Agent for improving the wet strength and how to obtain it

 

The invention relates to an agent that increases the strength of paper in the wet state, and the method of its production, and method for producing a paper containing this agent. The method of receiving agent includes the first stage of the interaction between polyamine or polyaminoamide with hydrophobic connection with the formation of the polymer hydrophobic substituents in the side chains, the second stage is the interaction of the obtained polymer with cross-linking agent with the formation of nitrogen-containing resin, and the third stage is the formation of particles by emulsion polymerization of one or more Ethylenediamine monomers in the presence of the obtained resin. The method of obtaining the resin comprises two above the stage. The method of obtaining thin paper includes adding resin or agent to the aqueous suspension of cellulose. Thin paper includes a resin or the agent that increases blagorodnost paper. The invention improves blagorodnost paper when applying the above agent. The invention provides a simple, convenient and effective way to obtain a resin and agent with high yield. 9 C. and 16 h.p. f-crystals, 4 PL.

The invention relates to an agent that increases the strength of paper in humid is the receipt paper including the addition agent for improving the wet strength of the paper to the aqueous suspension of pulp and paper containing the agent for improving the wet strength of paper. In addition, the invention relates to the use of an agent that increases blagorodnost paper, as an additive to the aqueous suspension of cellulose.

In paper production agents increasing blagorodnost paper, such as resin based on epichlorohydrin, for example, polyaminoamide-epichlorhydrine resin, was used to increase the strength of paper in a long time. Such resins are described in U.S. patents 3700623 and 3772076. Blagorodnost paper tied to its ability to preserve the physical integrity and to resist tear, tearing and grinding during use, especially when wet. Another important property of paper with increased vlagoperenosu is soft, especially for thin paper, etc., Softness can be described as tactile sensations that one experiences when touching or rubbing the paper on the skin.

In U.S. patent 5200036 described agent for improving the wet strength, which gives the paper an improved blagorodnost. Cationic polyaminoamide-epichlorhydrine resin modified entered and as side chains. The resin was then added to latexbased the monomers, resulting happened copolymerization with the formation of links between unsaturated polymerizable hydrocarbon groups of the resin and latexmaske monomers. The reaction was promoted by the addition of an emulsifier to obtain the desired suspension of the formed latex particles. Resin described above is also used as emulsifiers. Usually the resin is insufficiently effective, when used as the sole emulsifier, and therefore they are used in combination with another connection.

In U.S. patent 5314721 described a method of producing dispersions of vinyl polymers containing resin-based cationic polyaminoamide, whose end groups are substituted long-chain aliphatic hydrocarbon radicals containing at least 7 carbon atoms and which residues of monocarboxylic acids. The resulting product was used as a sizing agent.

In U.S. patent 4416729 describes a method for additives that increase blagorodnost, which includes stages of interaction linear polyamidoamine,-ethyleneamines carboxylester what aluminum with the formation of branched polyamidoamine, containing the lateral amino group, and interaction branched polyamidoamine with epiglottitis with the formation of side-curable ammonium groups in the branched polyamidoamine. In U.S. patent 4416729 not described the use of additives that increase blagorodnost, to obtain thin paper.

Although the above-described resin based on epichlorohydrin in some applications show very good properties as agents that increase blagorodnost, and emulsifiers, it would be desirable to create additional and improved agents for improving the wet strength of paper and methods of making such agents. It would be desirable to create a resin and agents that increase blagorodnost that provide superior softness. In addition, it would be desirable to create still other resins having improved emulsifying properties.

In accordance with the present invention it has been found that additional new and improved agents for improving the wet strength of paper can be obtained on the basis of the composition containing polymer particles and a hydrophobic hydrocarbon group, which is the lateral substituents in the resin, increasing blagorodnost. In addition, it was nye and resin, increasing blagorodnost obtained by the method in accordance with the present invention, give the paper an improved softness, without exerting a negative influence on the absorption capacity of paper.

More specifically, the invention relates to agents for improving wet strength paper containing polymer particles and resins to improve the wet strength containing cationic nitrogen-containing polymer having hydrophobic substituents as side chains. In addition, the invention relates to a method for producing agents for improving wet strength of paper comprising the first stage, the interaction of the nitrogen-containing polymer with a hydrophobic compound to obtain a nitrogen-containing polymer with hydrophobic substituents in the side chain; the second stage is the interaction of the obtained product with a cross-linking agent with the formation of the cationic resin, increasing blagorodnost, and a third stage comprising emulsion polymerization of one or more Ethylenediamine monomers in the presence of the obtained resin, increasing blagorodnost. In addition, the invention relates to an agent that increases blagorodnost paper obtained by the method described above. The invention also relates to new stadiam, as described here. The invention also relates to the production of paper comprising adding resin or agent that increases blagorodnost paper, the pulp suspension and the use of resin or agent that increases blagorodnost paper to get the paper. The invention also relates to a paper containing resin or agents that increase blagorodnost paper. The invention is further defined in the attached claims.

In the present invention created resins and agents with the ability to give the paper of improved strength properties in the wet state (blagorodnost). In addition, the invention provides a simple, convenient and effective way of synthesis for the preparation of resins and agents that increase blagorodnost. So by increasing blagorodnost resin and the agents of the present invention can be obtained with high yield.

