Ionic polyurethanes

 

The invention relates to a charged polyurethanes, intended for use as an additive in the manufacture of paper. Describes how to obtain charged polyurethanes, including the interaction of the isocyanate groups of MDI with hydroxyl groups of various alcohols, including (i) the first alcohol is selected from one or more diols containing at least 10 carbon atoms; (ii) a second alcohol selected from alkilbenzolov having not more than 8 carbon atoms, alkiloksibenzolov having not more than 8 carbon atoms, polyols with at least three hydroxyl groups and mixtures thereof; (iii) the third alcohol selected from (a) diols containing a charged group or atom, (b) diols containing uncharged group or atom capable of forming a charge and at least partial transformation of uncharged group or atom in a charged group or atom, (C) polyols, and further interaction with one or more hydroxyl groups derived from a polyol with a compound containing a charged group or atom, or a compound containing uncharged group or atom capable of forming a charge or at least partial conversion of the specified NESARA the AI have improved priklausomi properties and stability compared with known anionic polyurethanes. 4 C. and 13 C.p. f-crystals, 2 tab.

Field of invention the Present invention relates to a charged polyurethanes, aqueous dispersions of charged polyurethanes and method of their production and to their use as additives in the manufacture of paper.

Background of the invention From the prior art it is known the use of charged polyurethanes as external and internal sizing agents in paper production. For example, U.S. patent 3971764 discloses a sizing agent based on cationic polyurethanes obtained (i) by the interaction of the aliphatic diol having aliphatic Deputy with at least 10 carbon atoms, with the polyisocyanate with the formation of the prepolymer with terminal isocyanate groups, which then interacts with (ii) diola containing a tertiary nitrogen atom, which is then converted to ammonium compound, or (iii) diola containing a nitrogen atom, previously converted into ammonium compound. Similarly, U.S. patent 4096127 discloses a sizing agent on the basis of anionic polyurethanes obtained by the implementation of stage (i), described above, with the subsequent interaction of the obtained prepolymer (iv) aliphaticity acid group in salt by reaction with a base, or (v) aliphatic diola, including a group of salt. U.S. patent 4777224 also discloses a sizing agent on the basis of anionic polyurethanes obtained by implementing the above steps (i), (iv) and (v) with the additional use of polyurethane compounds with at least one group HE. Polyurethanes of this type usually have good size properties when using a small number of sizing agent. However, there is still a need for a sizing substances on the basis of charged polyurethanes with improved sizing performance, stability and usability.

The object of the invention, accordingly, is the provision charged polyurethanes and their aqueous dispersions with improved sizing performance, stability and applicability. The following objects will be described below. The purpose of the present invention are achieved by means of the method of obtaining charged polyurethanes, charged polyurethanes obtained in this way, aqueous dispersions of charged polyurethanes and their use, as defined below in the claims.

Summary of the invention the Present invention relates to a method for sergeybrin of one or more diols, containing at least 10 carbon atoms; (ii) a second alcohol selected from alkilbenzolov and alkiloksibenzolov containing not more than 8 carbon atoms, polyols and mixtures thereof; (iii) the third alcohol selected from (a) diols containing a charged group or atom, (b) diols containing uncharged group or atom capable of forming a charge and at least partial transformation of uncharged group or atom in a charged group or atom, (C) polyols, and further interaction with the connection, containing a charged group or atom, or a compound containing uncharged group or atom capable of forming a charge and at least partial transformation of uncharged group or atom in a charged group or atom, or mixtures of these compounds.

Detailed description of the invention the Present invention mainly relates to a method for obtaining charged polyurethanes and charged polyurethanes obtained in this way. The method includes the interaction of the isocyanate groups of MDI with hydroxyl groups of two - and/or polyhydric alcohols, including (i) the first alcohol is selected from one or more diols containing at least 10 carbon atoms; (ii) a second alcohol in the MOU carbon polyols and mixtures thereof; (iii) the third alcohol selected from (a) diols containing a charged group or atom, (b) diols containing uncharged group or atom capable of forming a charge and at least partial transformation of uncharged group or atom in a charged group or atom, (C) polyols, and further interaction with one or more hydroxyl groups of the polyol with a compound containing a charged group or atom, or a compound containing uncharged group or atom capable of forming a charge and at least to the partial transformation of uncharged group or atom in a charged group or atom, or mixtures of these compounds.

Charged polyurethane, covered by the present invention include polyurethanes containing anionic and/or cationic groups, forming through this anionic, amphoteric and cationic polyurethanes. In accordance with the present invention offers anionic, amphoteric and cationic polyurethanes with excellent properties. Aqueous dispersions of charged polyurethanes according to the invention provide improved sizing, which means that can be used smaller amounts of sizing agent with obtaining sootvetstvuyshee charged polyurethanes according to the invention include less foaming, very good or improved stability, compatibility, bond strength, characteristics, sizing and coating in a wide range of pH values used in the gluing surfaces for applying a preliminary coating and coatings in combination with conventionally used components such as electrolytes, starch and its derivatives, pigments, other synthetic polymers, and so on, as well as improved adhesion modifier colors and fluidity of ink.

