperature.
To 97.42 g of this solution was added 22.56 g octadecylamine (2 moles) and 7.5 g 2-methoxy ethanol (to assist solution). This slurry was slowly heated to 70C
and maintained at this temperature for 30 minutes. Further heating to 75C produced a highly exothermic reaction which required external cooling to maintain a temperature of 75C. After completion of the exothermic reaction, the mixture was heated at 90C for 2 hours. The product, which was in the form of a creamy emulsion, had a total solid content of 18%.
EXAM~LE 5 The product of Example 4 was evaluated using the method described in Example 3, bu~ a different synthetic pitch was used. This time a Pitch solution was made by adding a mixture of 2.0 g tall oil and 20.0 g glycerol ester of rosin to 10.5 g 5% potassium hydroxide to form an 13~6~'70 emulsion. This was then diluted with 1~7.5 g isoproPanol and l10 9 acetone to form a clear pitch solution. l5 ml of this solution was added to one litre water at 20C and a hardness of 200 p~m expressed aS calcium carbonate. The pH
was adjusted to 3.0 using concentrated hydrochloric acid and the test was carried out over three minutes.
Concentration (ppm) Deposit (mg) Blank 250 3.5 23 7.5 Nil Polydiallyl dimethyl ammonium chloride (poly DADMAC) is another poly quaternary resin suggested at a pitch control agent, in European Patent Application 58 621.
This resin was tested following the procedure in Example 5.
Concentration (ppm) Deposit (mg) ~0 1~ 27 trhe preferred type of quaternary compound for control of pitch deposition in US-A-3 619 351 is a ~3C~
methyltriethanolamine. ThiS material was synthesiæed from triethanolamine and dimethyl sulphate to form quaternary ammonium methyl triethanolamine monomethyl sulphate. This material was evaluated using the procedure in ~xample 3 with the following results:
Concentration (ppm) Deposit (mg) Blank 130 10 ppm 16~
100 p~m 102 A resin was prepared only from dimethylamine and epichlorohydrin following essentially the procedure of Example 1 of US reissue 28,807. A 500 ml round bottom flask equipped with condenser, mechanical stirrer, thermometer and pH electrodes was used for the preparation.
92.5 grams (1.0 mole) epichlorohydrin was added to the flask. 112.5 grams of 40% aqueous dimethylamine (45 grams real, 1.0 mole) was added with vigorous stirring over one hour keeping the temperature below 50C. Heating was applied ~or another two hours at 50C whereafter 70g water was added. The viscosity of this resin was determined to be 72 cps and dr~ content was ~ound to be 47 percent.
The same equipment as in Comparative Example 5 i30Ç~7~) was used: 63.S g water, 99 ethylenediamine and 121.99 aqueous solution (36.5%) of dimethylamine was added to the reaction flask. 1709 epichlorohydrin was added over a three hour period maintaining the temperature below 35C by cooling. Temperature was then increased to 80C. 11.89 epichlorohydrin was added in six portions over three hours and after the last addition the reaction mass was kept at 80C for an additional two hours, whereafter the product was cooled to room temperature. The product was a pale yellow slightly opaque liquid with a dry content of 65.8%
and a viscosity of 190 cps.
The same equipment as in Comparative Example 5 was used. Water t34.2g), dimethylamine (60.9g of an aqueous 36.9~ solution) and ethylenediamine (1.5g) were charged to the reaction flask. 51.0g epichlorohydrin was added with vigorous stirring over 2 hours. Temperature was raised to 80C and 10.6g epichlorohydrin was added in 9 portions over a 8 hour Period. The final product was a slightly opaque, pale yellow liquid. Dry content of this product was found to be 58.8~ and the viscosity approx 1000 cps .
The equipment of Comparative Example 5 was used.
~ resin was prepared in the following way: 112.5 grams 40%
~3~?~S'70 dimethylamine was added to the reaction flask together with 10.2 grams dimethylaminopropylamine. These two amines were mixed and 102 grams of epichlorohydrin was added over 30 minutes with vigorous stirring maintaining a temperature of 30-40C. Temperature was then increased to 60C which was maintained for 5 hours. During this period of time, 300ml of deionised water was added in small portions. This resin had a viscosity of 20 cps and a dry content of 33%.