The present invention also provides resins and agents that increase blagorodnost, which give the opportunity to obtain a paper having improved softness. The softness of the paper sheet can be evaluated by using the relative wet strength, which is defined as the ratio between the measure of the tensile strength in the wet state and the indicator procrastina blagorodnost, WS denotes the measure of the tensile strength of paper in the wet state and DS indicates the index of the tensile strength of paper in a dry condition. Therefore, RWS is a measure of the softness of the paper; the higher the RWS, the higher the softness of the paper. Resin and the agents of the present invention, increasing blagorodnost also have improved emulsifying properties, and therefore they can be used as the sole emulsifiers without the addition of other compounds that may cause undesirable foaming.

The term "agent that increases blagorodnost", as used herein, refers to an agent capable of imparting the best paper strength properties in the wet state compared with paper that does not contain such an agent. The agent that increases blagorodnost contains a resin that increases blagorodnost. The term "resin, increasing blagorodnost", as used herein, refers to a resin capable of imparting the best paper strength properties in the wet state compared with paper, not containing such resins.

The method of receiving agent that increases blagorodnost paper, includes the first stage, the interaction of the nitrogen-containing polymer with a hydrophobic compound for images of the obtained product with a crosslinking agent to form resin, increasing blagorodnost, and the third stage, including the formation of particles by emulsion polymerization of one or more Ethylenediamine monomers in the presence of the obtained resin, increasing blagorodnost. In accordance with a preferred embodiment of the invention no polyamine having at least 2 secondary and/or primary amino groups, is added between the first and second stage or after the second stage, is not involved in the reaction.

Suitable nitrogen-containing polymer is polyaminoamide, polyamine or other nitrogen-containing polymer. Preferably use polyaminoamide, which may be a product of the reaction of polycarboxylic acids, preferably dicarboxylic acids, and polyamino. The term "carboxylic acid" includes derivatives of carboxylic acids, such as anhydrides and esters. Suitable polycarboxylic acids are saturated or unsaturated aliphatic or aromatic dicarboxylic acid. Preferably polycarboxylic acids contain less than 10 carbon atoms. Suitable polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipinic compounds. Suitable polyamine include polyallylamine, for example, Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine, dipropylenetriamine, etc. or mixtures thereof. In addition, you can use any polyaminoamide obtained by the method described in European patent EP 802215 A1 included in this description by reference. A suitable molecular weight nitrogen-containing compounds is in the range from 100 to 50,000, preferably from 500 to 10000. Appropriate attitude polyamine to the polycarboxylic acid is from 0.49:1 to 1.49:1, preferably less than 1.3:1, for example from 1.3:1 to 0.7: 1. A suitable choice is the reaction between Diethylenetriamine and adipic acid with the formation of polyaminoamide.

Suitable hydrophobic compounds that can be used may contain carboxylate groups or their derivatives. The hydrophobization reaction between the nitrogen-containing polymer and a hydrophobic compound can be made by alkylation, joining minilogo or other reactions. Join minilogo can be illustrated in the following schematic reaction:where VVV-NH-VVV is part of a chain nitrogen-containing polymer, C=C-COOR is to gidrofobizirovan with the nitrogen atoms of the polymer. R is a hydrophobic group, the hydrophobic compound, which may represent an alkyl, alkenylphenol, aryl, cycloalkyl or cycloalkenyl group. In the case of reactions of addition of the vinyl group, an unsaturated vinyl group, a hydrophobic compound turns into a rich group after it has reacted with the nitrogen atom of the polymer.

In accordance with one preferred embodiment of the invention the hydrophobic compound is a saturated compound or an unsaturated compound, which leads to nitrogen polymer containing saturated substituents as side chains.

Hydrophobic compounds may contain a hydrophobic group containing up to 40 carbon atoms, preferably 6-40 carbon atoms and most preferably 8 to 40 carbon atoms.

Hydrophobic chains of hydrophobic compounds can join nitrogen-containing polymer through a chain of atoms, which may contain at least one heteroatom, through covalent bonds.

The hydrophobic compound may be selected from (meth)acrylate, alkenyl(meth)acrylates, alkyl(meth)acrylamides, esters, ethers, diazocompounds,s, containing a hydrophobic group, preferably from alkyl(meth)acrylates, alkyl(meth)acrylamides, alkyl sulphonates, alkyl sulphates, diazo compounds, ethers or epoxides or mixtures thereof, most preferably from alkyl(meth)acrylates, alkyl(meth)acrylamide or mixtures thereof. Examples of suitable compounds are esters or amides,unsaturated acids, such as laurelcrest, 2-ethyl hexyl acrylate, dodecylamine, N-alkyl(meth)acrylamide, N-acylaminoalkyl-(meth)acrylamide, N, N-dialkylaminoalkyl(meth)acrylamide, N-acylaminoalkyl(meth)acrylate, N, N-dialkylaminoalkyl(meth)acrylates, vexilloid, 2-etilgeksilhlorid, artilharia, deciphered, dodecachloro, hexadecylamine, octadecylamine, TelePACE, preprepared, (n-,tert-,ISO-)butylamide, pentlepoir, exilerated, 2-ethylhexyloxy, accelerated, decelerated, dodecyloxy, hexadecylamine, octadecylamine, hexene, 2-ethylhexan, octene, the mission dodecen, hexadecan and octadecan.

