阅读说明：本技术 组合物及其制备方法 (Composition and preparation method thereof ) 是由 亚里·库克康恩 蒂莫·尼斯辛恩 于 2018-03-09 设计创作，主要内容包括：本发明涉及用于处理木制品的阻燃剂组合物及其制备方法和应用。所述组合物包含选自1-羟基乙烷1,1-二膦酸的双膦酸盐、烷醇胺和任选地碱性试剂的水溶液,所述组合物的pH为4.0-7.0。所述组合物的制备方法包括将30-50重量份的1-羟基乙烷1,1-二膦酸、1-10重量份的烷醇胺或其混合物以及任选地0.1-40重量份的碱性试剂和水混合,所述烷醇胺以游离的形式加入。所述组合物不仅可以用于保护木材免于火灾,而且还可以用于防止霉菌、腐烂、蓝斑、昆虫(例如白蚁对木材的侵蚀)、尺寸变化或环境的综合影响。(The invention relates to a flame retardant composition for treating wood products, a preparation method and application thereof. The composition comprises an aqueous solution of a bisphosphonate selected from 1-hydroxyethane 1, 1-diphosphonic acid, an alkanolamine and optionally an alkaline agent, the composition having a pH of 4.0 to 7.0. The method of making the composition comprises mixing 30 to 50 parts by weight of 1-hydroxyethane 1, 1-diphosphonic acid, 1 to 10 parts by weight of alkanolamine added in free form or mixtures thereof, and optionally 0.1 to 40 parts by weight of alkaline agent and water. The compositions can be used not only to protect wood from fire, but also to protect against mold, rot, blue spots, insects (such as termite attack on wood), dimensional changes, or environmental complex effects.)

1. A flame retardant composition for treating wood products comprising an aqueous solution of a mixture or reaction product of a bisphosphonic acid, preferably selected from 1-hydroxyethane 1, 1-diphosphonic acid, an alkanolamine and optionally an alkaline agent, the composition having a pH of from 3.0 to 9.0.

2. Composition according to claim 1, characterized in that at least 75 mol% of the alkanolamine is added in free form, preferably at least 80 mol%, more preferably 90 mol% or more, e.g. all alkanolamine is added in free form.

3. Composition according to any one of the preceding claims, characterized in that it comprises a bisphosphonate present in the aqueous solution predominantly in the acid form, preferably at least 50 mol% of the bisphosphonate is present in the acid form.

4. Composition according to any one of the preceding claims, characterized in that the composition comprises 0.1-50 wt. -%, preferably 1.0-40 wt. -%, such as 20-40 wt. -% of 1-hydroxyethane 1, 1-diphosphonic acid, based on the total weight of the dissolved components in the composition, said 1-hydroxyethane 1, 1-diphosphonic acid being optionally mixed with other bisphosphonates, organic phosphonates or mixtures of said other bisphosphonates or organic phosphonates.

5. A composition according to any one of claims 1 to 3, comprising:

from 0.1 to 70% by weight, preferably from 1.0 to 60% by weight, for example from 20 to 50% by weight, based on the total weight of dissolved components in the composition, of 1-hydroxyethane 1, 1-diphosphonic acid or 1-hydroxyethane 1, 1-diphosphonic acid and/or other bisphosphonic acids or bisphosphonates, and/or mixtures of other organic phosphonates, the composition being in the form of a salt of an alkaline agent, for example ammonia; and

1-30 wt% alkanolamine or alkanolamine mixture based on the total weight of dissolved components in the composition.

6. Composition according to any one of the preceding claims, characterized in that the pH of the composition is between 4.0 and 7.0, preferably between 5.0 and 6.0.

7. Composition according to any one of the preceding claims, characterized in that the alkaline agent is chosen from calcium-free inorganic hydroxides and carbonates, such as one or more of hydroxides of alkali metals and alkaline earth metals, carbonates of alkali metals and alkaline earth metals, ammonia and ammonium hydroxide, preferably the alkaline agent is aqueous ammonia.

8. The composition of any of the preceding claims wherein the alkaline agent is in an amount sufficient to adjust the pH of the aqueous solution of 1-hydroxyethane 1, 1-diphosphonic acid to 4.0-7.0.

9. Composition according to any one of the preceding claims, characterized in that the amount of alkaline agent is between 0.1 and 40% by weight of the solution, preferably between 1 and 30% by weight.