The products of Comparative Example 5 and Examples 6 to 8 were evaluated following the procedure of Example 5 at an addition of l.Oppm polymer with the following results:
15 Product Deposit (mg~
Blank 272 Resin of Example 7 201 Resin of Example 6 138 Resin of Comparative Example 5 228 20 Resin of Example 8 186 Blank 260 The resin of Example 6 was evaluated using the method of Example 3. The following results were obtained:
13065'70 Concentration (ppm)~eposit ~mg) slank 133 2ppm 121 5ppm 29 lOppm 6 In order to evaluate the usefulness of polymers to combine with anionic dissolved components of paper pulp the rollowing experiment was made:
A dried groundwood pulp from pine was disintegrated for 30 minutes to prepare a 2.5% furnish.
The fibres were subsequently filtered off and the filtrate was used to evaluate the capacity of the resins to combine with dissolved anionic materials. The amount of anionic material was determined with a streaming current detector.
Polyethyleneimine (PEI) was used as standard. The efficiency to combine with anionic material was evaluated by adding to the filtrate various amounts of resin, stirring for 15 minutes and subsequently determining the residual concentration of uncombined anionic material by titration with the standard reagent. The results were as follows:
l~Q65~0 PEI mg/l Filtrate Blank 7,1 4ppm of resin of ~xample 7 4,8 8ppm of resin of Example 7 1,9 4ppm of resin of Example 8 4,6 8ppm of resin of Example 8 1,4 8ppm of resin of Example 2 ~,4 50ppm of resin of Example 2 2,3
CH3CHClCH(OH)CH2Cl CH3CH2CHClCHClCH20H
CH3CHClCHClCH(OH)CH3 cH3cH2cHclcH(OH) CH3CH2cH(oH)cHclcH
CH3CHClCH(OH)CHClCH3 13065~0 CH3CCHClCH2Cl OH
j~3 CH2ClfCHClCH3 and OH
CH2 (OH ) C-CHClCH3 As regards component (b) the alkyl amine may be a compound possessing two tertiary amino groups such as N,N,N',N'-tetramethyleneethylenediamine. Details of the preparation of products derived from such component (b1 and component (a) can be fo~nd in UK-A-l 486 396. However, component ~b) is preferably a dialkylamine in which the alkyl groups individually contain one to three atoms.
Dimethylamine is esPecially preferred.
As previously indicated, component (c) is an amine which possesses a functionality greater than two with respect to epihalohydrin and which does not possess any carbonyl groups; it can therefore act as a branching agent.
It has been found that the use of a branched polymer is an important feature in the performance of the polymer to 13~65`~0 prevent deposition of pitch, as the comparative experiments below show. ~ primary amino group is capable of reacting with three molecules of epihalohydrin so that a simple primary amine possesses a functionality of three.
Likewise, a simple secondary amine will possess a functionality of two and a simple tertiary amine a functionality o~ one. Accordingly, component (c) is typically ammonia, a primary amine, a primary alkylene polyamine having four to twenty-five, preferably four to twelve, carbon atoms and at least one, preferably one to six, primary amino groups per molecule including polyglycolamines as well as aromatic and heteroaromatic diamines but not polyamidoamines because they possess carbonyl groups. Preferred materials include ammonia, diethylaminobutylamine, dimethylaminopropylamine and ethylenediamine, the latter two being especially preferred.
If desired, the polymer may also be derived from a further component which generally has the ability to act as a "end-capping" agent. In general, these materials will also be amines or other material having reactivity towards epichlorohydrin and which possess a functionality less than two and which also possess some other functional group or a fatty chain of, say, at least 12 carbon atoms, such as a simple tertiary amine such as a trialkylamine, especially trimethylamine or a hydroxyalkylamine, typically triethanolamine, or a fatty amine such as octadecylamine.