The method according to the invention can be implemented in several ways. You can interact MDI with the first, second and third alcohols simultaneously, i.e. the so-called single-shot method. For example, this mode can be applied when using as a third of the alcohol (b) diol containing uncharged group or atom capable of forming charge, where the education of the eligible charge occurs when the polyurethane is already established. However, preferably the method is carried out as two-stage or three-stage method, for example, through the introduction of spirits, one after the other for the interactions. The terms "single-shot method", "two-stage FPIC reaction medium for interaction essentially simultaneously, in two stages or three stages, respectively. The implementation of the method in at least two stages makes it possible for the MDI interaction with alcohol(s) are initially introduced into the reaction medium, so as to form a pre-adduct or prepolymer with isocyanate(reference) group(s), usually in the limit position, and the lengthening of the chain prior adduct by reacting the alcohol(s), which is then injected into the reaction medium, the alcohol(s) acts as an extension agent or extension chain or as a branching agent. Preferably the first and second alcohols injected into the process to communicate prior to the introduction of the third alcohol. The first alcohol can be introduced into the process prior to, simultaneously with or after the second alcohol. In a preferred implementation of the invention, the polyurethane is obtained by the MDI interaction with the first alcohol with the formation of the pre-adduct having terminal isocyanate groups; extension chain pre-obtained adduct by reacting with a third alcohol, and optional conversion of any uncharged groups or atoms, as described above, in order to make the polyurethane charged, where the second SP, the RT type (b) or (C), that requires one or more additional reaction stages for the introduction of a charged group or atom, usually it is preferable to obtain polyurethane first interaction isocyanate groups MDI with hydroxyl groups of the first, second and third alcohol and then the implementation of any additional stage(s), for example, reaction of the resulting product with a compound containing uncharged group or atom capable of forming charge, and turning uncharged group or atom in a charged group or atom. However, this additional stage(s) can also be carried out at an earlier stage of the method, for example, before the introduction of the last of the alcohol in the interaction process.

In the method according to the invention the alcohol, called "first spirit" is diola or diatomic alcohol containing at least 10 carbon atoms. First, the alcohol may be selected from aliphatic and aromatic diols, preferably aliphatic diols. The term "aliphatic", as used herein, refers to essentially hydrocarbon structure, not including the specified functional groups, and the hydrocarbon structure may be interrupted by one or bore rotoma, for example, carbonyl and allochromatic. The term "aromatic", as used herein, refers to an aromatic, essentially hydrocarbon structure, not including the specified functional groups, and the hydrocarbon structure may be interrupted by one or more heteroatoms, such as oxygen and nitrogen, and/or one or more groups containing heteroatoms, for example, carbonyl and allochromatic. Suitable first alcohols include high molecular weight polymeric diols, for example, a complex polyester-easy polyester - and polybutadiene, and polimernye diols, preferably polimernye diols. Preferred first alcohols include aliphatic diols with aliphatic Deputy of the side chain. Aliphatic diols with aliphatic Deputy, may contain from 2 to 20, suitably from 2 to 10 carbon atoms in the chain connecting the two hydroxyl groups, for example, in the main chain, and the preferred aliphatic main chain include alkylene and diallylamine. Aliphatic Deputy may contain from 1 to 30, suitably at least 10 and preferably from 10 to 22 carbon atoms. Preferred first alcohols represent carbon atoms. When the main chain contains a heteroatom which is nitrogen, preferably nitrogen carried aliphatic Deputy. Examples of suitable first alcohols include complex monetary fatty acids and triolo, such as glycerin, trimethylated and trimethylolpropane, for example, monostearate, monoselenide, monopalmitate and monooleate glycerin and trimethylolpropane; oligomeric everday, such as definiely, for example, obtained by the interaction of dicarboxylic acids, e.g. adipic acid, with a molar excess of diol, for example, etilenglikola; N-alkyldiethanolamine, for example, N-stelldichein; dihydroxyethylene branched chain, for example, 1,2 - and 1,4-dihydroxyanthracene; and N,N-bis (hydroxyalkyl) bonds alkylamines, for example N,N-bis(-hydroxyethyl)stearylamine. Glycerylmonostearate is especially preferred. Examples of aromatic diols that may be used include bisphenol A. you Can also use a mixture of two or more of the first spirits.

In the method according to the invention the alcohol, which is called the "second spirit" may be a low molecular weight diola, or diatomic alcohol having not more than 8 carbon atoms. Diol may be selected from Leimer, diethylene glycol, triethylene glycol, tetraethyleneglycol and dipropyleneglycol and mixtures thereof. Preferred diols include ethylene glycol and diethylene glycol. Diols suitably contain from 2 to 6 carbon atoms and preferably from 2 to 4 carbon atoms. Alternative or additionally, the alcohol, which is here called the "second spirit" may be a polyol or polyhydric alcohol, i.e. an alcohol having at least three hydroxyine group. Preferably the polyol is aliphatic. Typically, the polyol contains from 3 to 10 carbon atoms, particularly preferably not more than 8 carbon atoms. Suitable polyols include glycerol, diglycerin, trimethylacetyl, trimethylolpropane and pentaerythritol. Preferred polyols include glycerol, trimethylolpropane and pentaerythritol. From polyols usually prefer to use trioli and tetraol, preferably trioli. The second alcohol are eligible should not contain charged groups and atoms, and the groups and atoms, capable of forming charge.