10. Composition according to any one of the preceding claims, characterized in that the alkaline agent is ammonia, which is added in the form of aqueous ammonia with a mass fraction of 1-25%, preferably 5-25%.

11. Composition according to any one of the preceding claims, characterized in that the alkanolamine is chosen from amines of formula:

NR¹R²R³ I

wherein R is¹，R²And R³Independently selected from hydrogen and alkyl groups having from 1 to 6 carbon atoms, optionally substituted with at least one substituent selected from hydroxyl, monoalkanolamine, dialkanolamine and trialkanolamine, for example monoalkanolamine, dialkanolamine, trialkanolamine and C1-C6 alkanolamine.

12. Composition according to any one of the preceding claims, characterized in that the alkanolamine is selected from the group consisting of monoethanolamine, monoisopropanolamine, mono-sec-butanolamine, diethanolamine, diisopropanolamine, di-sec-butanolamine, triethanolamine and triisopropanolamine and mixtures thereof.

13. Composition according to any one of the preceding claims, characterized in that the alkanolamine is selected fromFrom alkylalkanolamines, e.g. C_1-6alkyl-C_1-6Alkanolamines, preferably selected from methylethanolamine, butylethanolamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine and ethyldiethanolamine and mixtures thereof.

14. The composition of claim 13, characterized in that the alkanolamine comprises a mixture of the alkanolamine of claim 12 and the alkylalkanolamine of claim 13.

15. A composition according to any preceding claim comprising from 1 to 30 wt% of the alkanolamine or mixture of alkanolamines, based on the total weight of dissolved components in the composition.

16. The composition of any of the preceding claims, wherein the alkaline agent comprises ammonia, the bisphosphonate comprises 1-hydroxyethane 1, 1-diphosphonic acid, and the alkanolamine comprises a mixture of monoethanolamine or triethanolamine.

17. Composition according to any one of the preceding claims, characterized in that it has a shelf life of more than 6 months.

18. Composition according to any one of the preceding claims, characterized in that it comprises up to 95% by weight of water.

19. The composition of any one of claims 1-18, comprising 35 wt% or more than 35 wt% water; or less than 40 wt%, especially 35 wt% or less than 35 wt%, for example 10 to 35 wt% water.

20. Composition according to any one of the preceding claims, characterized in that it consists of an alkaline agent, 1-hydroxyethane 1, 1-diphosphonic acid and an alkanolamine, all dissolved or dispersed in water.

21. A composition according to any of claims 1 to 20, characterized in that it comprises a further flame retardant, preferably selected from ammonium phosphate, borate and boric acid and mixtures thereof.

22. A composition according to any one of claims 1 to 21, characterized in that it comprises a complexing agent, preferably selected from ethylenediamine succinic acid, iminodisuccinic acid, N-bis- [2- (1, 2-dicarboxyethoxy) -ethyl ] -aspartic acid, ethylenediamine tetraacetic acid and diethylenetriamine pentaacetic acid and mixtures thereof.

23. Composition according to any one of the preceding claims, characterized in that it has an ammonia release rate lower than 0.03mg/M as given in the M1 classification handbook and in the building materials chemistry and sensory test protocols, version22.1.2015²h。

24. Composition according to any one of the preceding claims, characterized in that it comprises, based on the dry weight of the composition:

30 to 50 parts by weight, preferably 35 to 45 parts by weight, of 1-hydroxyethane 1, 1-diphosphonic acid or 1-hydroxyethane 1, 1-diphosphonate;

1 to 10 parts by weight, preferably 2 to 8 parts by weight, of an alkanolamine or mixtures thereof, which alkanolamine is added in free form;

0.1 to 40 parts by weight of an alkaline agent, preferably 2 to 10 parts by weight of ammonia; and

and (3) water.

25. Composition according to any of the preceding claims, wherein the composition is prepared by mixing 1-hydroxyethane 1, 1-diphosphonate with alkanolamine, wherein the 1-hydroxyethane 1, 1-diphosphonate is preferably an alkaline agent salt of 1-hydroxyethane 1, 1-diphosphonic acid, and wherein the alkaline agent is ammonia.

26. Composition according to any one of the preceding claims, characterized in that it is obtained by components free from carboxylic acids, in free form or in combination with amines or basic components.