The reaction can be carried out in water, without solvent or in another solvent, for example in an organic solvent, such as methanol, ethanol, ethylene glycol, etc., that can at you Can also use a mixture of such solvents. The reaction is preferably carried out in water. The molar ratio of nitrogen-containing polymer (in terms of the number of moles of amino groups) to hydrophobic compound may be at least 1: 1, from 2:1 to 99:1, preferably from 3:1 to 40:1. The reaction temperature may be in the range of from about 25 to about 150oC, preferably from about 60 to about 90oC.

In the second stage hydrophobizated nitrogen-containing polymers react with a crosslinking agent. The term "crosslinker" or "crosslinking agent" as used herein, is intended to refer to compounds that have the ability to make the resin and/or to form a connection with cellulose fibers. Suitable cross-linking agents, sometimes referred to as the internal cross-linking agents in the European patent EP 802215 A1, which describes various internal cross-linking agents, which are included in this description by reference, can be epiglottitis, such as epichlorohydrin, diepoxide, diacrylate, dimethacrylate, diacrylate and dimethacrylate and their mixtures or derivatives. Preferable as the crosslinking agent used epichlorohydrin.

The reaction can be carried out in aqueous solution, without solvent or with IBI solvent could not react with the reacting substances in the environment, at which carry out the reaction. Preferably the reaction is performed in water. The reaction temperature may be in the range of from about 0 to about 150oC, preferably from about 4 to about 80oC. the Molar ratio gidrofobizirovannogo nitrogen-containing polymer (in terms of the number of moles of amino groups) to the crosslinking agent in the reaction mixture may range from 10:1 to 1:10, preferably from 2:1 to 1:2.

At the third stage in accordance with the invention, the method comprises the emulsion polymerization of one or more Ethylenediamine monomers in the presence of the resin, increasing blagorodnost obtained after the second stage. The monomers can be selected from styrene, butadiene, vinyl acetate, vinylamide, alkyl(meth)acrylamide, alkyl(meth)acrylate such as methyl(meth)acrylate, butyl(meth)acrylate, butylglycol(meth)acrylate, 2-ethylhexyl(meth)acrylate, dodecyl(meth)acrylate, octadecyl(meth)acrylate, (meth)Acrylonitrile, isoprene, 1,6-hexanediamine or their mixtures or derivatives thereof. In the process of polymerization of the obtained resin, increasing blagorodnost, can be attached to the formed polymer particles, and formed an agent that increases blagorodnost. As the initiator of the Wako VA 044. Preferably, the initiator should be soluble in water. In the reaction emulsion polymerization resin, increasing blagorodnost, acts as an emulsifier during the formation of particles. The resulting particle can consist of one or of a mixture of Ethylenediamine polymerizable monomers, as described in the examples above. The reaction is preferably carried out in water, in organic solvents, for example ethanol, propanol, etc., or in mixtures of organic solvents, or in mixtures of water with organic solvents. The reaction temperature may be in the range of from 4 to about 150oC, preferably from about 30 to about 90oC. the Mass ratio of resin to monomer can be from 100:1 to 1:100, more acceptable from 10:1 to 1: 50.

The invention also relates to a method for producing a resin that increases blagorodnost, including the first and second stage of the method, as described above.

The invention also relates to an agent that increases blagorodnost, which contains polymer particles and the resin, increasing blagorodnost containing cationic nitrogen-containing polymer having a saturated hydrophobic substituents as side chains and groups formed from cross-linking agent.

the suits are selected from styrene, acrylates and their mixtures or derivatives thereof.

Cationic nitrogen-containing polymer is saturated hydrophobic substituents as side chains and groups - derived cross-linking agent attached to the nitrogen atoms of the polymer.

Examples of suitable nitrogen-containing polymers are well known available commodity products that can be obtained, as described above, or conventional methods known in the art. Examples of suitable nitrogen-containing polymers are polyaminoamide, acylpolyamines, polyimide and polyvinylidene.

Hydrophobic saturated substituents as side chains attached to the nitrogen atoms of nitrogen-containing polymer. The term "hydrophobic substituent in the form of a side chain" refers to a hydrophobic group containing, for example, hydrophobic linear or branched hydrocarbon chain, which may be associated, for example, through a heteroatom, the covalent bond to the nitrogen atom of nitrogen-containing polymer. The hydrophobic group may also include cyclic chain, including cyclic hydrocarbons. Combinations of linear, branched and cyclic hydrocarbons are also included in the term "hydrocarbon group".

The hydrophobic group, the hydrophobic side is Ino 8-40 carbon atoms.