In the method according to the invention the alcohol, which is called the "third alcohol" is diola, or diatomic alcohol that is charged or capable of forming charge, or a polyol or polyhydric alcohol is to use third mixture of alcohols. Preferably the third alcohol is an aliphatic compound. Even more preferably, when the third alcohol is diola. In the preferred embodiment of the invention using the method according to the invention have the polyurethane, which is anionic in nature. In another preferred embodiment of the method leads to the production of polyurethane, which is in its cationic nature. In another preferred embodiment of the method according to the invention leads to the production of amphoteric polyurethane, which, in turn, may be inherently anionic or cationic.

Accordingly, the third alcohol can be selected from (a) a diol containing a charged group or atom, i.e., anionic or cationic group or atom. In the method according to the invention after interaction with a polyisocyanate or a pre-obtained adduct having isocyanate(s) group(s), this type of diol gives the charged prepolymer or polyurethane. Examples of anionic groups or atoms, which may be present in diola include carboxylate, phosphate and sulphonate groups, preferred carboxylates, which can be obtained by neutralizing diol having a carboxylic acid group or sulfonic acids, takoh the o acids or anhydrides of these acids (usually succinic acid or anhydride, terephthalic acid or anhydride), such as glycerylmonostearate, glycerylmonostearate, trimethylolpropane, trimethylolpropane, N,N-bis(hydroxyethyl)glycine, di(hydroxymethyl)propionic acid, N, N-bis(hydroxyethyl)-2-aminoetansulfonovaya acid, etc., by reaction with a base, such as alkali metal hydroxide, e.g. sodium hydroxide, or amine, such as triethylamine, with the formation of such by democraticheskogo or ammonium counterion. Examples of cationic groups or atoms, which may be present in diola include cation-charged sulfur, phosphorus or nitrogen, for example in the form of Solonevich groups, fofanah groups or ammonium groups, such as acid additive salts of primary, secondary or tertiary amino groups and Quaternary ammonium groups, preferably Quaternary ammonium groups, and most preferably an acid additive salt of the tertiary amine groups and Quaternary ammonium groups. Examples of suitable cationic diols (a) include acid additive salts and quaternization products of N-arcandyalagireeio and N-alkyldiethanolamine, such as 1,2-propandiol-3-dimethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propylnitrosamine, N is HN N-alkyldiethanolamine, alkyl groups which contain from 1 to 4 carbon atoms, in particular N-methyldiethanolamine. Acid additive salts can be obtained from acids such as formic acid, hydrochloric acid, sulfuric acid, etc. and the products of quaternization can be obtained from the alkylation agents such as methyl chloride, diallylsulfide, such as dimethylsulfate, benzylchloride, such as benzylchloride, epichlohydrin, such as epichlorohydrin, and alkalinity, such as ethylene oxide and propylene oxide. Examples of suitable diols containing cationic group, are disclosed in International patent publication WO 97/45395 and U.S. patent 5561187, the contents of which are incorporated in this description by reference.

Alternative or additionally, the third alcohol may be selected from (b) diol containing uncharged group or atom capable of forming charge. In the method according to the invention, after the reaction with the polyisocyanate or pre-obtained adduct containing isocyanate(s) group(s), this type of diols uncharged forms a prepolymer or polyurethane, which is subjected to further interaction with the aim of obtaining a charged polyurethane by the partial or complete conversion of NESARA is m, contains a group or atom, which are anionic in the reaction with the base. Examples of suitable uncharged groups or atoms of this type include acidic groups such as sulfonic group, phosphoric acid and carboxylic acid, typically a carboxylic acid group. Anionic charge can be formed by neutralizing the acid group by reaction with a base, such as alkali metal hydroxide, e.g. sodium hydroxide, or amine, such as triethylamine, forming melodramaticheskiy or ammonium counterion. Suitable non-ionic diols (b), which are potentially anionic include monetary the reaction product of trolov (usually trimethyloctane, trimethylolpropane, glycerol) and dicarboxylic acids or anhydrides of these acids (usually succinic acid or anhydride, terephthalic acid or anhydride), such as glycerylmonostearate, glycerylmonostearate, trimethylolpropane, trimethylolpropane, and N,N-bis(hydroxyethyl)glycine, di(hydroxymethyl)propionic acid, N,N-bis(hydroxyethyl)-2-aminoetansulfonovaya acid, etc., an Alternative second alcohol (b) can be diola, contains a group or atom that can clucalc sulfur atoms and nitrogen atoms, for example in the form of sulfide and amine groups, preferably a nitrogen atom, where the nitrogen may be present in the form of primary, secondary or tertiary amino groups, preferably tertiary amino group. The cationic charge can be formed by the reaction of uncharged groups or atoms present in the polyurethane, acid and/or alkylating agent with the formation of such by cationic groups or atoms, such as sulfonate or ammonium groups, for example in the form of an acid additive salts (protonated nitrogen atoms and Quaternary ammonium groups (stereoselectivity of the nitrogen atoms). Examples of suitable nonionic diols (b), which is potentially cationic include N-altingiaceae and N-alkyldiethanolamine, such as 1,2-propandiol-3-dimethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propylnitrosamine, N-n-butyldiethanolamine and N-tert-butyldiethanolamine, N-stelldichein and N-methyldiphenylamine, preferably N-alkyldiethanolamine, the alkyl groups of which contain from 1 to 4 carbon atoms, in particular N-methyldiethanolamine. Suitable acids include formic acid, hydrochloric acid, sulfuric acid, etc., Suitable alkylating agents include meillor the emer the epichlorohydrin, and alkalinity, such as ethylene oxide and propylene oxide.