27. A method of producing a flame retardant composition for treating wood products, said composition comprising an aqueous solution of a mixture or reaction product of a bisphosphonic acid, an alkanolamine and optionally a basic agent, said method comprising reacting a bisphosphonic acid with an alkanolamine

10 to 60 parts by weight, for example 30 to 50 parts by weight, of a bisphosphonic acid, for example 1-hydroxyethane 1, 1-diphosphonic acid;

1 to 10 parts by weight of an alkanolamine or mixtures thereof, the alkanolamine being added in free form;

optionally 0.1 to 40 parts by weight of an alkaline agent;

and water to prepare a composition having a pH of 3.0 to 9.0.

28. A method according to claim 27, characterized in that the total amount of base equivalents of the alkanolamine and alkaline agent is at least 50% of the acid equivalents of the bisphosphonic acid, such as 1-hydroxyethane 1, 1-diphosphonic acid.

29. The method according to claim 27 or 28, characterized in that 35-40 parts by weight of 1-hydroxyethane 1, 1-diphosphonic acid is mixed with 3-8 parts by weight of an alkanolamine selected from the group consisting of monoethanolamine, monoisopropanolamine, mono-sec-butanolamine, diethanolamine, diisopropanolamine, dibutanolamine, triethanolamine and triisopropanolamine and mixtures thereof, and 2-10 parts by weight of ammonia dissolved in water and optionally 0.1-5 parts by weight of an ionic surfactant.

30. The method according to claim 27 or 28, characterized in that 35-40 parts by weight of 1-hydroxyethane 1, 1-diphosphonic acid is mixed with 3-8 parts by weight of an alkanolamine selected from the group consisting of monoethanolamine, monoisopropanolamine, mono-sec-butanolamine, diethanolamine, diisopropanolamine, dibutanolamine, triethanolamine and triisopropanolamine and mixtures thereof, 2-10 parts by weight of ammonia in solution in water, and optionally 0.1-5 parts by weight of an ionic surfactant, the ammonia being added in the form of the ammonium salt of 1-hydroxyethane 1, 1-diphosphonic acid.

31. A method according to any of claims 27 to 30, wherein the composition is prepared by mixing components which are free of carboxylic acid, either in free form or in combination with an amine or base component.

32. The method according to any one of claims 27 to 31, wherein the temperature of the mixing is 10 to 100 ℃, preferably about 10 to 60 ℃.

33. The method of any one of claims 27-32, comprising preparing a composition having an ammonia release rate less than 0.03mg/M as set forth in the M1 classification handbook and building material chemistry and sensory test protocol, 22.1.2015 edition²h, pH is 4.0-7.0.

34. A method of treating wood products to impart flame retardancy thereto comprising contacting the wood products with the composition of any of claims 1-26.

35. The method of claim 34, comprising mixing 10-500g/m²E.g. 25-300g/m²The flame retardant composition of (1) is applied to a wood product.

36. The method according to claim 34 or 35, comprising contacting said wood product with a composition according to any one of claims 1-18 or 20-23, said composition being applied to said wood product by spraying.

37. A method according to any of claims 34-36, comprising the steps of: contacting said wood product with a composition according to any one of claims 1-18 or 20-26, said composition being applied by pressure impregnation.

38. A method according to any of claims 34-37, comprising the steps of: contacting the wood product with the composition by immersing the wood product in the aqueous composition.

39. The method according to any one of claims 34-38, wherein the wood product is selected from the group consisting of wood, engineered wood products, such as cross-laminated wood, laminated veneer wood and plywood, and other man-made boards, such as particle board, fiber board and oriented strand board.

40. A method according to any one of claims 34 to 39, wherein the composition is mixed with a glue for bonding two or more wood layers together to form a multi-ply structure.

41. A wood product having fire retardant properties and comprising 1-hydroxyethane 1, 1-diphosphonic acid and an alkanolamine, said wood product having been produced according to the method of any of claims 34-40.

42. The wood product according to claim 41, wherein the wood product is selected from the group consisting of wood, engineered wood products, such as cross-laminated wood, laminated veneer wood, wood-plastic composites, and plywood, man-made boards, such as particle board, fiber board, oriented strand board, and acoustical panels, and cellulose-based fibers or materials, such as cellulose insulation and carboxymethyl cellulose.

