Adhesive compositions

FIELD: chemistry.

SUBSTANCE: group of inventions relates to adhesive composition and method of its obtaining, to polyamidoamine-epihalogenhydrin resin (PAE), as well as to method of obtaining composite material based on wood, laminate, plywood, chipboard, fibreboard. Method on obtaining adhesive composition includes combination of PAE with protein source. Adhesive composition possesses content of solid substances exceeding 45 wt % counted per the total glue weight. The total content of solid substances in PAE resin and protein source constitutes not less than 45% of the total content of solid substances in glue. PAE resin possesses content of solid substances, exceeding 40% and is characterised by Brookfield viscosity, measured by means of Brookfield LV viscometer, equal less than 200 cP, content of azetidine groups equal more than 0.75 meq./g, RSV value, equal lower than 0.3 dl/g, stability in ageing, exceeding one week at 32°C. Method of composite material obtaining includes addition of adhesive composition to suitable substrate.

EFFECT: invention makes it possible to considerably increase content of solid substances in glue and characteristics of composite material.

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The technical field TO WHICH the INVENTION RELATES

The present invention relates to compositions, obtain, and use of composite materials based pressure sensitive adhesive having a high content of solids, which contains polyamidoamine-epichlorhydrin resins (PAE resins). The present invention also relates to the use of PROBES in combination with a source of soy protein. The present invention also relates to the application of the adhesive in the composite and, in particular containing wood composite materials.

The LEVEL of TECHNOLOGY

The PAE polymers are well known in the technology of production of paper, as additives, providing strength in the wet state. The use of these polymers PAE as components of a curing agent for adhesives based on protein or lignin (application US 2005/0282988). Known to use PAE together with proteins, such as soy flour, soy protein or lignin as an adhesive for lignocellulosic materials (US patent No. 7252735).

The currently available constraints for this type of glue is often associated with the desired solids content. In addition, the use of PAE resins having a high content of solids, was previously limited due to their high viscosity and poor stability during aging. With�Rastede the need to use containing PAE adhesives, the need for possessing a high content of solids stable PAE resins, allows you to get in with a high content of solids of the adhesive composition, which under normal conditions of use in a particular case, give the samples of composite materials strength and adhesion, which are almost the same or better than existing low solids compositions on the basis of PAE.

Known PAE resin having low molecular weight (US 2007895122A). Such materials have a low viscosity. However, to ensure a low viscosity at a higher content of solids and maintain stability during aging the necessary additional knowledge disclosed in the present invention.

In the patent US 5567798 (column 6, lines 60-61) States that "to increase the lifetime of residual preferably the solids content is 30% or less". In contrast PAE resins proposed in the present invention are unexpectedly stable at a solids content of about 40 wt.% or more.

In the US patent 3197427, 4853431, 6908983 B2, and 7291695 B2 indicated that the stability necessary low pH. In the first, the pH range is from 2.0 to 3.0, the second value is below 4.2 and most preferably from 3.2 to 3.4, stretham value is lower than the 3.3 and the fourth value is less than 3.0. In contrast and unexpectedly, the present invention PAE resin is stable at higher pH values. This is all the more unexpected given the high content of solid substances in the PAE resins proposed in the present invention, and even more unexpected given the fact that the resin is proposed in the present invention are characterized not only stable viscosity and high stability azetidine groups that, as ampichino below, is important.

In the patent application US 2005/0261404 A1 (paragraphs 32 and 33) the possibility of obtaining possessing a high content of solids suspension belkovogo material even when the content up to 50%. However, experts who are familiar with materials containing protein, you know that with such a large content of solid substances can be used not all sources of protein. For example, non-denatured soy flour when mixed with water can be used when the solids content of approximately 35%. When the solids content exceeding 35%, the viscosity rapidly increases until the material becomes impossible to mix, easy to mix or pump to pump. The viscosity remains high even when adding a viscosity modifier, such as sodium bisulfite. When the content of sodium bisulfite, equal to 1% based on the weight of dry soy flour, viscosity of water� mixture when the concentration of solids, equal to 30%, equal to about 400 SP, when the content of solids equal to 33%, it is approximately 1800 SP and when the content of solids equal to 36% it is equal to about 20,000 CPS. By increasing the solids content, the viscosity continues to increase exponentially. When the content of solids, greater than about 36%, a mixture of soy flour/water cannot easily be stirred or pumped by the pump. Therefore, as shown in the present invention, it is necessary to increase the solids content by increasing the solids content in the component PAE.

In the patent application US 2005/0261404 A1 (paragraph 21) patented compositions are also limited containing soy protein without urease. This is not a mandatory requirement for adhesives based on a combination of a protein source with PAE resin.

Having a high solids adhesives obtained by having a high solids PAE resins, in some cases, necessary for successful use and/or manufacture of a composite material. For example, in a typical manufacturing technology chipboards about 93 parts of wood combined with 7 parts of glue on the basis of the urea-formaldehyde resin and a typical urea-formaldehyde resin (MF) has a solid content of prophetic�STV, equal to 65%. Specialists in the art know that the use of much lower solids contents under normal conditions of production at the factory chipboards leads to disruption of the internal connections in a chipboard, which gives the defective plate (see Modern Particleboard &Dry-Process Fiberboard Manufacturing by T. M. Maloney, 1977 Miller Freeman Publ.).

Although MF resin are very durable, cure rapidly and fairly easy to handle, these resins have poor hydrolytic stability of the main polymer chain. This leads to the release of significant amounts of free formaldehyde from the finished product (and ultimately to its inhalation by residents). Undertaken a number of legislative measures to exclude these resins from the products used inside houses (Health and Safety Code Title 17 California Code of Regulations Sec. 93120-93120,12).

Replacement or improvement of glue at the base of MT are highly desirable due to the adverse effects of formaldehyde on the environment. Previously on an industrial scale were produced based adhesives PAE and soybeans, such as a mixture PAE/soy flour, in which the PAE resin ranged from 20 to 30% solids. If under normal conditions of use PAE and soy flour, then in the resulting adhesives do not contain 65% of the solids in the resin MT. Large solids ve�of the EU ETS is provided only by adding large amounts of low molecular weight components, such as urea and glycerol (patent application US 2009/0098387). Not previously received suitable adhesives having a viscosity of less than 5000 SP, such as on the basis of MF resin in which not less than 40 and preferably more than 50% of the composition is formed solids are a combination of EAP and a protein source such as soy flour.

A BRIEF SUMMARY of the INVENTION

The use of PAE resins having a high content of solids leads to an increase in achievable amounts of solid substances and the number of active solids in the adhesive. This also applies to other adhesive systems based on EAP and protein that compete with such adhesives, based on MOF and phenol-formaldehyde resins.

The present invention relates to compositions, obtain, and use of composite materials based pressure sensitive adhesive having a solids content exceeding 45%, and preferably greater than 50%, which include possessing a high content of solids polyamidoamine-epichlorhydrin resins (PAE resins). Having a high content of solids PAE resin, proposed in the present invention, has a solids content greater than 40% and preferably greater than 43%. From solids contained in the adhesive, at least 45% and preferably more than 50 wt.% total �leave solids PAE and a protein source. A relatively high solids PAE allows you to provide great content of solids in the adhesive. PAE applicable in the present invention is stable during aging exceeding one week at 32°C.

The present invention also relates to the use of compositions as adhesives for bonding wood products such as laminates, plywood, particleboard, chipboard, oriented with the layout of the chip and fiberboard.

The use of adhesive for the manufacture of various products, such as specialized timber and other types of useful materials can be accomplished in various ways known to those skilled in the art. In many such applications it is useful to use an adhesive composition having a high content of solids and low viscosity.

A DETAILED DESCRIPTION of the INVENTION

The present invention relates to compositions, obtaining and applying adhesive having a solids content exceeding 45% and preferably greater than 50 wt.%, which contains polyamidoamine-epichlorhydrin resins (PAE resins) having a solids content greater than 40 wt.% and preferably greater than 43%, in which a relatively high content of solid substances� in PAE allows you to provide great content of solids in the adhesive and in which the PAE also has stability during aging, exceeding one week at 32°C. in addition, the solids contained in the adhesive composition contain at least 45% and preferably more than 50 wt.% the combination of solids PAE and a protein source. The present invention also relates to the use of PROBES in combination with a source of soy protein. The present invention also relates to the application of the adhesive in the composite and preferably containing wood composite materials, and more preferably in composite materials based on wood fibers or chopped wood.