Third, the alcohol can be selected from (C) polyol. If you use this third type of alcohol, it is generally preferable that the first and second alcohol were already in the process, and thus was formed the pre-adduct with limit(s) isocyanate(s) group(s), so that the diol (C) could function as a chain extension by its interaction with pre-obtained adduct with the formation of the polyurethane, and also as a reagent for further reaction with compound (d), which interacts with hydroxyl groups and contains or introduces a charged group or atom, or uncharged group or atom, capable of forming charge. In the method according to the invention, when the polyol (C) was incorporated into the polyurethane by reaction with a pre-obtained adduct having isocyanate(s) group(s), at least one of the remaining hydroxyl group derived from a polyol, interacts with the compound (d) and, optionally, any uncharged groups or atoms capable of forming a charge obtained from the compound (d), then, at least partially, in turn charged groups or atoms. Usually polychaet glycerin, diglycerin, trimethylacetyl, trimethylolpropane and pentaerythritol. Preferred polyols include glycerol, trimethylolpropane and pentaerythritol. From polyols preferred for use are trioli and tetraol, preferably trioli. Preferred compounds (d) include dicarboxylic acids, anhydrides of dicarboxylic acids and anhydrides of dicarboxylic acids, preferably dicarboxylic acids and anhydrides, the most preferred anhydrides. Suitable dicarboxylic acid anhydrides and acid chlorides can be selected from aliphatic and/or aromatic compounds containing at least 2 carbon atoms, preferably from 4 to 10 carbon atoms, for example succinic acid and anhydride, glutaric acid anhydride, maleic acid and anhydride, and phthalic acid and anhydride. When using dicarboxylic acid or anhydride, the reaction with the hydroxyl groups of the polyol (C) leads to the formation of carboxyl groups, which can be converted into the corresponding carboxylate group by reaction with a base, such as alkali metal hydroxide, for example sodium hydroxide, or amine, such as triethylamine. Consequently, the use of the third with the x and amphoteric polyurethanes.

If the third alcohol is a polyol (C), is usually preferred that the second alcohol was selected from diols. However, if the third alcohol is a polyol (C), and the second alcohol is a polyol, it is preferable that they were different polyols. The polyisocyanates that can be used in the present invention include aliphatic, aromatic and mixed aliphatic/aromatic compounds. The term "polyisocyanate", as used in this description, refers to a compound with at least two isocyanate groups. Of the polyisocyanates is generally preferable to use diisocyanates. When using polyisocyanates containing more than two isocyanate groups, for example triisocyanate, it is preferable to mix them with diisocyanates. The polyisocyanates mainly known from the prior art, for example, as described in Encyclopedia of Polymer Science and Engineering, Vol. 13, Second Ed., 1988, pp. 243-303, included in this description by reference. Examples of suitable diisocyanates include toluene-2,4 - and 2,6-diisocyanates, difenilmetana-4,4'-diisocyanate, hexamethylenediisocyanate, dicyclohexylmethane-4,4'-diisocyanate, cyclohexane-1,4-diisocyanate, isophoronediisocyanate, etc. you can Also use blocks is the first SCP, the second and third alcohols and isocyanate groups MDI may vary within wide limits depending on, for example, the type of alcohol, the type of MDI, etc. Usually the molar ratio of hydroxyl groups and isocyanate groups is in the range from 0.5:1 to 2: 1, suitably from 0.7:1 to 1.3:1 and preferably about 0.9:1 to 1.1:1.

Typically proportional to the content of the first, second and third alcohols used in the method according to the invention, varies widely. The method is typically carried out using from about 1 to about 80 mol.% (I) hydroxyl groups of the first alcohol, from about 1 to about 75 mol.% (II) hydroxyl groups of the second alcohol and from about 20 to about 90 mol.% (III) hydroxyl groups of the third alcohol, the percentage sum of (I)+ (II)+ (III) is 100; eligible (I) is from 5 to 70 mol.%, (II) is from 2 to 65 mol.% and (III) is from 25 to 70 mol.% and preferably (I) is from 10 to 60 mol.%, (II) is from 3 to 50 mol.% and (III) is from 25 to 60 mol.%. In the preferred embodiment of the invention the first alcohol use in the prevailing quantity, so that the molar ratio of (I) hydroxyl groups of the first alcohol to (II) hydroxyl groups Vtorov the t improved sizing efficiency.