43. The wood product according to claim 41 or 42, wherein said wood product meets fire rating requirements according to B-s1, d 0.

44. A method for treating wood products to protect the wood against one or several harmful environmental factors including besides fire mold, rot, blue spots, attack of wood by insects such as termites, dimensional changes and combined environmental effects, said method comprising contacting the wood products with a composition according to any one of claims 1-26.

Technical Field

The present invention relates to fire protection of wood materials. In particular, the present invention relates to a method for treating a wood material, a composition for flame retardancy and a method for preparing the composition.

Background

Wood is the most abundant non-toxic, recyclable and biodegradable natural material, used as building material due to its appearance and high strength at low density. The design and construction of buildings has recently been increasingly trending towards high-rise buildings, the structural components of which are composed of engineered wood, wherein the engineered wood comprises: cross laminated wood (CLT), Laminated Veneer Lumber (LVL), glued laminated wood (Glulam), plywood or solid wood used as outdoor panel material.

Currently, a 10-storey apartment building in melbourne, australia is under construction and high-rise buildings of up to 30 storeys are being designed in norway, austria, wengowa and finland. These buildings have sustainability advantages due to the use of wood as a renewable building material.

On the other hand, the lack of adequate fire resistance is an important drawback for the use of wood in construction. Thus, in building codes throughout the world, including the european union and countries in the united states, japan and australia, it is required to use wood treated with a suitable fire retardant only in wall, floor and roof components. By properly protecting the wood, the spread of smoke and fire can be controlled, and the time for evacuating buildings and helping people to safely transfer can be prolonged.

Many flame retardant compositions, such as the types described in patent US9132569B2 and the patent documents mentioned therein, are based on pressure impregnation of the flame retardant in wood. In addition, the chemical components include inorganic phosphates such as ammonium phosphate salts APP, MAP and DAP or boron-containing substances such as borates or boric acid. However, these chemical compositions are not environmentally acceptable or their function is insufficient to achieve the B-s1, d0 fire rating at low retention levels. Furthermore, wood treated with APP, MAP and DAP type flame retardants is susceptible to physical and chemical degradation if the treated article absorbs moisture.

Some recent patents and literature disclose that organic phosphates, such as ammonium HEDP acid salts, can be used instead of inorganic phosphates or boron compounds as a promising flame retardant.

HEDP is an abbreviation for the bisphosphonate compound 1-hydroxyethane 1, 1-diphosphonic acid, also known as etidronic acid. HEDP is a chelating agent with antioxidant properties.

For example, in BirgitA REPORT entitled "Innovative eco-effective high fire performance products for demanding applications" (Final REPORT for Vinnova-Tekes project Innovere Wood. SP Wood Technology SP REPORT 2006:30) by et al suggests the use of ammonium salts of HEDP acid as flame retardants for Wood products.

The report describes the use of organophosphonates (including HEDP) as flame retardants for pine sapwood and thermally modified spruce. The liquid concentrations in the combustion test were 20, 40 and 60 wt-% prior to neutralization with ammonia. The pH of the test liquid is not mentioned. For pine sapwood, the average retention of the flame retardant (in a concentration of 100 wt%) was 89kg/m, respectively³(20wt％)、181kg/m³(40 wt%) and 290kg/m³(60 wt%). The treatment was carried out by immersing under a vacuum pressure of-92 kPa (92 kPa below the standard pressure) for 30 minutes and then under an absolute pressure of 1.0MPa for 120 minutes. All wood samples before and after impregnation were weighed separately at 23 ℃ and 50% RH. Using 50kw/m²Cone calorimeter testing with heat flux indicated that the fire rating was class B and in some cases class C for the pressure impregnated pine sapwood samples. The thermally modified spruce was pressure impregnated with 40 wt% ammoniated HEDP with a retention of 110kg/m². According to the fire rating prediction model used, 50kw/m is used²Cone calorimeter tests conducted on heat flux showed fire ratings of B or C.

US8361210B2A process is disclosedA method of wood by contacting wood with a mixture of a liquid or water-soluble ammonium organic carboxylate and an invertebrate-repelling active ingredient. The object of this prior art is to provide a method and a composition for treating wood, wherein the composition is both well absorbed and has a good retention capacity. In a most preferred embodiment, the ammonium organic carboxylate is selected from the group consisting of salts or complexes of formic acid and monoethanolamine, and salts or complexes of propionic acid and monoethanolamine.