The present invention relates to having a high content of solids of the adhesive composition and to its use, the adhesive consists of having a high content of solids thermosetting polyamidoamine-epichlorhydrin resins (PAE resins) and the protein or lignin. The solids content of the PAE resin of the present invention, greater than 40%, preferably more than about 43%. These adhesives are applicable for bonding wood and other materials. In accordance with the requirements that are set down to modern PAE resins, reopened with a high content of solids PAE resin should have a lower viscosity at a given concentration and they must be stable during aging exceeding one week �ri 32°C. Stability during aging is defined as the stability when using PAE solution at a given concentration and stability means an increase in viscosity of no more than 3 times, or preferably a viscosity increase of not more than 2 times. In addition, the stability means a loss of not more than 20% of its azetidine groups and more preferably the loss of not more than 15%. Having a high solids PAE resin also can be classified according to molecular weight, determined by using per, ber, and they must have the value of per, ber, equal to less than 0.3 DL/g.

According to the invention it has surprisingly been found that adhesive strength in dry and wet adhesive compositions made with having a high content of solids and low viscosity stable PAE resin, adhesive capacity equivalent in dry and wet conditions with high molecular weight stable PAE resin. This differs dramatically from application of PAE resins in the manufacture of paper, when it was shown to significantly increase the strength of the paper requires a large molecular weight.

SYNTHESIS PAE

Synthesis of PAE resins is two-stage. First polycondensation polyamine with a polybasic carboxylic acid or derivative with polybasic carboxylic collationkey polyamidoamine. Polybasic carboxylic acid is an organic compound containing at least two carboxyl groups (carboxylate). Then, the resulting polyamidoamine dissolved in water and in aqueous solution is introduced into the reaction with epichlorohydrin to obtain a final product PAE. Polyamidoamine usually prepared by heating the carboxylic acid with a polyamine at a temperature equal to 125-200°C for 1 to 10 h with removal of water formed in the condensation reaction, at atmospheric pressure. When using low pressure you can apply a lower temperature, such as equal to from 75 to 150°C. At the end of this reaction, the resulting product dissolved in water at a concentration equal to from about 25 to 80 wt.% in terms of the full content of solids in the polymer, more preferably in a concentration of approximately from 30 to 70% and most preferably at a concentration of approximately 40 to 60%.

To obtain polyamidoamine instead of the dicarboxylic acids can be used diester. When using diester, the polymerization can be done at a lower temperature, preferably equal to approximately 100-175°C, at atmospheric pressure. In this case, the byproduct will be alcohol, type of alcohol depends on the structure of the diester. For example, if you use dimethyl ether, alcohol side will be methanol, then kakabona product derived from diethyl ether, ethanol will be. When using low pressure you can apply a lower temperature, such as equal to from 75°C to 150°C.

Usually, to obtain polyamidoamine use dicarboxylic acids, although you can use polybasic carboxylic acids containing more than two carboxyl groups. Suitable polybasic carboxylic acids include, but are not limited to, malonic acid, glutaric acid, adipic acid, azelaic acid, citric acid, tricarballylic acid (1,2,3-propanetricarboxylic acid), 1,2,3,4-butanetetracarboxylic acid, nitrocresol acid, N,N,N',N'-ethylenediaminetetraacetic acid, 1,2-cyclohexanecarbonyl acid, 1,3-cyclohexanecarbonyl acid, 1,4-cyclohexanecarbonyl acid, phthalic acid, isophthalic acid, terephthalic acid, imidouksusnye acid, 1,2,4-benzotriazolyl acid (trimellitic acid) and 1,2,4,5 - sensortechnology acid (pyromellitic acid), and mixtures thereof.

To obtain polyamidoamine also possible to use derivatives of carboxylic acids. These derivatives can be esters of carboxylic acids, acid halides or acid anhydrides. These derivatives are usually more reactive towards amines than the corresponding derivatives ka�oil acids, so the conditions of the reactions for obtaining polyamidoamine using carboxylic acids are usually milder than the conditions used to obtain polyamidoamine of polybasic carboxylic acids and polyamines.

If obtaining polyamidoamine for the preparation of PAE proposed in the present invention, use esters of polybasic carboxylic acids, typically use methyl or ethyl esters. By - product alcohol (methyl alcohol or ethyl alcohol) in the synthesis of distilled off and the synthesis can be done at a lower temperature than when using the corresponding carboxylic acid. For the synthesis polyamidoamine esters of polybasic carboxylic acids and polyamines can be used by Slavnoi catalyst, such as sodium methoxide. Specific esters of polybasic carboxylic acids which are suitable include dimethyladipate, diethylmalonate, diethylmalonate, dimethylsuccinic, dimethylglutaric and diacylglycerol.

Suitable anhydrides of acids that can be used to obtain polyamidoamine include, but are not limited to, succinic anhydride, maleic anhydride, dianhydride N,N,N',N'-dianhydride ethylenediaminetetraacetic acid, phthalic anhydride, millitay anhydride and pyromellitic anhydride and mixtures thereof.

Gelegenheid m�oroonoko carboxylic acids can be introduced into the reaction with the polyamine with getting polyamidoamine. Particularly suitable are the anhydrides of polybasic carboxylic acids. The reaction can be done at a very low temperature. Suitable polybasic acid halides of carboxylic acids can be obtained from polybasic carboxylic acids in their reaction with thionylchloride or phosphorus trichloride. Examples include, but are not limited to, adipocere, putrilage and semicollared.

In the synthesis polyamidoamine you can use one polybasic carboxylic acid or its derivative, and a mixture of polybasic carboxylic acids. In addition, for this reaction is suitable mixture of polybasic carboxylic acids and derivatives of polybasic carboxylic acids.

To obtain polyamidoamine you can use various polyamines. They include the General class of polyalkyleneglycol, which can be polyethylenepolyamine, polypropyleneimine, polietilenimine, polyethylenepolyamine, polyhexamethylene and mixtures thereof. More precisely, polyallylamine intended for use, can be represented as polyamines in which the nitrogen atoms are linked together by groups of the formula CnH2n-, where n is a small integer greater than 1, and the number of such groups in the molecule is from 2 to about 8. The nitrogen atoms can be linked to adjacent carbon atoms�Yes group - CnH2n- or with more distant carbon atoms, but not to the same carbon atom.

This includes the use of not only polyamines such as Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine and dipropylenetriamine that can be obtained in a sufficiently pure form, but also mixtures and various noisenik polyamines containing materials. For example, for use as the initial substance satisfactory mixture of polyethylenepolyamines obtained by the reaction of ammonia and ethylene dichloride, which is clear only from chlorides, water, excess ammonia and Ethylenediamine. The term "polyalkyleneglycol" means and includes any of polyalkyleneglycol listed above, or mixtures of such polyalkyleneglycol and their derivatives.

Additional polyamines which are suitable for use include, but are not limited to, bis-hexamethylendiamine (BHMT), N-methylbis(aminopropyl)amine (MAPA), AMINOETHYLPIPERAZINE (AEDs) and other polyallylamine (e.g. spermine, spermidine). The preferred polyamines are Diethylenetriamine (DETA), Triethylenetetramine (THETA), Tetraethylenepentamine (TEP) and dipropylenetriamine (DPTA).

If diamines are used for the synthesis polyamidoamine, they should not introduce amino groups into the final product, since both end groups each�midastouch with the formation of amide linkages. This leads to the effect of "diluting" of the amino groups in the polymer, i.e. the equivalent of amine molecular weight increases. In some cases it is desirable to increase the distance between the secondary amino groups in the polyamide molecule to modify the reactivity of the complex polyamide-epichlorohydrin. This can be done by changing a part of polyallylamine a diamine, such as Ethylenediamine, Propylenediamine, hexamethylenediamine, etc., For this purpose, approximately 80% of polyallylamine you can replace a molecular equivalent amount of diamine. Usually for this purpose replace about 50% or less.

Similar to adding a diamine in the synthesis polyamidoamine, aminocarbonyl acids or lactams increase the distance between the amino groups without the introduction of amino groups into the polymer. Relevant aminocarbonyl acid containing at least 3 carbon atoms, or their lactams are also suitable in the present invention for use with the goal of increasing distance. For example, 6-aminohexanoic acid and caprolactam are suitable additives for this purpose.

Disclosed are various ways of obtaining polyamidoamine, which provides regulation of the molecular weight and structure polyamidoamine. They include the use of monofunctional reagents blocking end groups, for reg�of stimulation of molecular weight, disclosed in US patent No. 5786429, in US patent No. 5902862 and in US patent No. 6222006 that are all included in the present invention as a reference. Such use reagents blocking end groups in the synthesis polyamidoamine is useful because you can include them in polyamidoamine used as starting compounds in the present invention. For example, when receiving polyamidoamine with blocked terminal groups, you can substitute part of decicate monofunctional acid and/or you can replace part of the polyamine monofunctional amine.

Upon receipt polyamidoamine for blocking end groups can be used various methods, conditions, and materials, including conventional methods, conditions and materials, including those described in the present invention. When using, for example, an equimolar mixture of dicarboxylic acid and polyallylamine for every 1 mole removed decicate or polyallylamine preferably use about 2 moles of monofunctional carboxylic acids or monofunctional amine, a blocking end groups.