The method according to the invention can be performed in the usual way, for example as described in U.S. patent 3971764, 4096127, 4617341, 4777224 and 5561187 and in published International patent application WO 97/45395, instructions are included in this description by reference, except that in this way using other reagents. Since isocyanates are susceptible to nucleophilic attack and easily interact with water, the method preferably is carried out in a reaction medium containing water and unwanted nucleophiles. Suitably the reaction is carried out in is not water-containing inert organic solvent, for example acetone, optionally in the presence of a catalyst, for example diacetoxynaphthalene. After completion of the reaction can be performed any further interaction, and the reaction medium is treated in the usual way. Examples of these methods include the addition of water, acid and/or alkaline solution; evaporating the solvent, etc., Acid and alkali are often added for the formation of charged groups in the polyurethane. The resulting polyurethane shall be eligible to be soluble in water or dispersible in water, and thus water can be added to the formation water polyurea at least 1000.

The present invention further relates to aqueous dispersions of charged polyurethane and its use as an additive in the manufacture of paper. The dispersion may contain from about 1 to 50 wt.% polyurethane, suitably from 5 to 25 wt. %. The variance, of course, can be diluted with water before use. The term "paper" as used herein, refers to all types of cellulosic products, including paper, cardboard and pressed paper plate.

In a preferred implementation of the invention, the polyurethane dispersion is used as a sizing agent. The dispersion can be added to the raw material to obtain a paper sizing agent in the mass) or applied to the surface of the paper (the external agent sizing), it is preferable for the surface sizing of paper. In addition to a charged polyurethane aqueous composition used for gluing surface, which is usually referred to as a sizing liquid usually contains starch or its derivatives. In some applications, may be present pigments. The amount of polyurethane added to the raw material or applied to the surface of the paper may be from 0.001 to 25 wt.% per mass of dry charged polyurethane as far as Occitania embodiment of the invention the dispersion is used as a component of the coating or pre-applied coating usually for a paper coating. The coating composition according to the invention can contain any pigments traditionally used in the compositions of the coatings or previously applied coatings, including, for example, kaolin, titanium dioxide, calcium carbonate, chalk, alumina, aluminosilicate, white silk, barium sulfate, silica, talc, calcium sulfate, zinc oxide, zirconium carbonate, magnesium carbonate, the content of which is typically at least 20 wt.% based on the composition of the coating. The amount of dispersion of the charged polyurethane present in the coating composition may comprise from 0.01 to 25 wt.%, suitably from 0.01 to 8 wt.% calculated on the dry polyurethane relative to the dry coating composition. The amount of coating composition that includes a charged polyurethane applied to the surface of the paper may be in the range described above, calculated on a dry-charged polyurethane with respect to the dry pulp material, and an optional filler.

The present invention further relates to a method of surface treatment material in the form of a sheet or rod, such as paper or polymer film by applying onto the surface of the material composition, such as water compositional with the processed surface. The composition may be a composition for sizing the surface, a composition for applying a dye coating, and so on, usually applied to the surface in the amount described above, based on the dry polyurethane with respect to the dry material in the form of a sheet or cloth.

The invention is illustrated in more detail using the following examples which are not limiting. Parts and percentages are by mass and mass%, respectively, unless otherwise indicated.

Example 1 Charged polyurethane in accordance with the invention receive the following way: 60,0 ml (420 mmol) colordistance (hereinafter TDI) are added to a solution 73,1 g (204 mmol) of glycerylmonostearate (hereinafter GMS) in 200 g of acetone. The mixture is refluxed for 1 h in the presence of catalytic amounts diacetate dibutylamine. Then add 3,76 g (of 40.8 mmol) of glycerol and continue heating. After 35 min add 17.3 g (129 mmol) of di(hydroxymethyl) propionic acid (hereinafter DMPA) and 1.70 g (of 14.3 mmol) of N-methyldiethanolamine (hereinafter N-MDEA) in 200 g of acetone. The reaction mixture is refluxed for another 1 h and then treated with 116 ml of 1 M NaOH (aq.) and 1000 ml of water. The acetone is evaporated in vacuum with politenessto as well as in example 1, except that the TDI is added to the acetone solution as GMS, and glycerin.

After boiling under reflux for 70 min, add DMPA and N-MDEA, as described above, and then the reaction mixture is refluxed for another 2 h, the Reaction mixture was treated as described in example 1, to obtain the aqueous dispersion of anionic polyurethane.

Example 3-Charged polyurethane according to the invention receive essentially the same as in example 1, except that using 5.0 g (to 54.3 mmol) of glycerol, 14.8 g (110 mmol) of DMPA, 1,46 g (12.3 mmol) of N-MDEA and 100 ml of 1 M NaOH. The reaction mixture is treated with obtaining a water dispersion of an anionic polyurethane.

Example 4 Charged polyurethane according to the invention receive essentially the same as in example 1, except that the glycerol replace 3.8 g (61,2 mmol) of ethylene glycol. The reaction mixture is treated with obtaining a water dispersion of an anionic polyurethane.