According to US8361210B2, the wood preservative active ingredient used in combination with the above ammonium carboxylates may comprise a chelating agent selected from aminopolycarboxylic acids or salts thereof, hydroxy acids or salts thereof, or phosphonates (organophosphonates, organophosphates) or mixtures thereof. Preferably, the chelating agent of this patent is a chelating agent capable of binding iron and manganese ions and including phosphorus (P) in a molecular structure. The chelating agent is HEDP.

According to the examples of US8361210B2, the composition is applied to the surface of plywood made of spruce or birch. When used once, the absorption rate of the composition by wood is about 250g/m². The treated wood has fire-retardant properties in a fire test according to standard EN 5660.

US9125404B2(Vuori & nissnen) discloses a method of treating wood to improve its use and storage properties. In the method, wood to be treated is contacted with a treatment composition comprising a mono-ester, di-ester, tri-ester or mixtures thereof, the composition being formed from a water soluble C1-C10 alcohol and formic acid as equilibrium solutions. The composition comprises a formic acid ester of formic acid, preferably a glycerol formate, for treating wood, and it may comprise HEDP or a salt of HEDP. The composition for protecting wood from fire given in US9125404B2 comprises: 1-50% by weight of glycerol formate, 1-10% by weight of free formic acid, 1-5% by weight of HEDP or its salt, and the balance glycerol and water. By impregnation with this solution, a wood product is obtained which is the highest in fire resistance and very durable against decay agents and termites.

FI121917B (Mertaniemi et al) discloses a composition for treating wood-based materials, which comprises at least one C1-C7 monocarboxylate or C1-C7 monocarboxylate or a mixture thereof as an active agent for preventing deterioration of wood. The composition further comprises an aluminum ion containing compound in the form of an alkyd emulsion having a high unsaturated fatty acid content and/or a polyaluminium formate in the same aqueous liquid carrier as the C1-C7 monocarboxylic acid salt or the C1-C7 monocarboxylic acid or a mixture thereof. The composition may further comprise a complexing agent capable of binding a transition metal as a wood preservative aid. The complexing agent used as wood preservative aid is preferably an aminopolycarboxylic acid or salt thereof, a hydroxy acid or salt thereof or a phosphonate (organophosphonate, organophosphate, HEDP) or mixtures thereof. According to the invention, the pH of the composition is mainly neutral or weakly alkaline, since strongly acidic wood preservative or flame retardant compositions tend to destroy the structure of wood over time. The pH, measured directly from the solution, is preferably from 6 to 11, ideally from 7 to 10.

FI122723B(Kukkonen，Nissinen&Aksela) discloses a wood material treated with a composition comprising at least one C1-C7 monocarboxylic acid or salt thereof, or mixture thereof, and at least one chelating agent. According to this patent, the composition for protecting wood from fire should contain 5 to 20% by weight of a chelating agent, such as HEDP. The solution was immersed in the wood using pressure so that the total penetration of the fireproofing agent reached 22.7% of the total effective concentration, corresponding to 176.2kg/m³. The fire resistance of the impregnated specimens was evaluated according to ISO5660 fire resistance test, the material achieving class B fire resistance.

Disclosure of Invention

It is an object of the present invention to address at least some of the problems associated with the art.

In particular, it is an object of the present invention to provide new and improved flame retardant compositions containing bisphosphonates as a flame retardant or component thereof.

The present inventors have surprisingly found that by preparing an aqueous composition, a novel flame retardant composition can be obtained which gives wood products treated therewith good flame retardant properties. The aqueous composition comprises HEDP in combination with an alkaline agent and an alkanolamine, in particular the alkanolamine being added to the solution predominantly in free form. In contrast, the organic acid salt of ammonia of the prior art described above increases the smoke generation rate and the release of ammonia (ammonia odor) when the pH is close to 6, and loses chemical stability when the pH is lower than 6.

The compositions of the present invention may be prepared by mixing the components together and optionally reacting them.

The composition may be used in a method of treating wood and wood products to produce new wood and wood products comprising HEDP, an alkanolamine and optionally one or more other alkaline agents, which have good fire resistance.

More specifically, the invention has the features set forth in the characterizing part of the independent claim.