Hydrophobic substituents in the side chains can be obtained, for example, from alkyl(meth)acrylates, alkyl(meth)acrylamides, esters, ethers, diazo compounds, carboxylic acids, acid anhydrides, epoxides, alkyl sulphonates, alkyl sulphates or mixtures thereof, containing a hydrophobic group, preferably from alkyl(meth)acrylates, alkyl(meth)acrylamides, alkyl sulphonates, alkyl sulphates, diazo compounds, ethers or epoxides, or mixtures thereof, and most preferably from alkyl(meth)acrylates, alkyl(meth)acrylamide or mixtures thereof.

Specific examples are the substituents formed from esters or amides,unsaturated acids, such as laurelcrest, 2-ethyl hexyl acrylate, dodecylamine, N-alkyl(meth)acrylamide, N-acylaminoalkyl(meth)acrylamide, N, N-dialkylaminoalkyl(meth)acrylamide, N-acylaminoalkyl(meth)acrylate, N,N-dialkylaminoalkyl(meth)acrylates, alkyl sulphonates, alkyl sulphates, vexilloid, 2-etilgeksilhlorid, artilharia, deciphered, dodecachloro, hexadecylamine, octadecylamine, TelePACE, preprepared, (n-, tert-, ISO-)butylamide, pentlepoir, exilerated, 2-ethylhexyloxy, accelerated, dellepiane and octadecan.

Other suitable substituents can be obtained from substituted derivatives of succinic anhydride-containing group selected from alkyl, alkenyl, aralkyl or aralkyl, and of dimers or polymers of ketene. In addition, examples of suitable substituents may include substituents derived from the compounds described in the international application WO 98/39376 included in this description by reference.

The derived cross-linking agent may be added to the nitrogen-containing polymer, which gives the opportunity to form relationships with nitrogen-containing polymer and/or cellulose fibers. Derivative cross-linking agent can be formed from epiglotitis, such as epichlorohydrin, diepoxides, diacrylates, dimethacrylates, diarylamino and dimethacrylates, or you can use their mixtures or derivatives. Preferably the crosslinking agent is derived from epichlorohydrin.

In accordance with one preferred embodiment of the invention the cationic nitrogen-containing polymer is a or polyaminoamide-epichlorhydrine resin or polyamine-epichlorhydrine resin having a saturated hydrophobic side chains. Acceptable if at least 10% and preferably up to primet hydrophobic group, preferably to 50%, most preferably 5-30%. Acceptable, if the agent that increases blagorodnost, is a composition of polymer particles and the resin, increasing blagorodnost dissolved in a solvent, preferably an agent that increases blagorodnost, is an aqueous composition. Acceptable if the water composition contains 5-50 wt.% solid substances.

The invention also relates to a resin that increases blagorodnost described above.

The invention also relates to the application of the resin and agent that increases blagorodnost paper, described above, to obtain the paper, preferably of thin paper. The application includes adding resin or agent to the aqueous suspension containing pulp fibers. The amount of resin added to the pulp fibers, may be different with respect to the dry pulp fibers, acceptable 1-70, preferably 5-50, more preferably from 15 to 50 and most preferably 25-50 kg per tonne of dry pulp fibers. The mass of the obtained paper per unit area may be less than about 70 g/m2, preferably below about 60 g/m2and most preferably below about 40 g/m2. The resin and the agent that increases vegoprag particles of the emulsion. The dispersion can then be added to the aqueous suspension of cellulose for the processing of forming the paper pulp fibers. The resin and the agent that increases blagorodnost paper, you can also add to the finished paper and thus to carry out a surface treatment of the paper. In addition, the resin and the agent that increases blagorodnost, can be added together with any other chemical reagent known in the art, which is typically used in the manufacture of paper, for example, sizing agents, softeners, auxiliary substances for the "hold" fillers, drying agents, agents that increase the strength in the dry state, means for controlling the filler or any other commonly used chemicals, such as the guar gum, carboxymethyl cellulose, polyacrylamide, polystyrene. In addition, you can add the usual fillers, such as clay, calcium carbonate, titanium dioxide, talc, aluminum silicate, calcium sulfate, calcium silicate, etc. described in the international application WO 97/37080. Next, the agent that increases blagorodnost, can be added to the suspension containing cellulosic fibers, in any proportion. Before adding resin or agent, to remove toxic by-products by ion exchange, electrodialysis, processing enzymes, filtration, distillation with water vapor, etc. in order not to add any toxic products, for example chloropropanediol, dichloropropanol, to a suspension of cellulose. Such methods are also described, for example, in European patents EP 666242 A1, EP 510987 A1 and international application WO 92/22601.