Example 5 Charged polyurethane according to the invention receive essentially the same as in example 1, except that the glycerol replace 5.5 g (61,2 mmol) of 1,4-butanediol. The reaction mixture is treated with obtaining a water dispersion of an anionic polyurethane.

Example 6
Charged by the t 7.2 g (61,2 mmol) of 1,6-hexandiol. The reaction mixture is treated with obtaining a water dispersion of an anionic polyurethane.

Example 7
Charged polyurethane according to the invention receive essentially the same as in example 1, except that the glycerol replace 4.7g (61,2 mmol) of 1,2-propane diol. The reaction mixture is treated with obtaining a water dispersion of an anionic polyurethane.

Example 8
Charged polyurethane according to the invention receive essentially the same as in example 1, except that the glycerin substitute of 4.2 g (30,6 mmol) of pentaerythritol. The reaction mixture is treated with obtaining a water dispersion of an anionic polyurethane.

Example 9
Charged polyurethane according to the invention receive essentially the same as in example 1, except that glycerin is not used and the amount of DMPA, N-MDEA and 1M NaOH make up 24.6 g (183 mmol), 2,43 g (to 20.4 mmol) and 165 ml, respectively. The reaction mixture is treated with obtaining a water dispersion of an anionic polyurethane.

Example 10
For comparative purposes and charged polyurethane received in accordance with guidance issued by the U.S. patent 4777224 as follows: 15 ml (105 mmol) of TDI was added to a solution of 18.3 g (51,0 mmol) GMS in 50 g of acetone. The mixture was boiled under reflux for 1 h in the presence rolled the and and 13.8 g (6,89 mmol) of polyethylene glycol with an average molecular weight of 2000. The reaction mixture is boiled under reflux for another 90 min and then was treated to 14.4 ml of 1M NaOH (aq. ) and 250 ml of water. The acetone is evaporated in vacuum to obtain aqueous dispersions of anionic polyurethane.

Example 11
Charged polyurethane according to the invention receive the following way: 15 ml (105 mmol) of TDI are added to a solution of 18.3 g (51,0 mmol) GMS in 50 g of acetone. The mixture is refluxed for 1 h in the presence of catalytic amounts diacetate dibutylamine. Then add 0,94 g (10.2 mmol) of glycerol and heating continued. After 25 min type of 1.97 g (of 7.65 mmol) N-MDEA, quaternionic with epichlorohydrin (hydroxy-functional Quaternary ammonium compounds obtained in accordance with the instructions WO 97/45395; hereinafter referred to as N-MDEA-ECH), and then to 3.34 g (28.1 mmol) of N-MDEA in 50 g of acetone. The temperature was raised and the reaction mixture was refluxed for 50 minutes Obtained acetone solution was poured in 27 ml of 1M model HC1 (aq.) and 250 ml of water. The acetone is removed in vacuo to obtain a water dispersion of cationic polyurethane.

Example 12
Charged polyurethane receive basically by way of example 11, except using N-MDEA-ECH and the number of N-MDEA and model HC1 1M increased to 4.26 deaths g (35,7 mmol) is 13
For comparative purposes and charged polyurethane was obtained by the method of example 11, except that it is not used glycerin, and the number of N-MDEA and 1M model HC1 was increased up to 5.17 g (a 43.4 mmol) and 39 ml, respectively. The resulting product was a water dispersion of cationic polyurethane.

Example 14
For comparative purposes and charged polyurethane was obtained by the method of example 12, except that it is not used glycerol and N-MDEA-UST and the number of N-MDEA and 1M model HC1 (aq.) increased to between 6.08 g (51,0 mmol) and of 48.5 ml, respectively. The resulting product was a water dispersion of cationic polyurethane.

Example 15
Sizing efficiency of anionic polyurethane dispersions obtained in examples 1-10 were evaluated by the test method Cobb (Cobb) using standard German DIN 5312, which is commonly used in engineering method. Values Cobb60correspond to the absorption by the paper of water, expressed in g/m2water absorption after 1 min contact time.

Sizing liquid containing polyurethane dispersion was applied using a laboratory sizing press on unsized paper basis. Sizing liquid also contained 5% degradable number of polyurethane dispersion (expressed in %) is calculated on the dry anionic polyurethane in relation to the dry paper.

As can be seen from table 1, the sizing efficiency of the polyurethane dispersions of examples 1-8 according to the invention shows a significant improvement in comparison with the polyurethane dispersions of examples 9 and 10, taken for comparison.

Example 16
Sizing efficiency of cationic polyurethane dispersions according to examples 11 to 14 were evaluated as in example 15. The results are presented in table 2, where the amount of the polyurethane dispersion (expressed in %) is calculated on the dry cationic polyurethane relative to the dry paper.

As can be seen from table 2, the sizing efficiency of the polyurethane dispersions of examples 11 and 12 according to the invention shows a significant improvement in comparison with the polyurethane dispersions of examples 13 and 14, taken for comparison.