It is possible to regulate the molecular weight obtained by condensation polymer by adjusting the relative quantities of bifunctional and monofunctional reagents (reagents blocking end groups) in the system. Tuorerehupalvelu molecular weight and influence of the monofunctional additives on the resulting condensation polymer are well known. 1 DPnis defined as the degree of polymerization or average number of monomer units in the polymer chain. In equation 1 DPnis determined using the molar ratios of the amounts of the components under the assumption about the reaction of all functional groups:

DPn=(1+r)/(1-r)(1)

where r is defined as the ratio of monomer units and is calculated as follows:

r=A/(D+2C)(2)

A and b are dysfunctional Monomeric components and C is a monofunctional component of the reagent, the blocking end groups). The value of r is always less than 1.

The product with controlled molecular weight obtained using appropriate quantities of monofunctional reagent. The composition can be defined as polyamidoamine obtained from A parts dicarboxylic acid, In parts of polyallylamine and parts of monofunctional�th fragment, the blocking end groups are molar.

If A>, then the fragment, the blocking end groups, will be monofunctional amine and C will be equal to approximately 2(A-b). If>And, a fragment, a blocking end groups, will be monofunctional acid, and C is equal to about 2(B-A). In this case, equation [2] can be rewritten in the form:

r=B/(A+2C)(3)

Preferably, if polyamidoamine have values DPnin the range of from about 3 to less than 50, more preferably in the range of from about 3 to 40 and most preferably, if DPnis in the range of from about 3 to 30.

When the reaction for producing polyamidoamine you can use different temperature and duration of reaction. Temperature of approximately 125 to 260°C. are preferred, more preferred equal to approximately 155°C to 200°C, and the reaction mixture is preferably maintained at these temperatures for about 2 to 12 hours, more preferably for about 2 to 6 hours.

Suitable monofunctional amines are used as reagents blocking end �the group, include, but are not limited to, monofunctional primary amines, including monoalkylamines and monoalkanolamines, and monofunctional secondary amines, including diallylamine and dialkanolamine.

Monofunctional primary amines include, but are not limited to the butylamine, ethanolamine (i.e. monoethanolamine, or MEA), cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, benzylamine, isopropanolamine (i.e. monoisopropanolamine), mono-sec-butanolate, 2-amino-2-methyl-1-propanol, Tris(gidroximetil)aminomethan, tetrahydrofurfurylamine, furfurylamine, 3-amino-1,2-propandiol, 1-amino-1-deoxy-D-sorbitol and 2-amino-2-ethyl-1,3-propandiol. Monofunctional secondary amines include, but are not limited to, diethylamine, dibutylamine, diethanolamine (DEA), di-n-Propylamine, Diisopropylamine, di-sec-butanamine and N-methylbenzylamine.

Monofunctional carboxylic acids, applicable to obtain polyamidoamine with blocked terminal groups include, but are not limited to, benzoic acid, 2-hydroxybenzoic acid (i.e. salicylic acid), 3-hydroxybenzoic acid, acetic acid, phenylacetic acid, propionic acid, butyric acid, valeric acid, capreomycin, Caprylic acid, 2-ethylhexanoyl to�slot, oleic acid, ortho-Truelove acid, meta-Truelove acid and para-Truelove acid, ortho-methoxybenzoic acid, meta-methoxybenzoic acid and para-methoxybenzoic acid.

Esters of monofunctional carboxylic acids, applicable to obtain polyamidoamine with blocked terminal groups include, but are not limited to, methyl acetate, ethyl acetate, methylbenzoate, ethylbenzoic, methylpropionate, ethylpropane, methylbutyrate, ethylbutyrate, methylphenylacetic and ethylvinylacetate.

The volatility of the reagent, the blocking end groups must be sufficiently low so that the reagent, the blocking end groups, remained in the reaction mixture to polymerization at a temperature at which the reaction is carried out. In particular, if polyamidoamine get by thermal polycondensation, volatility is an important characteristic of the reagent, the blocking end groups; in this case, is the preferred reagent, a blocking end groups, having a lower volatility. The boiling point of the reagent, the blocking end groups, should be high enough so that at the temperature used to remove the condensation product - i.e. water, if the reagent used dikisloty, and alcohol in the case of the diester is not removed and the reagent.

Another �] regulation of molecular weight polyamidoamine described in US patent No. 6908983 and in US patent No. 6554961, which in its entirety is included in the present invention as a reference. To obtain substances with terminal amino groups use an excess of amine. The presence of end amino groups leads to an increase in the content of amino groups in polyamidoamine and also limits the molecular weight. When you increase the excess amine increases the amount of amino groups in polyamidoamine and decreasing molecular weight. This method in the present invention is usually called "reaction with excess amine", "polyamidoamine with an excess of amino groups or a polymer with an excess of amino groups". It is assumed that polyamidoamine with an excess of amino groups can be used to gain PAE resins proposed in the present invention.

Polyamidoamine disclosed in US patent No. 6294645, which is included in the present invention by reference, include reagents, blocking end groups, and polyamidoamine, the molecular weight of which is controlled by adjusting the degree of completion of reaction. The molecular weight polyamidoamine can be adjusted by controlling the amount of distillate (water), removed during the polycondensation reaction of dicarboxylic acid and a polyamine. In accordance with well known main provisions of polymer chemistry, the molecular weight increases with increasing sovershenno� reaction and the amount of the resulting distillate. Smaller molecular weight can be achieved by stopping the reaction before the formation of the amount of distillate, the corresponding theoretical value.

The second stage of the synthesis the resin or polymer PAE is the reaction polyamidoamine with epichlorohydrin with the formation of thermosetting cationogenic resin. Obtaining thermosetting PAE resins is well known.

The synthesis of the PAE resin is usually carried out in aqueous solution. For turning polyamidoamine in cationogenic thermosetting polymer polyamidoamine injected into a reaction with epichlorhydrin, preferably epichlorohydrin, at a temperature of from about 25 to about 100°C and preferably from about 35 to about 70°C. To slow this reaction, it is preferably carried out in aqueous solution. It is possible, though not necessary, to adjust the pH value to increase or decrease the speed of crosslinking.

After reaching the desired end point of the reaction can be added an amount of water sufficient to establish the required content of solids in the resin solution, and the product can be cooled to ambient temperature and then stabilized for storage by increasing the viscosity and stability azetidine groups by changing the pH from 6.5 to 4.0 and more preferably from 6 to 4.2, and most preferably from 5.5 to 4.5 To stabilize the product can be used any suitable inorganic or organic acid, preferably sulfuric acid. Similarly, the pH value can be increased by any suitable inorganic or organic base, preferably sodium hydroxide. Usually to ensure the stability of the pH of the resin solution should be decreased by increasing the content of solids in the resin (US 2009/0036577, paragraph 8).

In the reaction polyamidoamine-epichlorohydrin is the preferred use amount of epichlorohydrin is sufficient for turning the most part, primary and secondary amine groups to tertiary amino group. For polyamidoamine that contain tertiary amino group, it is preferable to use the number of epichlorohydrin, sufficient for the conversion of the greater part of the tertiary amino groups in evertyone amino group. However, you can add more or less to increase or decrease the speed of the reaction. More traditional PAE resin is produced by using about from 0.35 to 0.65 parts of epichlorohydrin and 1 part polyamidoamine. In the present invention is preferred to use from 0.7, and 0.75 and 0.8, about 0.85, about 0.90 to 1.0, and 1.1, 1,2, 1.3 parts of epichlorohydrin and 1 part polyamidoamine. In the present invention it is preferable to use from 0.7 to 1.3 parts of epichlorohydrin and 1 part polyamidoamine and more preferably from 0.75 to 1.2 parts, and most before�occhialino from 0.8 to 1.1 parts of epichlorohydrin and 1 part polyamidoamine.

Epichlorohydrin is the preferred epichlorhydrine for use in the present invention. The present invention relates to epichlorohydrin in particular, and in some cases, however, the specialist in the art should understand that these provisions are epichlorohydrin in the General case.

It is known that higher molecular weight leads to greater strength of paper. This provision differs from the present invention. In the present invention is the provision of a large molecular weight is not desirable and steps are being taken to prevent a significant increase in molecular weight. The main task of the reaction polyamidoamine-the epichlorohydrin is carried out in the present invention is functionalization polyamidoamine the epichlorohydrin and education necessary reactive functional groups (aminomorpholine and/or azetidine group) without a significant increase in molecular weight, which limits the solids content of the finished resin.

In the present invention, it is desirable to conduct the reaction of epichlorohydrin to the point where content is provided azetidine groups exceeding about 0.75 mEq./G. the Number of milliequivalents calculated according to equation: mEq./g=(number of moles azetidine groups)/(HSMAI)* 1000. The number of moles azetidine groups contained in the resin, determined by NMR.