The polymers used in the present invention may be 13V6S~O
prepared by first reacting components (a) and (b) to obtain a "coupling agent" and then reacting this with component (c) and, if desired, the fourth component. Preferred polymers for use in the present invention include those in S which the coupling agent is derived from epichlorohydrin and dimethylàmine, which is subsequently reacted with ethylenediamine and, iE desired, also with trimethylamine, triethanolamine or octadecylamine.
The polymers may also be prepared by reacting a mixture of components (b) and (c) with component (a). The preferred raw materials for such a process are the same as those given above.
In general, the reaction is carried out in an aqueous medium, typically maintaining the reaction temperature at 5 to 125C, preferably 30 to 95C. The equivalent ratio of component (b) to component (c) is suitably 1:0.009 to 1.0 and preferably 1:0.02 to 0.5 while the equivalent ratio of component (a) to components (b) and (c) may vary widely depending on the amount and nature of component (b). Generally, the ratio of component (c) to component (a) and component (b), together should be selected so that the viscosity of the aqueous polymer solutlon is at least 20 Cps at 50~ dry content. Typically, the ratio is from 1:0.22 to 2.5 and preferably 1:0.25 to 1.3. In general, the reaction can be continued until the desired viscosity, and therefore molecular weight, has been achieved although acid can be used to reduce the pH and 1306S~0 thereby terminate the reaction. A pH of 1 to 7.5, especially 2 to 6.5, is generally preferred for the inal solution.
The upper viscosity limit is not critical provided it is consistent with having a workable solution;
the upper limit is normally about 2000 Cps.
Further details regarding the polymers which can be used and their preparation is to be found in, inter alia, UR-A-2 085 433, US-A-3 855 299 and US Patent Re-Issue 28 808 and, for certain polymers, in "Polyelectrolytes for Water and Wastewater Treatment", ed W L K Schwoyer, CRC
Press Inc, pages 26 - 35. A particularly preferred polymer for use in the present invention is formed by reacting ethylenediamine with a precondensate of dimethylamine and epichlorohydrin, and reacting the product with triethanola~ine to form a water-soluble reaction product.
Another preferred product is formed by reacting a mixture of dimethylamine and ethylenediamine or dimethylaminopropylamine with epichlorohdyrin to form a water-soluble reaction product.
The polymer is generally added to the aqueous system with the furnish containing the paper pulp but it is possible to add it at different points in the system depending on the precise nature of the problem.
2~ The amount of polymer required will, of course, depend to some extent on the nature of the wood or other material used to prepare the paper pulp. Also, some ~ ~V65~70 polymer once added will tend to recirculate in the system thus requiring a lower addition rate. In general, however, from 0.1 to 20 ppm of polymer by weight based on the aqueous medium is suitable. Pre~erably, the amount is 1 to 10 ppm. This corresponds in the normal cas~ to an addition of lo to 2,000 grams, preferably 100 to 1,000 grams, polymer per tonne fibre. ~owever, in cases where the polymer is required to neutralize anionic dissolvea materials, generally higher amounts are desirable, in the normal case from 1,000 grams to 50,000, especially from 1,500 to 1~,000 grams, per tonne fibre depending on the process by which the fibres are produced (see, for example, Progr. Colloid & Polymer sci. 65, 251-264 (1978) for a discusssion of the amounts of anionic material likely to be present). Fibres produced by a mechanical process generally require a higher addition than fibre prepared by a chemical process. It is, of course, also possible to only partly neutralize the total amount of dissolved anionic materials. In such cases amounts from as little as, say, 10 grams per tonne of paper may be effective.
Sometimes it can be preferred to spray the reaction product used in this invention onto a particular part of the pulp- or paper-making machinery such as the wire or press felts. In such cases, the polymer is preferably pre-diluted with water, generally to a concentration below 10~ by weight and preferably 1 to 5% by weight.