Claims

1. The method of obtaining charged polyurethanes, including the interaction of the isocyanate groups of MDI with hydroxyl groups of various alcohols, including (i) the first alcohol is selected from one or more diols containing at least 10 carbon atoms; (ii) a second alcohol selected from alkilbenzolov having not more than 8 carbon atoms, alkiloksibenzolov, with no more than the security of (a) diols, containing a charged group or atom, (b) diols containing uncharged group or atom capable of forming a charge and at least partial transformation of uncharged group or atom in a charged group or atom, (C) polyols, and further interaction with one or more hydroxyl groups derived from a polyol with a compound containing a charged group or atom, or a compound containing uncharged group or atom capable of forming a charge or at least partial conversion of the specified uncharged group or atom in a charged group or atom, and mixtures thereof.

2. The method of obtaining charged polyurethanes under item 1, wherein the second alcohol is selected from alkilbenzolov having not more than 8 carbon atoms, alkiloksibenzolov having not more than 8 carbon atoms and mixtures thereof.

3. The method of obtaining charged polyurethanes under item 1, wherein the second alcohol is selected from polyols containing from 3 to 10 carbon atoms.

4. The method of obtaining charged polyurethane on PP.1, 2 or 3, wherein the first alcohol is introduced into the process before the introduction of the second alcohol or simultaneously with the second alcohol.

5. The method of obtaining charged polyurethanes on the tsya aliphatic diola, having the aliphatic substituent in the side chain containing at least 10 carbon atoms.

6. The method of obtaining charged polyurethanes according to any one of the preceding paragraphs, characterized in that the polyurethane is anionic.

7. The method of obtaining charged polyurethane on PP.1, 2, 3 or 4, characterized in that the polyurethane is cationic.

8. The method of obtaining charged polyurethane on PP.1, 2, 3 or 4, characterized in that the polyurethane is amphoteric.

9. The method according to any of the preceding paragraphs, characterized in that the third alcohol selected from (a) diols containing a charged group or atom, (b) diols containing uncharged group or atom capable of forming charge, and mixtures thereof.

10. The method according to any of the preceding paragraphs, characterized in that the first and second alcohols injected into the process to communicate before the introduction of the third alcohol.

11. The method according to any of the preceding paragraphs, characterized in that (i) the first aliphatic alcohol is diola having aliphatic Deputy with at least 10 carbon atoms; (ii) a second alcohol selected from diols, triolo, tetraols and mixtures thereof, and (iii) third, the alcohol is chosen from N-arcandyalagireeio, hell the acids and quaternization products of these compounds, diols containing the group of carboxylic acids, diols containing carboxylate group, diols containing group, sulfonic acids, diols containing sulphonate group, and mixtures thereof.

12. The method according to any of the preceding paragraphs, characterized in that it is carried out by using 10 to 60 mol.% (I) hydroxyl groups of the first alcohol, 3 - 50 mol.% (II) hydroxyl groups of the second alcohol and 25 to 60 mol. % (III) hydroxyl groups of the third alcohol, and the percentage sum of (I)+(II)+ (III) is 100.

13. Charged polyurethanes obtained by the method according to any of paragraphs.1-12.

14. Aqueous dispersion containing charged polyurethane on p. 13 or containing charged polyurethane obtained by the method according to any of paragraphs.1-12.

15. The method of surface treatment of cellulosic material in the form of a sheet or cloth by applying the composition on the surface of the material, characterized in that the composition comprises charged polyurethane on p. 13 or the aqueous dispersion containing the charged polyurethane under item 14, the number of polyurethane applied to the paper surface is 0.001 to 25 wt.%, calculated on a dry-charged polyurethane on a dry cellulosic material and possibly the filler.

16. The way the eating the aqueous sizing composition.

17. The method according to p. 15, characterized in that it is a method of coating paper, which is carried out using aqueous compositions containing pigments.

 

Same patents:

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The invention relates to the field of polyurethane materials and method of production thereof

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FIELD: self-crossing dispersion for dressing of glass-fiber.

SUBSTANCE: the invention is pertaining to the field of the self-crossing dispersion for dressing of glass-fiber on the basis of polyurethane, polyurethane-polyurea or polyurea used for dressing glass-fiber. The invention is also dealt with a method of production of the indicated dispersion and with a sizing compound for glass-fiber. The indicated dispersion contains the blocked isocyanate groups bound with the polymer and in addition the reaction-capable hydroxyl or amino groups bound with the polymer. The dispersion is stable at storing up to 50 °C and is self-crossing at the temperature of 90°C up to 280°C. The dispersion represents a reaction product - a) at least one polyolic component; b) at least one di-, tri- and / or a polyisocyanate component, c) at least one hydrophilic nonionic or a (potentially) ionic component; d) at least one component, which is distinct from a)- or b)-, having molecular mass - 32-500 and at least one isocyanate-reaction capable group; and e) at least one monofunctional blocking component. The offered dispersions are suitable for use in the capacity of coatings for mineral emulsion carriers, textile and leather, lacquers and polishes for wood, and also may be applied as paint primers, bases, joint fillers or finishing coatings.