To obtain the low molecular weight of the PAE resin reaction polyamidoamine-epichlorohydrin can be conducted in one stage or you can use a two-stage method. In the single stage method, the epichlorohydrin was added to the aqueous solution polyamidoamine and injected into the reaction at a temperature at 35-70°C. To reduce the pH of the reaction mixture and regulation increasing the molecular weight of the PAE resin is possible to add acid. To stabilize the product can be used any suitable inorganic or organic acid. Examples include, but are not limited to hydrochloric acid, sulfuric acid, methanesulfonic acid, nitric acid, formic acid, phosphoric and acetic acid. The reaction is stopped by cooling, adding water to dilute and stabilize with added acid, before there will be any significant increase in the molecular weight of the resin.

For better control of the reaction and reduce the content formed from epichlorohydrin by-products in the final product, you can use a two-stage method. The first stage of this process is carried out at low temperature (10-45°C) and it is called the stage alkiline�position. This low-temperature stage of the epichlorohydrin interacts with the amino groups polyamidoamine education aminochlorides functional groups. The epichlorohydrin was added to the aqueous solution polyamidoamine (usually from 30 to 55% based on the full content of solids in polyamidoamine and the epichlorohydrin was then added and the temperature of the reaction mixture was maintained equal 10-45°C for 1 to 12 h. At this time, to reduce the rate of crosslinking is possible to add water. After stage alkylation reaction mixture is heated to 50-80°C for turning aminochlorides functional groups in azetidinone group. Depending on the molecular weight polyamidoamine and the required duration of the reaction it is possible to add inorganic acid (H2SO4for pH adjustment (4,0-6,0) to reduce the speed of crosslinking of the polymer. This is usually carried out at 50-55°C, however, can be made in the earlier period of the reaction or in the later period of the reaction.

PAE obtained using prepolymer having a large molecular weight, or entered into reaction with an insufficient number of epichlorohydrin, or entered into reaction with the formation of too high or too low molecular weight, or not enough azetidine groups not �can be used when a high content of solids due to excessive viscosity or insufficient stability during aging or insufficient reactivity.

Upper limit of the content of solids in a liquid adhesive composition is determined by the content of solids in the ingredients. The solids content and the viscosity of the PAE resin is determined mainly by molecular weight. The molecular weight PAE can also be expressed using the specific viscosity unit (puv). The PAE resin having a molecular weight proposed in the present invention have a solids content greater than 40%, and a viscosity in water at a solids content of 40%, equal to less than 200 SP. Such PAE resin should have a value per, ber, equal to less than 0.3 DL/g. These have a low molecular weight or low viscosity PAE should be distinguished from having a large molecular weight PAE prior art, which have values per, ber, greater than 0.3 DL/g. Typical PAE resins have values per, ber, greater than 0.3 DL/g, as a higher molecular weight is required for use in the paper industry to impart strength. The PAE resin having values per, ber, less than 0.3 DL/g, cannot be effectively used in the industry to give strength to the paper. In addition, to ensure the effectiveness of the adhesive is desirable that the PAE resin glue to the point of use had a population�of azetidine groups, greater than 0.75 mEq./g of the resin or, more preferably, greater than 1.5 mEq./g and most preferably greater than 2 mEq./G.

The molecular weight of the PAE resin used in the present invention can be described with the help PWV and its value is less than 0.3 DL/g, more preferably less than 0.25 DL/g and most preferably less than 0.2 DL/g according to the measurement of the concentration, equal to 2%, in 1 n solution of ammonium chloride at 25°C. puv is a measure of the viscosity of polymer solution and directly correlated with its molecular weight.

The viscosity of the PAE is defined as the viscosity Brookfield viscosity containing 40% solids aqueous solution of the PAE resin should be less than 200 SP.

The pH value of the PAE resin 4,0 more and less than 6.5. Preferably more than 4.2 and less than 6.0 and most preferably greater than 4.5 and less than 5,5.

The content azetidine groups must be greater than 0.75 mEq./g, more preferably greater than 1.5 and most preferably greater than 2 mEq./G.

Stability during aging should be such that when stored for one week at 32°C viscosity did not increase by more than 3 times, and more preferably, during this time, she did not increase by more than 2 times.

In one embodiment of the present invention have a low molecular weight polymer is produced by use of� in the synthesis of an excess of polyallylamine. This means the use of a reaction mixture in which the ratio of the total number of amino groups of polyamine to the total number of carboxyl groups polybasic carboxylic acid is greater than 1, which gives polyamidoamine with a predominance of terminal amino groups. The ratio of the polyamine to the number of polybasic carboxylic acids, for example, the ratio of Diethylenetriamine to the amount of adipic acid can vary in the range from greater than about 1.0:1.0 molar ratio of 1.7:1.0 and more preferably, from greater than about between 1.01:1.0 to 1.4:1.0 in. The use of an excess of a polyamine gives polyamidoamine who have lower molecular weights than that obtained by the reaction of an equimolar mixture under the same conditions. Polyamidoamine by the values DPnin the range of from about 3 to 50, more preferably in the range of from about 3 to 40 and most preferably, if DPnis in the range of from about 3 to 30. Then polyamidoamine injected into a reaction with epichlorhydrin. In the present invention it is preferable to use from 0.7, and 0.75 and 0.8, about 0.85, about 0.90 to 1.0, and 1.1, 1,2, 1.3 parts of epichlorohydrin and 1 part polyamidoamine.

The preparation of adhesives

The adhesive composition proposed in the present invention, is obtained by combining with a high content of TVE�the gut substances PAE resin with the protein and/or lignin. Suitable protein sources include, but are not limited to, soy protein, blood meal, flour of feathers, keratin, gelatin, collagen, gluten, spirulina and casein. Protein can be pushed to modify or to improve its solubility, dispersibility and/or reactivity. In US patent No. 7060798, the entire contents of which is included in the present invention by reference, describes methods of modification of the protein and its inclusion in the glue. To the adhesive composition can also be added to the diluent. Some examples of diluents include, but are not limited to, polyols such as glycerine, ethylene glycol, propylene glycol, neopentylglycol and polymer options.

In one embodiment of the present invention is disclosed a method of producing the adhesive composition. The method includes combining the PAE resin with the protein source, where the adhesive composition has a total content of solids, greater than 45 wt.% in terms of the total mass of the adhesive composition, where the total solids content of the PAE resin and the protein source is at least 45% of the total content of solids in the adhesive composition, where the PAE resin has a solids content greater than 40%, and where the PAE resin is characterized in that it has the stability during aging, previews� one week at 32°C. In some embodiments of the present invention, the adhesive composition may further contain a diluent.

Another variant of implementation of the present invention is an adhesive composition comprising a PAE resin and a protein source, where the adhesive has fully solids content exceeding 45 wt.% in terms of the total mass of the adhesive, where the total solids content of the PAE resin and the protein source is at least 45% of the total content of solids in the adhesive, where the PAE resin has a solids content greater than 40%, and where the PAE resin is characterized in that it has the stability during aging exceeding one week at 32°C. In some embodiments of the present invention, the adhesive composition may further contain a diluent.

One particularly suitable protein source for the present invention is soy. Soy protein can usually be obtained from soy flour (about 50 wt.% protein based on dry matter), soy protein concentrate (about 65 wt.% protein based on dry matter) and soy protein isolate (HMB, not less than about 85 wt.% protein based on dry matter). A suitable source of soybean in the present invention may contain urease.

The present invention provides a useable cliodna soy/PAE regardless of the value of the MDB used soy flour. Figure despergiruemaya protein (PDB) is a means of mapping the solubility of proteins in water, and it is widely used in industry of soy products. The applicability of the present invention is that the adhesive soy/PAE you can use soy flour with low or high value of the MDB, and get usable adhesives.

Lignin can be a industrial lignin, such as Kraft lignin obtained by using the Kraft process of making pulp from wood.

Combination with a high content of solids PAE resin and containing the protein material and/or lignin is obtained in the form of an aqueous mixture in which the components are combined and, if necessary, mixed with additional amounts of dilution water. In the adhesive composition can include other additives such as fillers, viscosity modifiers, protivovospalitel, biocides and fillers such as wheat flour, wood flour crust, flour made from the shell of nuts and flour from the core of corncobs. The components of the adhesive composition are combined in a suitable mixer and mixed to obtain a homogeneous mixture.

In the present invention is obtained adhesive composition having a solids content exceeding 45% and more preferably greater than 50%. In addition�about, contained solids include at least the combined solids PAE and a protein source comprising at least 45% based on the full content of solids, preferably more than 50 wt.% and more preferably more than 55%. For illustration only, is shown as follows: 200 g of the sample of the adhesive containing 50% solids: 100 g may be water; 100 g, which is not water, not less than 50 g must be the total mass of solids PAE and a protein source. The remaining 50 g of solids can come from PAE, a protein source, fillers, diluents or other solid substances. To increase the total content of solids can contain additional additives or fillers known to those skilled in the art. The most efficient value of the ratio of the number of PAE resin to the number containing protein substances and/or lignin in the adhesive composition depends on the bonded substrate, the potential stress source of protein and/or lignin and physico-chemical characteristics of the PAE resin. The ratio of the amount of protein and/or lignin to the number of PAE resin used in the adhesive composition, is preferably in the range from 95:5 to 20:80, more preferably from 93:7 to 50:50 and more preferably in the range from 90:10 to 35:65 and most preferred�Uo in the range from 80:20 to 45:55.