13065'70 In some instances, it will be convenient to add the polymer together with a biocide. Examples of suitable biocides include those in the :Eollowing classes:
(i) a substituted 5- or 6-membered ring heterocyclic compound in which the hetero atom or atoms are one or more of nitrogen, oxygen or sulphur and the substituent is an alkyl group, a keto group or a hydroxyl group or a halogen atom, such compounds include isothiazolones, and in particular, those having the formula:
S - ~ R
CH - N
wherein R represents hydrogen or chlorine. A blend of these two isothiazolones is commercially available, the weight ratio of the chloro-substituted compound to the unsubstituted compound being about 2.66:1;
(ii) a phenol or chlorinated phenol such as pentachlorophenol (iii) an amine or amide including 2,2-dibromo-3-nitrilopropionamide;
(iv) an organic cyanide or thiocyanate, particularly methylene bis(thiocyanates3;
(v) a sulphone including halosulphones, particularly hexachlorodimethylsulphone:
13~6S~
(vi) a straight chain aliphatic aldehyde, particularly glutaraldehyde;
(vii) a triazine, particularly thio and/or amino-substituted alkyl triazines;
(viii) bis bromo acetoxy butene- and ( ix) a dithiocarbamate, especiallY the monomethyl, dimethyl, monoetnyl and diethyl derivatives, typically in the form of sodium salts.
The polymer is generally compatible with the usual pulp and paper making additives including starch, for example potato or corn starch, titanium dioxide, a de-foamer such as a fatty acid alcohol, a size, for example a rosin size based on abietic acid, a neutral size based on alkyl ketene dimer or a succinic acid anhydride based size and a wet strength resin such as, if neutral, an epichlorohydrin polyamide or, if acid, a melamine- or urea-formaldehyde resin.
The precise nature of the pH of the system is unimportant since the e~fectiveness of the polymer is substantially unaffected by changes in pH.
Some of the polymers used in the present invention are commercially available, typically as aqueous solutions containing a concentration of 40 to 50% per cent.
Typically, the compositions used in the present invention will possess from 1 to 70%, especially 10 to 30~, by weight of the polymer.
The following examples ~urther illustrate the ~30f~5~0 present invention.
Into a reaction flask fitted with reflux condenser, mechanical stirrer and thermometer were placed 183.5 g of 32.7% dimethylamine and 270g of water. 76.04 g of 36% hydrochloric acid was added while maintaining a temperature maximum of 35C by cooling. 208.12 g epichlorohydrin was added during 30 minutes. Cooling was applied to keep the temperature not above 4~C. This temperature was maintained for two hours to produce a stock solution of so-called "coupling agent". 176.9 g of the aqueous solution of the coupling agent was, using the same equipment, heated to 60C. 5.94 g of ethylenediamine was added dropwise over a 30 minute period. The temperature was then kept at 60C for one hour. The reaction mixture was heated to 90C and 32.48 g of 30% trimethylamine was added during ten minutes; gnc was then maintained for two hours and the reaction mixture cooled to room temperature.
This reaction mixture had a total solids content of 40.7%.
using the equipment described in Example 1, 25.35 g of 36% hydrochloric acid was added to a mixture of 68.81 g of 32.7% dimethylamine solution and 121.4 g water. The temperature was kept below 35C by cooling. 83.25 g epichlorohydrin was added at such a rate that temperature was maintained at 40C. This temperature was then kept for one hour. The reaction mixture was heated to 60C and 1306S~0 7.5 9 ethylene diamine was added over 15 minutes while maintaining the temperature at 60c. This temperature was kept for another 30 minutes. The reaction mixture was heated to 90C and 37.25 g triethanolamine was added dropwise over 30 minutes. This temperature was maintained for a further two hours to complete the reaction. The total solids content was 44.6%.
The products prepared in Examples 1 and 2 were evaluated using essentially the method described in 1977 TAPPI paper makers Conference p 23-32 by Ch E ~arley. This method is built on TAPPI Standard Method RC324 which is a recognised method for evaluating depositability of pitch.
The standard pitch solution was prepared as described in the above references. A synthetic pitch emulsion/dispersion was prepared by adding one litre volume of deionised water at 50C to the synthetic pitch to reach a 1200 ppm concentration.