The invention has significant advantages. According to the present invention, a flame retardant treated wood product can be produced in the most cost-effective, safe and environmentally friendly manner. The treated wood has excellent fire resistance and does not generate smoke or release ammonia. Wooden articles treated with the flame retardant of the present invention meet the most stringent fire ratings of B-s1, d0, for example, in the european union.

The composition has little ammonia odor at a pH that ensures good stability and extended shelf life. This advantage is achieved both during production and during storage. In addition, the ammonia release rate of the composition is generally lower than 0.03mg/M given in the M1 classification handbook and Building materials chemistry and Sensory Testing protocol (M1 classification and protocol for Chemical and Sensory Testing of Building materials, version22.1.2015) version22.1.2015²h。

The compositions of the invention are also stable in the neutral or weakly acidic pH range, especially at pH values of less than 7.0, for example at pH values of 4.0 to 6.2, preferably 5.0 to 6.2 or 5.2 to 6.0. The shelf life of the composition is over 6 months. Thus, the composition is still useful for the intended use, at least for a period of more than 6 months. Typically, the composition has a pH in the range of less than 7.0, for example a pH of 4.0 to 6.2, preferably 5.0 to 6.2 or 5.2 to 6.0, for more than 6 months.

Furthermore, it is very surprising that the novel composition of the present invention has excellent wood penetration, can be well absorbed into treated wood products, and has excellent retention.

Further, there is little or no loss of strength properties of plywood when treated with the composition of the invention.

The compositions according to the invention can be prepared in high concentrations of active substances without loss of stability and with a long shelf life, which active substances have the advantage that even at low amounts they achieve the object of improving the fire resistance, which in turn makes possible the use of conventional adhesive or application techniques. Although this technique is also feasible when using dilute solutions, pressure impregnation is not mandatory.

No separate drying step is required after use.

Further features and advantages will be described in the following detailed description of embodiments.

Detailed Description

As mentioned above, the composition of the present invention comprises an aqueous solution of a mixture or reaction product of a bisphosphonic acid selected from 1-hydroxyethane 1, 1-diphosphonic acid, an alkanolamine and optionally an alkaline agent, the pH of the composition being in the range of 3.0 to 9.0, preferably in the range of 4.0 to 7.0.

According to some embodiments of the invention, the HEDP forms a salt (acid salt) with the alkanolamine and/or the alkaline agent. Acid salts are salts formed from acids (i.e., HEDP) and bases (i.e., alkanolamines and/or basic agents) by only partially replacing hydrogen ions from the associated acid, i.e., HEDP, with some degree of acidity.

Thus, according to some embodiments of the invention, a flame retardant composition comprising HEDP, a basic agent, and an alkanolamine, which flame retardant composition is added to a solution in predominantly free form to form a pH of 4 to 7, contains primarily or at least partially HEDP in protonated form. This is merely a suggestion and does not limit the scope of the invention.

According to other embodiments of the invention, the alkaline agent is added in the form of a HEDP salt. HEDP in acid form and at least one alkaline agent to form a HEDP salt, which is mixed with an alkanolamine in the presence of water to obtain an aqueous composition comprising a mixture or reaction product of a bisphosphonic acid, an alkaline agent and an alkanolamine, the pH of the aqueous composition being in the range of 3.0 to 9.0, preferably in the range of 4.0 to 7.0.

According to some embodiments of the present invention, by first reacting the alkaline agent with HEDP, the alkaline agent reacts more efficiently without remaining as a free component in the final solution. By this neutralization reaction, the pH of the solution is increased, which can then be adjusted to a suitable level by adding an alkanolamine to form the amine-HEDP complex. The alkaline agent in the form of a HEDP salt may be introduced as part of the process or generated directly in the process.

The composition prepared according to the invention can provide wood products treated by the composition with good flame retardant performance. In contrast, in the above-cited prior art, organic acid salts of ammonia, such as ammonium carboxylates, increase the rate of smoke generation and increase ammonia release (ammonia odor) even at pH values close to 6, and furthermore, lose chemical stability when the pH value is lowered below 6.

According to some preferred embodiments of the invention, the composition does not comprise a carboxylic acid in free form or in combination with an amine or basic component.

According to other embodiments of the invention, the composition contains almost no carboxylic acid, i.e. contains no more than 1% by weight of carboxylic acid, preferably no more than 0.5%.