It is established that the adhesive mixture are in the range of pH values from 4 to 9 and more preferably, if they operate in the range from 4.5 to 8, and most preferably, when operating in the range of 5 to 7.

Adhesive compositions are thermosetting materials and cure when exposed to heat and optionally pressure. Typical temperature curing adhesive compositions are in the range from 50 to 250°C, more preferably in the range from 80 to 200°C and most preferably in the range from 100 to 170°C. curing Time at these temperatures may be in the range of 30 s to 1 h, more preferably from 1 min to 30 min and most preferably from 2 min to 10 min.

The application of adhesives

Adhesive composition can be added to a suitable substrate in an amount in the range from 1 to 25 wt.%, preferably in the range from 1 to 15 wt.% and most preferably in the range from 2 to 10 wt.%. Some examples of suitable substrates include, but are not limited to, lignocellulosic material, cellulose or fiberglass. Adhesive composition can be applied using a roller, the cutter device, by extrusion, watering, devices for applying foamed coating devices for coating by spraying or other means. Use the�owns a high content of solids PAE, which is characterized by low viscosity, contributes to the coating/treatment. Low viscosity ensures a smooth and even distribution of the adhesive on the substrate and a higher solids content provides a higher concentration of active material in a given quantity of the coating and the degree of processing.

The use of adhesives for the manufacture of lignocellulosic composites known in the art. Using the adhesive composition proposed in the present invention, it is possible to make a number of materials, including particleboard, particleboard oriented with the layout of the chip (OSB), wafer plate, a wood-fiber plate (including fibreboard medium density and high density), wood with parallel stacking (PSL), laminated lumber (LSL) and other similar products. For the manufacture of thermosetting products proposed in the present invention can make use of lignocellulosic materials, such as wood, wood pulp, straw (including rice, wheat or barley), flax, hemp, and bagasse. Lignocellulosic usually prepared by mixing the adhesive with the substrate being in the form of powders, crushed particles, fibers, chips, bundles of fibers, place�monk, scraps, sawdust, stalks or chips, followed by pressing and heating the resulting combination with obtaining the cured material. Humidity lignocellulosic material prior to mixing with the adhesive composition typically is in the range from 2 to 20%.

There are restrictions on the moisture content of the finished composite materials. Too high moisture content of the final composition of the composite material can result in poor quality products that do not meet specifications, or may lead to difficulties during curing of the finished product (for example, when heated to the curing of the adhesive produces a lot of steam). Therefore, it is preferable to use low humidity and a higher solids content of the adhesive, so that in the final composition of the composite material may remain limited moisture even if the moisture content is high. Moreover, it ensures the reduction of energy consumption for drying wood to match the technical conditions of low humidity, the moisture content of the finished product does not exceed the maximum permissible values. Use with a high content of solids PAE resin for preparation having a high content of solids of the adhesive provides a bearing Myung�higher the amount of moisture in the finished composite material. The higher the moisture content in comparison with the maximum permissible moisture content of the final mixture, the more preferable is having a high content of solids glue and especially preferred is having a high content of solids PAE resin.

The adhesive composition can also be used for the manufacture of plywood or laminated veneer (LVL). Adhesive composition can be applied on the surface of the veneer with a roller, a cutter device, watering or spraying. Then the set of leaves of veneer stack with receiving sheets of the required thickness. Then bundles or sheets are placed in a drying press (for example, between the heated plates and pressed for hardening and curing of materials with the formation of the plate. Fiberboard can be manufactured by the technology of wet felting and wet pressing technology of dry felting/dry pressing or on the technology of wet felting/dry pressing.

For use in chipboard glue proposed in the present invention must have a viscosity equal to less than about 10000 CPS (according to the changes with a viscometer Brookfield RV), more preferably equal to less than 7,000 JV and most preferably equal to less than 5000 SP.

In addition to use with the lignocellulosic substrate�and, the adhesive composition can be used with substrates such as glass wool, glass fiber and other inorganic materials. The adhesive composition can also be used with combinations of lignocellulosic and inorganic substrates.

Preparation of glue proposed in the present invention, may be part of the manufacture of chipboard. Typical technology for manufacturing particle Board lies in the preparation of the adhesive on the basis of the MOF containing 65% solids, and mixing of the glue with wood mass, intended for the manufacture of particle Board. Typical mass ratio of glue to the amount of wood is approximately from 7 to 93. Glue and wood are mixed and then molded into sheets, which compress and then subjected to hot pressing. Typical oven temperature/temperature of the press is equal to 170°C and the typical duration of the press at this temperature and is equal to approximately 3 to 5 minutes Typical total moisture of the wood and glue before pressing is from 8 to 12 wt.%. Glue proposed in the present invention, which does not contain formaldehyde, can be used instead of adhesives on the basis of Matt. Get environmentally friendly product without significant modifications, which are made of composite material�ial, such as particleboard. Glue proposed in the present invention, which does not contain formaldehyde, can also be used as filler for adhesives based on MOF (the urea-formaldehyde resin), IFF (melamine-formaldehyde resin) or MMF (melamine-urea-formaldehyde resin).

EXAMPLES

Example 1

Have a low molecular weight and a high content of solids polyamide obtained by combining 109,28 part of Diethylenetriamine (DETA) (high purity) (109,28 g of 1.06 mol) and adipic acid (120,0 g, 0,819 mole). The flask is added DEET and with stirring for about 50 minutes slowly add adipic acid. Then heated and the temperature is slowly and continuously increased to 175°C for 140 min and Then the temperature is maintained equal to 170°C for 150 min During heating and curing of the reaction mixture with water is released and it is collected by means of cooling column, Dean-stark. Collect water (29,6). At the end of the exposure period at 170°C, slowly add water (360 g) for cooling and dilution of the material. The final polymer solution has a solids content equal to 60.3 percent. POV equal 0,077 DL/g. the content of the acid and amine are equal 0,131 and 4.75 mEq./g (the method of determining PWV below).

The flask was added the above polyamide (180,6, theoretical� importance of the content of amino groups is equal 0,84 mole and the experimental value of the content of amino groups is equal 0,86 mole) and water (37.2 g). With stirring for 10 min add the epichlorohydrin (88.8 g, 0.96 mole). The temperature begin to increase and by heating and cooling support equal to 40°C for 110 min Then add water (111,9 g). Then the temperature was raised to 70°C for 70 min, and support equal to 70°C for 150 min Viscosity, measured by the method of Gardner Holt and in accordance with the standards, during the time of incubation increases approximately from "C" to "G". The pH value is reduced to 4,69. Add water (24.3 g) was added and the solution was cooled to room temperature. The final material has a solids content equal to 44.5% and a Brookfield viscosity equal to 96 SP, when the content of solids is equal to 44.5%, and the value of pH of 4.95. According to NMR, the content azetidine groups is about to 92.3 mol.% in terms of the repeating unit of adipic acid. The content azetidine groups can also be expressed in mEq./g if you know the number of moles of functional groups per 1 g.

The prepolymers of the present invention, theoretical content of adipic acid equal to 2.3 mEq./g and based on this content azetidine groups must be equal to 2.1 mEq./G. adipic acid is only approximate and easier for characterization based on the values obtained by NMR.

After 3 weeks stare�Oia at room temperature, the contents azetidine groups is reduced to 88.4 mol.% links of adipic acid, the decrease of 9.6%.

Prepare a mixture of water (135,14 g), soy flour (Prolia 200/90), sodium metabisulphite, glycerol and dimethylurea in the ratio 300: 200: 1: 200: 150. Soy mixture has a solids content equal to 64,75%. The PAE resin (by 39.33 g solids) combined with the mixture to prepare the adhesive. This adhesive mixture was stirred for 5 min until smooth and she has a solids content equal to 60,19%, and a viscosity according to Brookfield, is $ 2799 SP. 45% contained in the adhesive solids comes from PAE and soy flour. The pH value is equal to 6,94. The material is evenly sprayed onto the mixture for the production of chipboards and mix with a large shear force for 1 min to ensure equal treatment of wood. The amount of wood (including 5.1% of water) is equal 536,01 G. the Amount of glue used is equal 88,98 G. of Treated wood is formed into a flat layer and slightly compressed to seal and then pressed in a press at a temperature equal to 170°C, to a thickness equal to ½ of an inch.