~ solution of calcium chloride was added to reach a hardness of 340 ppm expressed as calcium carbonate. The pH was adjusted to 8Ø To evaluate the products as pitch control agents, the products were added to obtain a concentration of polymer as specified in Table I. The depositability of the pitch was evaluated according to the procedure in the above references. The test duration was always five minutes. The results are presented in Table I
(mg deposited pitch).
13(:~65'7~) TABLE I
PRODUCTCONCENTRATION (PPM) DEPOSITED PITCH (MG) ~lank -- 280 Example 1 2 252 5 Example 1 10 2 Example 2 2 255 Example 2 10 28 An amino~last resin was prepared essentiall~
according to Example III in US Patent 3 582 461 for comparison.
84 g tl mole) of dicyandiamide, 196 (2.4 moles) of 37% by weight inhibited aqueous formaldehyde solution, 126 g tmole) o~ 85% active formic acid were charged into a 1 litre four neck flask equipped with an agitator, thermometer and condenser. The mixture was agitated for 0.5 hours at room temperature. External heat was applied to the reaction mixture and the mixture was heated to 60C
over a 0.5 hour period. The reaction temperature was gradually raised from 60C to the boiling point of the mixture. The exothermic reaction, which occurred when the temperature was raised above 60C, was controlled by intermittent cooling. The boiling point of the reaction mixture was reached after three hours heating. The mixture was boiled for 15 minutes and then cooled rapidly to 55C.
42 g of methanol was added to etherify free methylol groups 13~65'~0 and the mixture was agitated for 2.5 hours and then cooled to 25C. The resulting reaction product was a water soluble dicyandiamide-~ormaldehyde condensate in the form of a clear water soluble syrup containing 40~ by weight solids.
This resin was evaluated according to procedure in Example 3 with the following results.
concentration (ppm) Deposit (mg) Blank 299 2 ~ 93 10 ppm 80 Some other products with potential as pitch control agents were evaluated following the procedure of ~xample 3 with the following results.
15 Product Concentration ~eposit (mq) . . .
Blank - 299 Polyacrylate100 Ppm 212 Cationic starch 100 ppm 94 Paper makers' alum 100 ppm 41 To a mixture of 68.81 g of 32.7% dimethylamine and 121.4 g water was added 25.35 g of 36% hydrochloric 130~;5~(~
acid dropwise over 30 minutes. The temperature of the reaction mixture was not allowed to e~ceed 35C, some cooling was req~ired. 83.25 g of epichlorohydrin was added at such a rate that the temperature of the reaction mixture was maintained at 40C. After the exothermic reaction was completed the solution was maintained at 40C until it became clear (1 hour). After heating to 60C, 7.5 g of ethylenediamine was added quickly over 5 minutes. The reaction mixture was maintained at 65C for a further hour.
The reaction mixture was then cooled to room temperature.
To 97.42 g of this solution was added 22.56 g octadecylamine (2 moles) and 7.5 g 2-methoxy ethanol (to assist solution). This slurry was slowly heated to 70C
and maintained at this temperature for 30 minutes. Further heating to 75C produced a highly exothermic reaction which required external cooling to maintain a temperature of 75C. After completion of the exothermic reaction, the mixture was heated at 90C for 2 hours. The product, which was in the form of a creamy emulsion, had a total solid content of 18%.
EXAM~LE 5 The product of Example 4 was evaluated using the method described in Example 3, bu~ a different synthetic pitch was used. This time a Pitch solution was made by adding a mixture of 2.0 g tall oil and 20.0 g glycerol ester of rosin to 10.5 g 5% potassium hydroxide to form an 13~6~'70 emulsion. This was then diluted with 1~7.5 g isoproPanol and l10 9 acetone to form a clear pitch solution. l5 ml of this solution was added to one litre water at 20C and a hardness of 200 p~m expressed aS calcium carbonate. The pH
was adjusted to 3.0 using concentrated hydrochloric acid and the test was carried out over three minutes.