EFFECT: the invention allows to use the dispersions as coatings for mineral emulsion carriers, textile and leather, lacquers and polishes for wood and to applied them as paint primers, bases, joint fillers or finishing coatings.

21 cl, 4 ex

FIELD: polymer production.

SUBSTANCE: rigid filled polyurethane foams are prepared by reaction of hydroxyl-containing component A, polyisocyanate component B with 29-33% of NCO groups, and liquid glass as inorganic filler (C) possessing modulus 4 and density 1.3-1.5 g/cm3 in amount 50-150 wt parts per 100 wt parts of sum of A and B components, reaction being carried out in presence of special additives. According to invention, liquid glass is potassium liquid glass and A, B, and C components are mixed simultaneously using counter-jet technique in mixing head of three-component of priming machine under pressure 15-22 MPa. Thus obtained polyurethane foams are inflammable and show compaction strength up to 0.73 MPa at 10% deformation, heat conductivity 0.025 W/m K at 25°C, heat resistance up to 265°C, and moisture absorbance about 0.02 kg/m2. The foams can be employed in manufacture of heat-insulation materials for needs of construction and refrigeration engineering as well as in mechanical engineering.

EFFECT: improved performance characteristics.

2 tbl, 3 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to polyester-based resins and utilization thereof in two-component compositions and water-based coating compositions and provides a resin based on ramified hydroxyl-functional polyester with average hydroxyl functionality >2, hydroxyl number 25-300 mg KOH/g and average number molecular mass 500-3000, which resin contains poly(alkylene oxide) groups and optionally sulfonate groups. Resin is characterized by that it contains reaction product of (i) carboxylic acid mixture containing 50-80 mol % m- and/or p-aromatic and/or cycloaliphatic monocarboxylic acid containing more than 6 carbon atoms and, optionally, acid containing three or more functional groups; and (ii) alcohol mixture including aliphatic diol containing at least 4 carbon atoms, C1-C4-alkoxypolyalkyleneoxyde glycol and/or C1-C4-alkoxypolyalkyleneoxyde-1,3-diol with average number molecular mass 500-3000 and, optionally, polyatomic alcohol containing 3 or more functional groups. Resin is further characterized by carboxylic number ≤20 mg KOH/g (less than 0.357 mequ COOH groups per 1 g polymer) and, optionally, sulfonate number ≤4 mg KOH/g (less than 0.070 mequ sulfonate groups per 1 g polymer), wherein acid groups are at least partly neutralized. Resin is used as a base for preparing aqueous dispersion, aqueous cross-linkable binding composition, and aqueous coating composition.

EFFECT: facilitated removal of water from resulting coating layer and accelerated setting velocity for binding composition.

14 cl, 7 tbl, 82 ex

FIELD: production of fireproof polyurethane foam.

SUBSTANCE: proposed method includes interaction of composition containing polyether polyol, polyisocyanate, expanded graphite, amine activator-stabilizer, foaming agent (water or freon) and modifying agent: multi-atom alcohols and melamine cyanurate. Prior to interaction of polyether polyol with polyisocyanate, polyether polyol is mixed with amine activator, stabilizer, modifying agent and foaming agent; then expanded graphite and melamine cyanurate are added at ratio of 1-2 : 1 in the amount of 15-30 mass-% of total amount of components. Said composition contains additionally phosphate antipyren trichloroethyl phosphate. Proposed method enhances fire-retarding quality of polyurethane foam at retained physico-chemical characteristics (apparent density 45 kg/m3, breaking stress at compression of 330 kPa, heat conductivity coefficient 0.025 W/m2 and heat absorption of 1.0% per 24 h) characterizing heat- and sound-insulating properties.

EFFECT: enhanced efficiency.

2 cl, 2 tbl, 3 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to ionomer thermoplastic polyurethane, method for preparation thereof, use of indicated ionomer thermoplastic polyurethane to prepare aqueous dispersions thereof, as well as to a method for preparing aqueous dispersions of ionomer thermoplastic polyurethanes. Ionomer thermoplastic polyurethane is prepared via continuous reaction of (i) 4-50% if diisocyanate; (ii) 35-95% of bifunctional polyatomic alcohol selected from group comprising (a) polycaprolactone with mean molecular mass between 500 and 15000 and general formula I: (I), (b) polyesterdiol with mean molecular mass between 500 and 15000 and general formula II: (II), (c) polyesterdiol selected from polypropylene glycol, polytetramethylene glycol, and polyethylene glycol, (d) polycarbonatediol with mean molecular mass between 500 and 15000 and general formula III: (III), and (e) copolymers obtained from two bifunctional polyatomic alcohol from groups (a), (b), (c), or (d); (iii) 0.2-16% of chain-elongation glycol of general formula IV: (IV); and (iv) 0.2-3% of chain-elongation anionic-type ionomer glycol of general formula V: (V).

EFFECT: enabled preparation of ionomer polyurethane suitable for being stored in solid form for subsequent preparation of aqueous dispersions of thermoplastic polyurethanes appropriate as industrial adhesives and coating materials for flexible and rigid substrates.

34 cl, 2 tbl, 10 ex

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