The invention also relates to a method for production of paper, preferably of thin paper, which includes adding resin and/or an agent that increases blagorodnost paper, to the water suspension of cellulose, as here described and illustrated by examples. The invention also relates to paper, preferably a thin paper-containing resin and/or an agent that increases blagorodnost, as here described and illustrated by examples. Thin paper is usually called such products as paper handkerchiefs, paper napkins and toilet paper are used as personal hygiene items, which contain two basic elements: a base formed from a sheet material, commonly known as thin paper, and the means of imparting softness, which is applied to the substrate. In this context, thin paper can also be used for household and industrial p is one of suspension of cellulosic fibers, to which is added agents increasing blagorodnost. Aqueous suspension containing cellulosic fibres, and then dehydrated to a suitable consistency, corresponding to a water content of from about 7 to 25% by operations of the vacuum dewatering and compaction, such as transmission between opposite each other mechanical elements, such as cylindrical rollers to receive the wet paper web containing pulp fibers. Dewatered paper web is further pressed in the course of its movement and usually dried by a drying cylinder with steam heating, known in the art as the drying cylinder Yankees. Can also be used for drying the paper web vacuum, as well as several drying cylinders of the Yankees, between which the paper web is not necessarily subjected to additional pressing and thereby form the structure of thin paper. The base may consist of either a single layer of paper, or it may be a laminate of two or more layers of paper. In any case, since the Foundation is formed of thin paper, it can be expected that it will have a relatively small thickness compared to its size in the main plane. As otnosite securities are their strength, soft, absorbent capacity, especially for aquatic systems, and their stability against the formation of paper dust, especially the resistance against the formation of paper dust in the wet state, as described in the application WO 95/01478. Production methods for the production of thin paper, in addition, as described in the application WO 95/01478 included in this description by reference. More specific applications or use thin paper include the reception and retention of secretions of the human body, and the paper can be used for drying of parts of the human body to remove released from his substance, and can be used to put off such substances. Resin or the agent of the present invention, increasing blagorodnost paper, usually have hydrophobic side chains containing 6-40 carbon atoms, preferably 8 to 40 carbon atoms. Hydrophobic side chains can be derived from (meth)acrylate, alkenyl(meth)acrylate, alkyl(meth)acrylamides, esters, ethers, diazo compounds, carboxylic acids, acid anhydrides, epoxides, alkyl sulphonates, alkyl sulphates and mixtures thereof or derivative containing a hydrophobic group, preferably from alkyl(meth)acrylate, and the compounds and most preferably from alkyl(meth)acrylate, the alkyl(meth)acrylamide or mixtures thereof. Other suitable hydrophobic side chains can be obtained from substituted derivatives of succinic acid anhydride-containing group selected from alkyl, alkenyl, aralkyl or aralkyl, or dimers or polymers of ketene. Additional examples of suitable hydrophobic side chains are side chains, which can be obtained from hydrophobic compounds described, for example, in international application WO 98/39376 and in U.S. patent 9922243 included in this description by reference. Weight in grams per unit area obtained thin paper may be less than about 70 g/m2, preferably below about 60 g/m2and most preferably below 40 g/m2. The amount of resin or agent that is added to a certain amount of dry cellulose fibers, can be any, but a suitable ratio is from about 1 to about 70 kg per tonne of dry pulp fibers, preferably from about 5 to about 50, more preferably from about 15 to about 50 and most preferably from about 25 to about 50 kg / ton dry cellulosic fibres. In accordance with one preferred embodiment of the invention together with the agent, increasing the strength of paper in a dry condition, for example starch, guar gum, carboxymethyl cellulose or synthetic agent that increases the strength in the dry state, such as anionic or amphoteric polyacrylamides, even if added to the aqueous suspension of cellulose the amount proposed in the invention resin or agent that increases blagorodnost paper, is from about 5 to about 50 kg / ton dry cellulosic fibres. In order to get the right strength in the dry state obtained thin paper, the person skilled in the art can select suitable hydrophobic resin or the agent that increases blagorodnost to obtain the desired thin paper, while the strength of thin paper in the wet state can be adjusted by adding to a water suspension of an appropriate quantity of resin or agent. Thus, it is possible to easily obtain a thin paper having a high relative blagorodnost.

From the description, it is obvious that it can be modified in various ways. Such changes should not be considered as deviations beyond being and scope of the present invention, and all such modifications as may armoloy invention. Although the following examples give more specific details of the reactions, they can be disclosed to subsequent General principles. The following examples will further illustrate how you can implement the described invention without limiting its scope.

Example 1 Reaction polyaminoamide (here below also called PAIM) (obtained from adipic acid and Diethylenetriamine) with a hydrophobic compound (vinyl accession): 240 g (of 0.60 mol. equivalents of amine) PAIM (53% solution in water) and 27.3 grams (0.15 mol) of 2-ethylhexyl acrylate (2-ENES) was heated for 6 h and 30 min at 80oC. Then was added 176 g of water and the solution was cooled to room temperature. Conversion of the acrylate was equal to 99.7%.

Spent the reaction 307 g obtained as described above, the solution gidrofobizirovannogo PAIM with 30 ml of epichlorohydrin (ECH) in 6oC for 6 minutes then the temperature was increased until it reached a temperature of 20oC. Then increase the temperature until it reaches 50oC and a viscosity of 120 MPawith, after which was added to 155 ml of water and the temperature was brought to 65oWith, giving the viscosity to reach the value of 120 MPaC. the Reaction was stopped by adding 11 ml of sulfuric to g obtained as described above, the resin, increasing blagorodnost, 104 g of water and 1.5 ml of protivovospalitel (10% solution in water) was purged with nitrogen. Then the temperature was raised to 50oWith, and then to the solution was added 0.5 g of initiator Wako VA 044 and 1 ml of styrene. After 10 min was added an additional amount of styrene (total 25 g). After 5 h at 50oWith the temperature raised to 70oC and at this temperature the solution was kept for one hour.