Concentration (ppm) Deposit (mg) Blank 250 3.5 23 7.5 Nil Polydiallyl dimethyl ammonium chloride (poly DADMAC) is another poly quaternary resin suggested at a pitch control agent, in European Patent Application 58 621.
This resin was tested following the procedure in Example 5.
Concentration (ppm) Deposit (mg) ~0 1~ 27 trhe preferred type of quaternary compound for control of pitch deposition in US-A-3 619 351 is a ~3C~
methyltriethanolamine. ThiS material was synthesiæed from triethanolamine and dimethyl sulphate to form quaternary ammonium methyl triethanolamine monomethyl sulphate. This material was evaluated using the procedure in ~xample 3 with the following results:
Concentration (ppm) Deposit (mg) Blank 130 10 ppm 16~
100 p~m 102 A resin was prepared only from dimethylamine and epichlorohydrin following essentially the procedure of Example 1 of US reissue 28,807. A 500 ml round bottom flask equipped with condenser, mechanical stirrer, thermometer and pH electrodes was used for the preparation.
92.5 grams (1.0 mole) epichlorohydrin was added to the flask. 112.5 grams of 40% aqueous dimethylamine (45 grams real, 1.0 mole) was added with vigorous stirring over one hour keeping the temperature below 50C. Heating was applied ~or another two hours at 50C whereafter 70g water was added. The viscosity of this resin was determined to be 72 cps and dr~ content was ~ound to be 47 percent.
The same equipment as in Comparative Example 5 i30Ç~7~) was used: 63.S g water, 99 ethylenediamine and 121.99 aqueous solution (36.5%) of dimethylamine was added to the reaction flask. 1709 epichlorohydrin was added over a three hour period maintaining the temperature below 35C by cooling. Temperature was then increased to 80C. 11.89 epichlorohydrin was added in six portions over three hours and after the last addition the reaction mass was kept at 80C for an additional two hours, whereafter the product was cooled to room temperature. The product was a pale yellow slightly opaque liquid with a dry content of 65.8%
and a viscosity of 190 cps.
The same equipment as in Comparative Example 5 was used. Water t34.2g), dimethylamine (60.9g of an aqueous 36.9~ solution) and ethylenediamine (1.5g) were charged to the reaction flask. 51.0g epichlorohydrin was added with vigorous stirring over 2 hours. Temperature was raised to 80C and 10.6g epichlorohydrin was added in 9 portions over a 8 hour Period. The final product was a slightly opaque, pale yellow liquid. Dry content of this product was found to be 58.8~ and the viscosity approx 1000 cps .
The equipment of Comparative Example 5 was used.
~ resin was prepared in the following way: 112.5 grams 40%
~3~?~S'70 dimethylamine was added to the reaction flask together with 10.2 grams dimethylaminopropylamine. These two amines were mixed and 102 grams of epichlorohydrin was added over 30 minutes with vigorous stirring maintaining a temperature of 30-40C. Temperature was then increased to 60C which was maintained for 5 hours. During this period of time, 300ml of deionised water was added in small portions. This resin had a viscosity of 20 cps and a dry content of 33%.
The products of Comparative Example 5 and Examples 6 to 8 were evaluated following the procedure of Example 5 at an addition of l.Oppm polymer with the following results:
15 Product Deposit (mg~
Blank 272 Resin of Example 7 201 Resin of Example 6 138 Resin of Comparative Example 5 228 20 Resin of Example 8 186 Blank 260 The resin of Example 6 was evaluated using the method of Example 3. The following results were obtained:
13065'70 Concentration (ppm)~eposit ~mg) slank 133 2ppm 121 5ppm 29 lOppm 6 In order to evaluate the usefulness of polymers to combine with anionic dissolved components of paper pulp the rollowing experiment was made:
A dried groundwood pulp from pine was disintegrated for 30 minutes to prepare a 2.5% furnish.
The fibres were subsequently filtered off and the filtrate was used to evaluate the capacity of the resins to combine with dissolved anionic materials. The amount of anionic material was determined with a streaming current detector.