The duration of the hot pressing is equal to 3 minutes, Extruded, now firmly cured composite material is extracted, cooled, they age over for a relative humidity of 50%, and cut into samples of size 1×8×½ inch. The average density of samples equal 44,58 lb/ft3. The modulus of rupture (MDE) on�Radelet using 3-point bending tests.

Control sample is prepared in the same manner, with the difference that instead of the above PAE resin using commercially available having a large molecular weight and low solids content of the resin (Ashland product SA). Use 58,33 g of a commercially available containing 30% solids material together with 135,14 g of soy mixture. The pH of the adhesive is equal 7,12, it has a solids content equal to 54,27%, and a Brookfield viscosity equal 3649 SP. The average density is subjected to hot pressing of samples equal 45,15 lb/ft3(FCCP). Difficult, if not impossible, to manufacture on an industrial scale particle Board with a lower solids content, since usually use MF resin containing 65% solids. The use of resins having a lower solids content when adding an equivalent amount leads to the formation of blisters and other defects of the plate due to high humidity of the slab, which leads to a high internal pressure of the gas (vapor).

The average value of the MDE for 8 samples of commercially available material 2 is 1658 lbf/in2with a standard deviation equal to 218 lbs/in2. The average value of the MDE for 8 samples fabricated using with a high content of solid�x substances sample 2 PAE is equal 1756 lbf/in 2with a standard deviation equal to 177. The MDE values for commercially available sample and possessing high solids PAE sample is equal 1596 lbf/in2and 1696, respectively, in the interpolation 44 FCCP. Having a high content of solids material PAE on the value of the FRN is not worse than a commercially available low solids content of the material. This shows that the adhesive is proposed in the present invention, has an equivalent or better characteristics than low solids content of the product and significantly reduces the difficulties associated with excessive humidity.

The value PWV measured as follows. Prepare a 2% solution of the polymer in 1 n of the ammonium chloride. The value PWV measured at 25.0°C using an automatic capillary viscometer Cannon. For this purpose you can use the viscometer model PolyVISC or AutoVISC, both of them are issued by the firm of Cannon Instrument Company, State College, Pa. Measure the flow rate of a 2% solution of the polymer and the pure solvent and calculate the relative viscosity (Nrel). Given the viscosity is calculated by the relative viscosity and the results of the specific viscosity is calculated by dividing the reduced viscosity on the concentration of the solution at 22°C.

Example 2

4 is at a round bottom flask obhama l put polyamidoamine (493,63 g), obtained from Diethylenetriamine (DETA) and adipic acid. Polyamidoamine prepared from a mixture of Diethylenetriamine and adipic acid with a molar ratio of 1.13:1 and it has the complete content of solids in water, equal 49,43%. The results of the specific viscosity of a 2% solution of the polymer in 1 n of the ammonium chloride is from 0,100 to 0,115 DL/g according to the definition at 25°C using an automatic capillary viscometer Cannon described above. At 20°C adding water (190,23 g), and then for 20 min added epichlorohydrin (195,77 g) and the reaction mixture heated to 40°C. the Reaction mixture was kept at this temperature for 180 min after the addition of epichlorohydrin. After 180 min for dilution of the reaction mixture is added water (97,64 g) until the solids content of 45%, and then the reaction mixture was heated to 65°C. After establishing the temperature of the reaction mixture, equal to 57.5°C, was added concentrated sulfuric acid (to 8.41 g) until the pH of the reaction mixture, equal to 7.09. The reaction mixture was incubated at 65°C until the temperature of the reaction mixture is >64°C for 90 min Then add sulfuric acid (2.18 g) before establishing a pH value equal to 4.98. The full content of solids=44,1%, a Brookfield viscosity equal 71,2 SP. The Brookfield viscosity is measured at 25°C and at 60 rpm with used�using spindle #61 with a viscometer Brookfield LV DV-II+Pro.

20 parts of PROBES having the same solids content as obtained above in solution PAE when the content of solids is 44.1%, combined with 100 parts of the dry matter of the mixture of soy flour containing at 1.33 parts of glycerin to 1 part soy and having a solids content equal to 61%. Soya blend also contains small amounts of sodium bisulfite as a means of viscosity changes. The adhesive also contains protivovospalitel and biocide. The resulting glue PAE/soy flour has a solids content equal to 57.3 per cent. This solids content of 52.4% of the total weight of the PAE resin and soy flour. For comparison serves the same mixture using with less solids, higher molecular weight, higher viscosity PAE brand SA produced by the firm. The resulting paste has a solids content equal to 52,0%. Both glue mixed with wood mass, intended for the manufacture of particle Board and a relative humidity of 5.1 percent. In both cases, 8 parts of glue in the dry matter is added to 100 parts of wood in terms of dry matter. The obtained pulp to manufacture has a moisture content equal to 9.3 and 10.4% respectively. Each wood pulp for the same amount of wood from�otaplivaet plate thickness of 1/2 inch and get plates, with sredneoblastnoy approximately 44 lb/ft3. Both in the furnace is subjected to hot pressing for 4 minutes at a temperature of the press, equal to 170°C. the Internal temperature of the panel in about 2 min is equal to approximately 120°C. Measure the modulus of rupture (MDE) and the strength of internal communication (SC). A sample having a high content of solids PAE has 2 strength MDE for MO, $ 1890+/-31 to 125+/-24 lbf/in2. A sample having a lower solids content of the PAE resin has a strength MDE for VS equal to from 1794+/-45 to 80+/-16 lb - 2 strength/in2. In addition, the viscosity of the adhesive containing having a high content of solids PAE proposed in the present invention, is 2050 SP (Brookfield, spindle 64, 12 rpm) and has a pH value equal to 5,93; whereas based adhesive having a low content of solids PAE has a viscosity equal to 3749 CPS and a pH value equal to 5.61. In the present invention, the resulting paste was characterized by an equivalent characteristics, but has a smaller viscosity and a much higher solids content than that obtained using currently available for sale PAE.

Example 3

4 is at a round bottom flask of 1 liter volume placed polyamidoamine (190,23 g), obtained from titilation�to (DETA) and adipic acid. Polyamidoamine prepared from a mixture of Diethylenetriamine and adipic acid with a molar ratio of 1.13:1 and it has the complete content of solids in water, equal to 42.1%. The results of the specific viscosity of a 2% solution of the polymer in 1 n of the ammonium chloride is from 0,100 to 0,115 DL/g according to the definition at 25°C using an automatic capillary viscometer Cannon described above. When 21,3°C add water (65,16 g), and then for 20 min added epichlorohydrin (122,38 g) and the reaction mixture heated to 40°C. the Reaction mixture was kept at this temperature for 180 min after the addition of epichlorohydrin. After 180 min for dilution of the reaction mixture is added water (35,09 g) until the solids content equal to 47%, and then the reaction mixture was heated to 65°C. After establishing the temperature of the reaction mixture, equal to 53.7°C, was added concentrated sulfuric acid (4.33 g) until the pH of the reaction mixture is equal to the 5.56. The reaction mixture was incubated at 65°C until the temperature of the reaction mixture is >64°C for 90 min, the pH Value of the material for the aging set equal to 5. The full content of solids=46,95%, the Brookfield viscosity is $ 118 SP. The Brookfield viscosity is measured at 25°C and at 60 rpm using spindle #61 with a viscometer Brookfield LV DV-II+Pro.

Aging at 25°CAging at 32°C
DaysThe viscositypHThe viscositypH
011851185

Aging at 25°CAging at 32°C
DaysThe viscositypHThe viscositypH
7112,55,121785,09
14at 149.5191,5
21175234
35 2455,093604,96

The PAE resin obtained in this example has a high content of solids, low viscosity and acceptable stability during aging.

Example 4

4 is at a round bottom flask of 1 liter volume placed polyamidoamine

(122,38 g) obtained from Diethylenetriamine (DETA) and adipic acid. Polyamidoamine prepared from a mixture of Diethylenetriamine and adipic acid with a molar ratio of 1.13:1 and it has the complete content of solids in water, equal to 42.1%. The results of the specific viscosity of a 2% solution of the polymer in 10 1 called the ammonium chloride is from 0,100 to 0,115 DL/g according to the definition at 25°C using an automatic capillary viscometer Cannon described above. When 21,3°C add water (65,16 g), and then for 20 min added epichlorohydrin (122,38 g) and the reaction mixture heated to 40°C. the Reaction mixture was kept at that temperature for 15 for 180 min after the addition of epichlorohydrin. After 180 min for dilution of the reaction mixture is added water (61,08 g) until the solids content of 45%, and then the reaction mixture was heated to 65°C. After establishing the temperature of the reaction mixture, equal to 53.6°C, was added concentrated sulfuric acid (4.2 g) to 20 establishing pH, p�ate the 5.56. The reaction mixture was incubated at 65°C until the temperature of the reaction mixture is >64°C for 90 min, the pH Value of the material for the aging set equal to 5. The full content of solids=44,8%, a Brookfield viscosity equal to 78.5 SP. The Brookfield viscosity is measured at 25°C at 60 rpm using

25 spindle #61 with a viscometer Brookfield LV DV-II+Pro.