Example 2 Reaction polyaminoamide (PAIM) 2-hexyl acrylate (2-ENES)(vinyl accession): 82 g (0,20 mol. equivalent of amine) PAIM (52% solution in water) of 18.4 g (0.01 mol) 2-ethylhexyl acrylate (2-ENES) and 43 g of water was heated for 2 h at 80oC. Conversion of acrylate 98.9%. of 15.4 ml of epichlorohydrin (ECH) was added to 125 g of the solution gidrofobizirovannogo, as described above, PAIM in 6oC for 6 minutes then the temperature was raised to 20oC. Then the temperature was raised to 50oC and the viscosity was reached 120 MPawith, after which was added to 86 ml of water. The temperature was raised to 65oWith and kept the mixture at 65oWith up until the viscosity reached 120 MPaC. the Reaction was stopped by adding 11 ml of sulfuric acid (50%), bringing rely, increasing blagorodnost, 92 g of water and 1.5 ml of protivovospalitel (10% solution in water) was purged with nitrogen. The temperature was raised to 45oC. was Added 0.04 g Wako VA 044 and 2 ml of styrene, after which the temperature was raised to 50oC. After 10 min was added an additional amount of styrene (total 12 g). After incubation for 3 h at 50oTo the reaction mixture was cooled to room temperature.

Example 3 260 g (0,65 mol. equivalent of amine) PAIM (53% solution in water) and 41,0 g dodecylamine (25%, 0.16 mol) (vinyl accession, was heated for 4 h 30 min at 80oC. then was added 211 g of water, after which the mixture was cooled to room temperature.

Then there was the reaction of 302 g of the obtained gidrofobizirovannogo PAIM with 30 ml (0.20 mol) of epichlorohydrin (ECH) in 6oC for 4 minutes then increase the temperature until it reached 20oC. Then the temperature was increased until it reached 50oAnd until the viscosity reached 120 MPaC. Then was added 185 ml of water, the temperature was raised to 65oWith and kept the mixture at this temperature until the viscosity reached 120 MPaC. the Reaction was stopped by adding 10 ml of sulfuric acid (50%), bringing the pH to 3.5.

< described above, resin, increasing blagorodnost, 100 ml of water and 1 ml of protivovospalitel (10% solution in water) was purged with nitrogen. The temperature was raised to 50oWith, after which was added 30 mg Wako VA 044 and 1 ml of styrene. After 10 min was added an additional amount of styrene (total of 20.5 g). After keeping 5 h at 50oWith the temperature raised to 70oC and kept at this temperature for one hour.

Example 4 emulsion polymerization instead of the styrene used the butyl acrylate. The solution containing 75,0 g resin, increasing blagorodnost, from example 3 (13% solids) and 1.5 g of protivovospalitel (10% solution in water) was purged with nitrogen. The temperature was raised to 45oC. was Then added 0.03 g Wako VA 044 and 2 ml of butyl acrylate, after which the temperature was increased up to 50oC. After 10 min was added styrene (total of 14.2 ml). After incubation for 2 h 50 min at 50oWith the temperature raised to 70oC and at this temperature withstood the mixture for one hour.

Example 5 For the hydrophobization PAIM used 25% 2-ethylhexyl acrylate. Emulsion polymerization: a solution of 121 g of the resin, increasing blagorodnost, from example 1 (solid content 28%), 131 g of water and 1 mg protivovospalitel (10 is the Windows (styrene : 1,6-hexanediamine = 0,375 : 0,125), then the temperature was raised to 50oC for 10 minutes After this was added a mixture of monomers (the total number of 17 g). After incubation for 3 h at 50oTo the reaction mixture was cooled to room temperature.

Example 6 For the hydrophobization PAIM used 25% 2-ethylhexyl acrylate. Used a Monomeric mixture of styrene and tert-butyl acrylate (0,45:0,05). Emulsion polymerization: a solution of 121 g of the resin, increasing blagorodnost, from example 1 (solid content 28%), 131 g of water and 1 ml of protivovospalitel (10% solution in water) was purged with nitrogen. The temperature was raised to 45oC. Then was added 0.04 g Wako VA 044 and 2 ml of monomer mixture (styrene, tert-butyl acrylate = 0,45 : 0.05) and the temperature was raised to 50oWith in 10 minutes After this was added a monomer mixture (the total number of 17.0 g). After 3 h at 50oTo the reaction mixture was cooled to room temperature.

Example 7 630 g (1,67 mol. equivalents of amine) PAIM (56% solution in water) and 12% (0.2 mol) of dodecylamine (vinyl accession) was heated for 6 h at 80oC. Then was added 326 g of water, after which the mixture was cooled to room temperature. Conversion of acrylate >99%.

Then there was the reaction 1005 g obtained as described above, gidrofobizirovannogo PAI 20oC. Then the temperature was increased until it reached 50oWith and viscosity reached 120 MPaC. Then was added 287 ml of water, the temperature was raised to 65oC and kept at this temperature until the viscosity reached 100 MPaC. the Reaction was stopped by adding 50 ml of sulfuric acid (50%) and 513 ml of water, bringing the pH to 3.5.