Polyethyleneimine (PEI) was used as standard. The efficiency to combine with anionic material was evaluated by adding to the filtrate various amounts of resin, stirring for 15 minutes and subsequently determining the residual concentration of uncombined anionic material by titration with the standard reagent. The results were as follows:
l~Q65~0 PEI mg/l Filtrate Blank 7,1 4ppm of resin of ~xample 7 4,8 8ppm of resin of Example 7 1,9 4ppm of resin of Example 8 4,6 8ppm of resin of Example 8 1,4 8ppm of resin of Example 2 ~,4 50ppm of resin of Example 2 2,3
Claims (18)
1. A method for the control of pitch in an aqueous system used in pulp or paper making which comprises adding to the system, or to the pulp making or papermaking machinery, a water soluble polyquaternary branched polymer derived from (a) an epihalohydrin, a diepoxide or a precursor of an epihalohydrin or diepoxide, (b) an alkyl amine having a functionality with respect to an epihalohydrin of 2 and (c) an amine having functionality which has a functionality with respect to an epihalohydrin of greater than 2 and which does not possess any carbonyl groups under one or more of the following conditions:
i) the polymer is added to the pulp making or papermaking machinery, ii) the pulp is of recycled paper containing adhesive, and, iii) components (a) and (b) are reacted to form a coupling agent which is then reacted with component (c).
i) the polymer is added to the pulp making or papermaking machinery, ii) the pulp is of recycled paper containing adhesive, and, iii) components (a) and (b) are reacted to form a coupling agent which is then reacted with component (c).
2. A method according to claim 1 in which component (a) is epichlorohydrin or epibromohydrin.
3. A method according to claim 1 in which component (b) is a dialkyl amine in which the alkyl groups individually contain 1 to 3 carbon atoms.
4. A method according to claim 3 in which component (b) is dimethylamine.
5. A method according to claim 1 in which component (c) is a primary amine or a primary alkylene polyamine.
6. A method according to claim 5 in which component (c) is diethylaminobutylamine, dimethylamino-propylamine or ethylene diamine.
7. A method according to claim 1 in which the polymer is also derived from a tertiary amine or a hydroxy alkylamine.
8. A method according to claim 7 in which the polymer is also derived from trimethylamine or triethanol amine.
9. A method according to claim 1 in which the polymer is one formed by reacting ethylene diamine with a precondensate of dimethyl amine and epichlorohydrin and reacting the product with triethanolamine to form a water soluble reaction product.
10. A method according to claim 1 in which the polymer is one formed by reacting a mixture of dimethylamine and ethylene diamine or dimethylamino propylamine with epichlorohydrin to form a water soluble reaction product.
11. A method according to claim 1 in which the equivalent ratio of component (c) to components (a) and (b) together is from 1:0.22 to 2.5.
12. A method according to claim 1 in which the polymer is added to the aqueous system with the furnish containing the paper pulp.
13. A method according to claim 1 in which the polymer is added in an amount from 1,000 to 50,000 grams per tonne of fibre.
14. A method according to claim 1 in which the polymer is sprayed onto at least a part of the pulp or paper making machinery.
15. A method according to claim 1 in which a biocide is also added to the aqueous system.
16. A method according to Claim 14 wherein the polymer is sprayed onto the papermaking wires.
17. A method according to Claim 14 wherein the polymer is applied as an aqueous solution having a polymer concentration below 10 percent by weight.