Aging at 25°CAging at 32°C
DaysThe viscositypHThe viscositypH
0of 78.55of 78.55
793,65,14116,5
14123152
21129155

Aging at 25°CAging at 32°C
DaysThe viscositypHThe viscositypH
42174of 4.92344,84

The PAE resin obtained in this example has a high content of solids, low viscosity and acceptable stability during aging.

1. A method of producing the adhesive composition, comprising combining polyamidoamine-epichlorhydrin resin (PAE) with a protein source,
where the adhesive composition has a total content of solids, greater than 45 wt.% in terms of the total mass of the adhesive,
where the total content of solids in the PAE resin and the protein source is at least 45% of the total content of solids in the adhesive composition,
where the PAE resin has a complete solids content of greater than 40%, and
where the PAE resin is characterized in that it has the stability during aging exceeding one week at 32°C.

2. A method according to claim 1, wherein the source� protein is a soy protein.

3. A method according to claim 1, wherein the PAE resin with a solids content equal to 40%, has a viscosity of equal to less than 200 SP.

4. A method according to claim 1, wherein the PAE resin has a specific value of a given viscosity unit (puv), equal to less than 0.3 DL/g.

5. A method according to claim 1, wherein the PAE resin has a content azetidine groups, equal to more than 0.75 mEq.

6. A method according to claim 1, wherein the viscosity of the adhesive composition is less than 10000 CPS.

7. A method according to claim 1, wherein the adhesive composition has a total content of solids greater than 50 wt.% in terms of the total mass of the adhesive composition.

8. A method according to claim 1, wherein the total solids content of the PAE resin and the protein source is at least 50% of the total content of solids in the adhesive composition.

9. The method for producing a composite material comprising adding the adhesive composition according to claim 1 to a suitable substrate.

10. A method according to claim 9, in which the protein source is a material on the basis of soybeans containing soy protein.

11. A method according to claim 9, in which the PAE resin with a solids content equal to 40%, has a viscosity of equal to less than 200 CPS and in which the viscosity of the adhesive is equal to less than 10000 CPS.

12. A method according to claim 9, in which the PAE resin has a value per, ber, equal to 0.3 DL/g, and the content azetidine groups, equal to more than 0.75 mEq.

13. A method according to claim 9, in to�Thor adhesive composition has a total content of solids, exceeding 50 wt.% in terms of the total mass of the adhesive.

14. A method according to claim 9, in which the total solids content of the PAE resin and the protein source is at least 50% of the total content of solids in the adhesive.

15. A method according to claim 9, in which the composite material is a particleboard wood-based.

16. A method according to claim 15, in which the protein source is a material on the basis of soybeans containing soy protein adhesive when the content of solids equal to 40%, has a viscosity of equal to less than 200 CP, PAE resin has a value per, ber, equal to less than 0.3 DL/g, the PAE resin has a content azetidine groups, equal to more than 0.75 mEq., and viscosity of the adhesive is equal to less than 10000 CPS.

17. A method according to claim 9, in which the composite material is a wood-fiber plate on the basis of wood.

18. A method according to claim 17, in which the protein source is a material on the basis of soybeans containing soy protein adhesive when the content of solids equal to 40%, has a viscosity of equal to less than 200 CP, PAE resin has a value per, ber, equal to less than 0.3 DL/g, the PAE resin has a content azetidine groups, equal to more than 0.75 mEq., and viscosity of the adhesive is equal to less than 10000 CPS.

19. Polyamidoamine-epichlorhydrin resin, characterized in that it has a solids content exceeding 4%, the viscosity according to Brookfield, izmerenii using a Brookfield viscometer LV, equal to less than 200 CN, content azetidine groups, equal to more than 0.75 mEq./g, the value of a given unit of viscosity equal to less than 0.3 DL/g, and stability exceeding one week at 32°C.

20. Adhesive composition containing polyamidoamine-epichlorhydrin resin (PAE) and a protein source,
where the adhesive has a solids content exceeding 45 wt.% in terms of the total mass of the adhesive,
where the total content of solids in the PAE resin and the protein source is at least 45% of the total content of solids in the glue,
where the PAE resin has a solids content greater than 40%, and
where the PAE resin is characterized in that it has the stability during aging exceeding one week at 32°C.

21. A composition according to claim 20, which contains a diluent.

22. A composition according to claim 20, in which the source of protein is a soy protein.

23. A composition according to claim 20, in which the PAE resin with a solids content equal to 40%, has a viscosity of equal to less than 200 SP.

24. A composition according to claim 20, in which the PAE resin has the meaning given specific viscosity equal to less than 0.3 DL/g.

25. A composition according to claim 20, in which the PAE resin has a content azetidine groups, equal to more than 0.75 mEq.

26. A composition according to claim 20, in which viscous�you glue equal to less than 10000 CPS.

27. A composition according to claim 20 in which the adhesive has a solids content greater than 50 wt.% in terms of the total mass of the adhesive.

28. A composition according to claim 20, in which the total solids content of the PAE resin and the protein source is at least 50% of the total content of solids in the adhesive.



 

Same patents:

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EFFECT: improved operational properties and high strength and water resistance.

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3 cl, 1 tbl

FIELD: construction.

SUBSTANCE: composition for obtention of building coating and products contains filler and magnesian binder - sludge of carnallite chlorates. According to the invention, in order to enable the possibility of rapid application of composition mixed with water, on the coated surface, fluff pulp and / or fluff wood sawdust is used as a filler in relation filler to binder from 30/70 to 80/20%. Method for applying the composition on the surface, comprising mixing of composition with water in the spray water process through the air mixture of the filler and binder forming the composition, is proposed. For the preparation of composition, the cellulose cotton or fluff wood sawdust in dry form is mixed with crushed sludge of carnallite chlorates. At the mounting place of blowing machine the mixture is fed through the hose by means of air, at the downstream end of which there is a tip with nozzles, spraying water under high pressure. By wetting the mixture sticks to any surface due to excellent adhesion of binder. Optimum amount of water is about 50% from weight of magnesia binder. At least 20% of water is needed for reaction of the binder, and at more than 150%, the applied coating dries for too long.

EFFECT: invention makes it possible to expand the resource base and reduce manufacturing costs.

2 cl

FIELD: chemistry.

SUBSTANCE: invention relates to polymer chemistry and specifically to polyvinyl chloride-based wood-polymer compositions which can be used to produce shaped and linear articles. The wood-polymer composition for shaped and linear articles based on polyvinyl chloride and wood flour includes a complex stabiliser, an acrylic processability modifier, chlorinated polyethylene and stearic acid, and may also contain a metal-containing lubricant and an acrylic impact strength modifier.

EFFECT: invention improves the quality of shaped and linear articles, processability of the polymer material into shaped and linear articles by an extrusion method owing to improved thermal stability and impact viscosity and also reduces power consumption of extrusion equipment.

3 cl, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method of producing highly filled wood-polymer composition includes pretreatment of wood flour with an aqueous solution of a binding agent - silica sol, followed by thorough mixing and drying to constant weight at temperature of 100±2°C and further mixing of the treated wood flour, polyvinyl chloride (PVC), complex heat stabiliser and impact strength modifier. The PVC is pretreated with a binding agent containing 0.1-2.5 pts.wt silica sol, thoroughly mixed, dried to constant weight at temperature of 60±2°C, and the wood flour is treated with a binding agent containing 0.1-4.9 pts.wt silica sol. Content of the ingredients is as follows, pts.wt: PVC - 100, wood flour - 50-220, complex heat stabiliser - 4.5-7, impact strength modifier - 4.8-9, binding agent - 0.2-7.4.

EFFECT: wood-polymer materials based on the obtained highly filled PVC composition have an improved melt flow index, high tensile strength and thermal stability.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to wood and/or composite wood materials, in particular to wood-fibre boards, widely used as an initial material in many processing industries. Described is application of a material, selected from the group of phenol derivatives of formula IV, V, VI and their mixture as a mediator in production of lignocellulose-containing moulded articles, in particular the wood-fibre and/or composite materials. Especially preferable materials in the group of phenol derivatives of formula IV are: acetosyringone with R1, R2, R3 = methyl, and syringaldehyde with R1, R2 = methyl, R3 = H; in group of formula V - acetovanilone with R1, R2 = methyl, R3 = H, vanillin with R1 = methyl, R2, R3 = H and ethyl vanillin with R1 = ethyl, R2, R3 = H; in group of formula VI - methylsyringate with R1, R2=methoxy, R3=methyl and vanillic acid with R1, R3=H, R2=methoxy. The said material is applied together with, at least, one phenol-oxidising enzyme with ratio, equal ≥ 0.5 unit/ml of enzyme per 1 mmol of the mediator to ≤ 40 unit/ml of enzyme per 1 mmol of the mediator. Also described is a method of manufacturing the lignocellulose-containing moulded articles with application of the said material and the moulded article obtained thereby.