Example 8
309,5 g (0,81 mol. equivalent of amine) PAIM (55% solution in water) and 15% (0.12 mol) of benzylchloride (alkylation reaction) was heated for 6 h at 60oC. then the mixture was cooled to room temperature.

Then there was the reaction of 125 g obtained as described above, gidrofobizirovannogo PAIM from 17.7 g (to 0.19 mol) of epichlorohydrin (ECH) in 6oC for 4 minutes then the temperature was increased until it reached 20oC. Then increase the temperature until it reached 50oAnd until the viscosity reached 120 MPaC. Then was added 33 ml of water, the temperature was raised to 65oC and kept at this temperature until the viscosity reached 100 MPaC. the Reaction was stopped by adding 6 ml of sulfuric acid (50%), bringing the pH to 3.5.

Example 9
350 g (0/91 mol. equivalent of amine) PAIM (55% solution in the mixture is cooled to room temperature. Then there was the reaction 130,4 g gidrofobizirovannogo, as described above, PAIM from 17.7 g (to 0.19 mol) of epichlorohydrin (ECH) in 6oC for 4 minutes then the temperature was increased until it reached 20oC. Then the temperature was increased until it reached 50oC and the viscosity was reached 120 MPaC. Then was added 33 ml of water, the temperature was raised to 65oC and kept at this temperature until the viscosity reached 100 MPaC. the Reaction was stopped by the addition of 5.7 ml of sulfuric acid (50%), bringing the pH to 3.5.

Example 10
274 g (0,71 mol. equivalent of amine) PAIM (55% solution in water) and 3.8% (or 0.027 mol) of dimer of alkylbetaine (chain-18) was heated for 6 h at 60oC. then the mixture was cooled to room temperature.

Then there was the reaction to 127.2 g gidrofobizirovannogo, as described above, PAIM from 17.7 g (to 0.19 mol) of epichlorohydrin (ECH) in 6oC for 4 minutes then the temperature was increased until it reached 20oC. Then the temperature was raised to 50oC and the viscosity was reached 120 MPaC. Then was added 33 ml of water, the temperature was raised to 65oC and kept at this temperature until the viscosity reached 100 MPa. is equivalent amine) PAIM (55% solution in water) and 5% (being 0.036 mol) alkenylsilanes anhydride of succinic acid (C18 chain) was heated for 6 h at 60oC. then the mixture was cooled to room temperature.

Then there was the reaction 124,3 g gidrofobizirovannogo, as described above, PAIM from 17.7 g (to 0.19 mol) of epichlorohydrin (ECH) in 6oWith 4 minutes then the temperature was increased until it reached 20oC. Then the temperature was increased until it reached 50oC and the viscosity was reached 120 MPaC. Then was added 33 ml of water, the temperature was raised to 65oC and kept at this temperature until the viscosity reached 100 MPaC. the Reaction was stopped by the addition of 5.7 ml of sulfuric acid (50%), bringing the pH to 3.5.

Example 12
185,4 g (0,48 mol. equivalent of amine) PAIM (54% solution in water) and 10% (0,048 mol) of hexaniacinate (90%) was heated for 4.5 hours at 80oC. then the mixture was cooled to room temperature. Conversion of acrylate >99%.

Then there was the reaction 124,0 g gidrofobizirovannogo, as described above, PAIM from 17.7 g (to 0.19 mol) of epichlorohydrin (ECH) in 6oWith 4 minutes then the temperature was increased until it reached 20oC. the Temperature is then raised until it deteetor increased to 65oC and kept at this temperature until the viscosity reached 100 MPaC. the Reaction was stopped by the addition of 5.7 ml of sulfuric acid (50%), bringing the pH to 3.5.

Tests for the application
Sheets of paper were cast on dynamic paper machine "Formette". The composition of the paper consisted of 35% mixed waste paper (STMR) and 65% cellulose fiber (TCF), refined to 25 degrees refining the instrument shopper-Rigler (25oSR). The paper was subjected to the accelerated drying 10 minutes at 105oAnd then kondicionirovanie paper in accordance with DIN 5312. Rupture test tensile carried out as described in DIN 53112. For trials at the gap of wet paper were soaked for 60 min at room temperature. For comparison also the data for the paper are obtained using conventional polyaminoamide-epichlorhydrine resin. It should be noted that the sheets of paper, the details of which are shown in tables 1-4 were subjected to three different series of tests using different amounts of added agent that increases blagorodnost. In examples 1-6 was added to 20 kg of an agent that increases blagorodnost, per ton of pulp fibers. The weight of paper per unit area was wiseuse blagorodnost, was 15, 20 and 30 kg per ton of pulp fibers. As a consequence, the observed magnitude of the relative strength for each test series differed. Therefore, for each series of tests conducted measurements for the control resin, i.e., the commonly used resin, as can be seen from tables 1-4, below. As you can see from the examples, resins and agents that increase blagorodnost show better effect than ordinary resin used as a comparison with the same quantities of the added resin.