18 A method according to any one of claims 1-17 in which the papermaking process uses recycled paper containing adhesive.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8600506A GB2186895B (en) | 1986-01-09 | 1986-01-09 | Pitch control aid |
| GB8600506 | 1986-01-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1306570C true CA1306570C (en) | 1992-08-18 |
Family
ID=10591145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000526936A Expired - Lifetime CA1306570C (en) | 1986-01-09 | 1987-01-08 | Pitch control aid in paper making |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0232015B1 (en) |
| JP (1) | JPH07113200B2 (en) |
| AT (1) | ATE59068T1 (en) |
| CA (1) | CA1306570C (en) |
| DE (1) | DE3766623D1 (en) |
| ES (1) | ES2019376B3 (en) |
| FI (1) | FI88814C (en) |
| GB (1) | GB2186895B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE467667B (en) * | 1988-08-11 | 1992-08-24 | Grace W R & Co | PROCEDURES CONCERN REGULATION OF PRODUCTION CONTROLLING MICROBIOLOGICAL PROVISIONS ON PAPER MANUFACTURING EQUIPMENT |
| US4995944A (en) * | 1988-09-16 | 1991-02-26 | Dearborn Chemical Company Ltd. | Controlling deposits on paper machine felts using cationic polymer and cationic surfactant mixture |
| AR247436A1 (en) * | 1988-09-16 | 1994-12-29 | Dearborn Chemical Company Ltd | Controlling deposits on paper machine felts and the like |
| US4997523A (en) * | 1990-06-20 | 1991-03-05 | Betz Panerchem, Inc. | Method for effectively breaking up latex-coated paper during pulping to decrease the potential for white pitch deposition |
| GB2251868B (en) * | 1990-12-24 | 1994-07-27 | Grace W R & Co | Pitch control |
| TW202043331A (en) * | 2018-11-30 | 2020-12-01 | 美商Ｂｌ科技公司 | Fouling abatement for coker heaters |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3248353A (en) * | 1963-05-17 | 1966-04-26 | American Cyanamid Co | Alkylene polyamine resin |
| USRE28808E (en) * | 1972-02-04 | 1976-05-11 | American Cyanamid Company | Polyquaternary flocculants |
| US3855299A (en) * | 1973-06-11 | 1974-12-17 | Grace W R & Co | Water soluble reaction product of epihalohydrin and alkylamines |
| US4093605A (en) * | 1975-01-24 | 1978-06-06 | Wolff Walsrode Aktiengesellschaft | Auxiliary agent for improving retention, drainage and treatment |
| US4250269A (en) * | 1979-11-26 | 1981-02-10 | Buckman Laboratories, Inc. | Water-soluble mixtures of quaternary ammonium polymers, nonionic and/or cationic vinyl-addition polymers, and nonionic and/or cationic surfactants |
| CA1150914A (en) * | 1980-11-28 | 1983-08-02 | Margaret J. Molnar | Amine-epichlorohydrin polymers for pitch control |
-
1986
- 1986-01-09 GB GB8600506A patent/GB2186895B/en not_active Expired
-
1987
- 1987-01-08 FI FI870072A patent/FI88814C/en not_active IP Right Cessation
- 1987-01-08 CA CA000526936A patent/CA1306570C/en not_active Expired - Lifetime
- 1987-01-09 ES ES87300212T patent/ES2019376B3/en not_active Expired - Lifetime
- 1987-01-09 EP EP87300212A patent/EP0232015B1/en not_active Expired - Lifetime
- 1987-01-09 DE DE8787300212T patent/DE3766623D1/en not_active Expired - Lifetime
- 1987-01-09 AT AT87300212T patent/ATE59068T1/en not_active IP Right Cessation
- 1987-01-09 JP JP62001956A patent/JPH07113200B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ATE59068T1 (en) | 1990-12-15 |
| GB8600506D0 (en) | 1986-02-12 |
| JPH07113200B2 (en) | 1995-12-06 |
| EP0232015B1 (en) | 1990-12-12 |
| EP0232015A1 (en) | 1987-08-12 |
| FI88814C (en) | 1993-07-12 |
| GB2186895B (en) | 1989-11-01 |
| FI870072A0 (en) | 1987-01-08 |
| FI88814B (en) | 1993-03-31 |
| ES2019376B3 (en) | 1991-06-16 |
| DE3766623D1 (en) | 1991-01-24 |
| GB2186895A (en) | 1987-08-26 |
| FI870072A (en) | 1987-07-10 |
| JPS62223394A (en) | 1987-10-01 |
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