EFFECT: invention provides simplification of technology of the wood-fibre boards with preservation of their physical-chemical parameters.

9 cl, 2 dwg, 1 tbl, 6 ex

FIELD: process engineering.

SUBSTANCE: invention relates to woodworking industry and may be used for making slats. Said composition includes for inner layer 10-40% of rotten blank waste chips and 20% of wastes after roundup lumber chips as well as 40-70% of chips produced from pulp chips of PS grade with the help of binder based on low-molecular urea-formaldehyde resin and emulsion. Note here that said binder consists of low-molecular urea-formaldehyde resin of 60-62% concentration and aqueous solution of ammonia chloride of 20% concentration. Emulsion consists of the following components, in wt %: paraffin - 21, brown coal wax - 14, emulsifier - 1, water - 64.

EFFECT: lower material input, power savings, higher efficiency of equipment, lower toxicity.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: crude mixture for making heat-insulation articles contains, wt %: wood aggregate ground until passage through sieve N5 77.0-79.0; liquid phenol-formaldehyde resin 7.0-8.0; hydrolysed lignin 5.0-6.0; textile wastes 5.0-6.0; carboxymethyl cellulose 3.0-4.0. Articles are made by hot-pressing the mixture at pressure of 1.3-1.5 MPa and temperature of about 160°C.

EFFECT: obtaining articles with low content of a toxic component - phenol-formaldehyde resin.

1 tbl

FIELD: chemistry.

SUBSTANCE: hydrophilic plasticine is a product of comprehensive recycling of concentrated steep water from starch production, having sufficient plastic properties. The hydrophilic plasticine is obtained by heat treatment at 90°C, while simultaneously mixing the mixture of dry sieved moss peat with moisture content of not more than 20% and a thickened corn-steep extract, formed during starch production when corn is soaked in warm water at 45-52°C, which contains up to 0.35% sulphuric acid with respect to SO2 and less than 2% fatty acids and dry substances boiled down to concentration of not less than 48%. Components of the mixture are taken in ratio of 1:(4-6), respectively. If content of fatty acids in the thickened corn-steep extract is higher than 2%, the components are first heated to different temperatures before mixing.

EFFECT: plasticine is plastic and dissolves in water.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to the fur industry and can be used in finishing ship-fur and fur half-finished products. The composition for colour finishing of fur coat contains products of dissolving collagen, dexpanthenol, an acid dye and water, wherein components of the composition are foamed by mixing in a double-blade mixer with a revolution speed.

EFFECT: composition improves aesthetic and colour properties, increases lustre of the fur coat, reduces susceptibility to felting, thereby preserving heat-insulating properties.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a mixture of graft copolymers for use as an additive in chemical materials, as well as in development, exploitation and integration of underground deposits of oil and natural gas and in case of deep wells. The mixture of graft copolymers contains at components, at least one representative of brown coal, brown coal coke, lignite and a brown coal derivative, at least one representative of natural polyamides and different vinyl-containing compounds. The grafting base is selected from at least one representative of brown coal, brown coal coke, lignite and a brown coal derivative such as tannin and/or such a polyphenol derivative as lignosulphonate, or a polyamide component. Suitable polyamide components are natural polyamides, preferably caseins, gelatins and collagens, bone glues, blood albumins, soya proteins and products of splitting thereof, which are formed via oxidation, hydrolysis or depolymerisation, as well as mixtures thereof. The grafting component used is representatives of brown coal, brown coal coke, lignite, a brown coal derivative and natural polyamides, as well as vinyl-containing compounds in their O-, S-, P- and N-forms and styrenes, which can be in sulphonated form, or as a graft product. The graft product is obtained by grafting a vinyl-containing compound to at least one representative of natural polyamides or mixtures thereof, or grafting a vinyl-containing compound to at least one representative of brown coal, brown coal coke, lignite and a brown coal derivative. Graft copolymers with preferred molecular weight are used as a mixture, particularly in chemical construction materials and during development, exploitation and integration of underground deposits of oil and natural gas and in case of deep wells or as an additive for compositions containing hydraulic binding substances, as a water-retaining agent and/or liquefier.

EFFECT: graft copolymers have excellent resistance to salt and temperature and are also water-soluble and/or biodegradable.

17 cl, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemical and food industry, particularly to production of biodegradable plastic materials and can be used to make moulded or film articles for various purposes, including food purposes. In the method of producing a universal additive which initiates polymer decomposition, exclusively consisting of natural material which includes a matrix, natural polysaccharides, binder, a heat stabiliser and a culture medium, involving mixing said components in a heated mixer at temperature 40-70°C and further granulation or pelletisation of the obtained mixture, the novelty lies in that the matrix contained in the additive is edible paraffin (food additive E905), oxidised polyethylene wax (food additive E914), the natural polysaccharide is starch, the binder is collagen-containing products (gelatin, belkozin, hide glue etc), the heat stabiliser is modified starch THERMTEX and the culture medium is phospholipids.

EFFECT: invention increases biodegradability of the compositions and improves heat stabilisation properties thereof, enables to control the biodegradation duration of the compositions and water-absorption of the material and improves rheological properties of the compositions.

1 tbl, 4 ex

FIELD: textile industry.

SUBSTANCE: invention relates to integrated methods for manufacturing nonwoven materials involving impregnation with liquid binder. Impregnating composition contains polymeric binder: starch, gelatin, polyacrylic acid, or polyacrylamide; filler: zeolite or activated carbon; plasticizer: vegetable or liquid paraffin; and water. Composition can be used in manufacture of filled filter materials.

EFFECT: increased sorption capacity of materials with regard to impurities in liquid media.

1 tbl, 8 ex

FIELD: polymers.

SUBSTANCE: invention relates to technology for making molded articles made of biologically decomposing polymers. The composition for molding comprises biologically decomposing polymer and material preparing from marine plants and/or shells of marine animals, or at least two components taken among group consisting of saccharides and their derivatives, proteins, amino acids, vitamins and metal ions. The composition elicits good stability and ability for processing. Articles made of this composition show low capacity to fibrillation. Invention can be used in manufacturing package materials or fibrous materials - yarn, nonwoven or textile articles.

EFFECT: improved method for making, valuable properties of articles.

15 cl, 18 tbl, 3 dwg, 16 ex

The invention relates to compositions for chalky paper coating containing as adhesive binding protein, and particularly to compositions containing a modified vegetable protein as an adhesive binder

The rubber mixture // 2125067

The invention relates to the production of building materials and can be used for the manufacture of linopirdine plastics

FIELD: chemistry.

SUBSTANCE: invention relates to drilling mud emulsifiers. Disclosed is a polyamide compound of formula (A), where a is an integer from 1 to 5, b and c are each independently selected from integers from 0 to 10, under the condition that b and c are not equal to 0 at the same time, d is an integer from 0 to 10, e is an integer from 1 to 5, Y is selected from H, X, -C(O)R1 or -C(O)R2 and Z is selected from -C(O)R1 or X, where R1 and R2 are linear or branched, saturated or unsaturated hydrocarbyl groups having 7 to 30 carbon atoms, and X is a carbonyl group obtained from a carboxylic acid. The invention also discloses a method of producing said compound, use thereof as an emulsifier in drilling mud and the respective drilling mud composition.

EFFECT: disclosed compound is an effective emulsifier at high temperature and pressure, which reduces the required amount of the emulsifier and the cost of the system; Y{O(CH2)e}a{NX(CH2)e}b{N[C(O)R2](CH2)e}c{NH(CH2)e}d NHZ (A).

15 cl, 2 dwg, 6 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: described are compositions for hair care, containing a β-aminoether compound in a cosmetically acceptable carrier, such as a spray or cream. Described is a compound of formula

:

in which n represents an integer number from 1 to 100; Z and Z′ together with atoms, which they are bound to, represent acrylate, methacrylate or amino-terminal groups; R2 represents C1-C20alkyl, possibly substituted with: hydroxyl, siloxyl, C1-C20alkoxygroup, substituted with hydroxyl, amino-C1-C20alkyl, substituted with from one to two hydroxyl groups, C6-C10aryl, substituted with C1-C20alkoxygroup, or C5-C10heteroaryl, containing one nitrogen heteroatom; and A contains a rubber fragment, which has a molecular weight in the range from approximately 1000 g/mol to approximately 10000 g/mol, selected from the group, consisting of butadiene and isoprene units. Also described is a cosmetic composition for hair, containing the said compound and cosmetically acceptable carrier. The application of the said cosmetic composition for scalp care is described.

EFFECT: obtaining the cosmetic composition for hair, increasing adhesion of hairs to each other, adding volume, texture and shape to the hair.

10 cl, 4 tbl, 17 ex

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