Claims

1. The method of receiving agent that increases blagorodnost paper, characterized in that it includes a first stage, the interaction of the nitrogen-containing polymer is a polyamine or polyaminoamide, with hydrophobic connection with the formation of the polymer hydrophobic substituents in the side chains, the second stage is the interaction obtained gidrofobizirovannogo nitrogen-containing polymer with cross-linking agent with the formation of the cationic nitrogen-containing resin, and the third stage, including the formation of particles by emulsion polymerization of one or more Ethylenediamine monomers in the presence of the obtained resin, increasing prisoedinenie or alkylation, where the hydrophobic compound is chosen from alkyl(meth)acrylates, alkyl(meth)acrylamides, alkyl sulphonates, alcaparrado, diazo compounds, ethers and epoxides or mixtures thereof.

3. The method according to p. 1 or 2, characterized in that the hydrophobic compounds contain a hydrophobic chain having 6-40 carbon atoms.

4. The method according to any of paragraphs.1-3, characterized in that the hydrophobic compounds contain a hydrophobic chain having 8-40 carbon atoms.

5. The method according to any of paragraphs.1-4, characterized in that the hydrophobic compound contains a chain of atoms containing at least one heteroatom.

6. The method according to any of paragraphs.1-5, characterized in that the crosslinking agent is an epichlorohydrin.

7. The method according to any of paragraphs.1-6, characterized in that the monomers chosen from styrene, butadiene, alkyl(meth)acrylates, alkyl(meth)acrylamides, (meth)Acrylonitrile, vinyl acetate or vinylamide, or their mixtures or derivatives thereof.

8. The method according to any of paragraphs.1-7, characterized in that the hydrophobic compound is a saturated compound or an unsaturated compound giving the nitrogen-containing polymer having a saturated substituents as side chains.

9. The agent that increases blagorodnost paper, which can poluchit resin, increasing blagorodnost containing cationic nitrogen-containing polymers having a hydrophobic saturated substituents as side chains, and groups derived from a crosslinking agent, and polymer particles.

11. Agent p. 10, characterized in that the hydrophobic substituents as side chains containing a hydrophobic group connected to the nitrogen atom of nitrogen-containing polymer through a chain of atoms containing 6-40 carbon atoms.

12. Agent p. 10 or 11, characterized in that the hydrophobic substituents selected from derivatives of alkyl(meth)acrylates, alkyl(meth)acrylamides, alkyl sulphonates, alkyl sulphates, diazo compounds, ethers or epoxides, or mixtures thereof.

13. A method of obtaining a resin that increases blagorodnost paper, characterized in that it includes a first stage, the interaction of the nitrogen-containing polymer with a hydrophobic compound containing 6-40 carbon atoms selected from alkyl(meth)acrylates, alkyl(meth)acrylamides, alkyl sulphonates, alkyl sulphates, diazo compounds, ethers or epoxides, or mixtures thereof, with the formation of hydrophobic substituents as side chains containing 6-40 carbon atoms, and the second stage is the interaction obtained gidrofobizirovannogo azotsodyerzhascimi fact, the hydrophobic compound is a saturated compound or an unsaturated compound giving the nitrogen-containing polymer which has saturated substituents as side chains.

15. Resin, increasing blagorodnost paper obtained by the method defined in any of paragraphs.13 and 14.

16. Resin, increasing blagorodnost paper, characterized in that the resin contains a cationic nitrogen-containing polymers having a saturated hydrophobic substituents as side chains containing 6-40 carbon atoms, selected from compounds derived from alkyl(meth)acrylates, alkyl(meth)acrylamides, alkyl sulphonates, alkyl sulphates, diazo compounds, ethers or epoxides, or mixtures thereof; and groups formed from cross-linking agent.

17. The method of obtaining thin paper, comprising adding resin or agent that increases blagorodnost paper, which contain cationic nitrogen-containing polymer having hydrophobic substituents as side chains containing 6-40 carbon atoms, to a water suspension of pulp.

18. The method according to p. 17, characterized in that the resin, which increases blagorodnost paper, add in the amount of from about 5 to about 50 kg per ton of dry cellulosic fibers.

19. Ability to about 50 kg per ton of dry cellulosic fibers.

20. The method according to p. 17, characterized in that the resin, which increases blagorodnost paper, add in the amount of from about 25 to about 50 kg per ton of dry cellulosic fibers.

21. The method according to any of paragraphs.17-20, wherein the agent that increases the strength of the paper in a dry condition, type in combination with a resin or the agent that increases blagorodnost paper.

22. The method according to any of paragraphs.17-21, characterized in that the thin paper has a weight per unit area is lower than about 70 g/m2.

23. Thin paper-containing resin or the agent that increases blagorodnost paper, which contain cationic nitrogen-containing polymer having substituents in the form of hydrophobic side chains containing 6-40 carbon atoms.

24. Thin paper by p. 23, characterized in that it contains a resin or the agent that increases blagorodnost paper, in an amount of from about 5 to about 50 kg per ton of dry cellulosic fibers.

25. Thin paper-containing resin or the agent that increases blagorodnost paper obtained by the method according to any of paragraphs.17-22.

 

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