In the present invention, the term "bisphosphonic acid" refers to the 1-hydroxyethane 1, 1-diphosphonic acid component, i.e., HEDP, and the term "bisphosphonate" refers to its anion. It is clear that even if added as a HEDP salt, it is possible for HEDP to be present partially or totally in dissociated form (i.e. in protonated form), depending on the pH of the composition.

The salt may be an inorganic salt or an organic salt, preferably an inorganic salt. Preferably, the salt is formed from ammonia, although alkali and alkaline earth metal salts are also possible.

In the present invention, the term "bisphosphonate component" encompasses bisphosphonates and bisphosphonate anions or "classes".

Similarly, as used herein, the abbreviation "HEDP" and the name "1-hydroxyethane 1, 1-diphosphonic acid" include both the bisphosphonic acid itself and the corresponding bisphosphonate anion.

The "pH" of the composition is measured directly from a solution, preferably an aqueous solution.

Other bisphosphonates and bisphosphonic acids useful in the invention include the following examples: clodronate, tiodronate, pamidronate, ceramidate, olbardronate, alendronate, ibandronate, risedronate, zoledronate or organic phosphonates, for example aminomethylphosphonic acid (AMPA), vinylphosphonic acid, dimethyl methyl Dimethylphosphonate (DMMP), aminotrimethylene phosphonic Acid (ATMP), ethylenediamine tetramethylene phosphonic acid (EDTMP), tetramethylenediamine tetramethylene phosphonic acid (TDTMP), hexamethylenediamine tetramethylene phosphonic acid (HDTMP), diethylenetriamine pentamethylene phosphonic acid (DTPMP), phosphono N-butyl trimethylphosphonate, 2-carboxyethylphosphonic acid (CEPA), 2-hydroxyphosphonocarboxylic acid (HPAA), aminotrimethylene phosphonic Acid (AMP) and N, N-Bisphosphonomethylglycine (BPMG).

While the present invention is primarily directed to compositions and methods utilizing HEDP as a bisphosphonate, it should be understood that HEDP may also be partially or fully substituted with another bisphosphonate or mixture of bisphosphonic acids (e.g., a bisphosphonate or mixture of bisphosphonic acids, as described below), or even HEDP may be substituted with any other acid that functions in the same manner as HEDP in combination with the other components of the composition.

Thus, according to some embodiments of the present invention, there is provided a flame retardant composition for treating wood products comprising an aqueous solution of a mixture or reaction product of a bisphosphonic acid selected from 1-hydroxyethane 1, 1-diphosphonic acid, clodronate, oolong phosphonate, pamidronate, neuraminic acid phosphonate, obenzonate, alendronate, ibandronate, risedronate or zoledronate or an organic phosphonate, such as aminomethylphosphonic acid (AMPA), vinylphosphonic acid, Dimethylmethylphosphonate (DMMP), aminotrimethylene phosphonic Acid (ATMP), ethylenediaminetetramethylenephosphonate acid (TDTMP), hexamethylenediaminetetramethylene phosphonic acid (HDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP), phosphonobutane tricarboxylic acid (PBTC), phosphonic acid (PBTC), and optionally an alkaline agent, N-phosphonomethyliminodiacetic acid (PMIDA), 2-carboxyethylphosphonic acid (CEPA), 2-hydroxyphosphonic acid (HPAA), aminotrimethylene phosphonate, N-Bisphosphonomethylglycine (BPMG) and combinations thereof. And the pH of the composition is in the range of 3.0 to 9.0, preferably 4.0 to 7.0.

In the present invention, the term "alkanolamine" includes "alkylalkanolamine", as described below.

The 1-hydroxyethane 1, 1-diphosphonic acid in aqueous solution is present predominantly in the acid form, preferably at least 50 mole% of the diphosphonic acid is present in the acid form.

According to some embodiments of the invention, the composition of the invention comprises:

0.1 to 50% by weight, preferably 1.0 to 40% by weight, for example 20 to 40% by weight, of 1-hydroxyethane 1, 1-diphosphonic acid or of a mixture of 1-hydroxyethane 1, 1-diphosphonic acid with other bisphosphonic acids or bisphosphonates and/or other organic phosphonates and/or other bisphosphonic acids or bisphosphonates, based on the amount of dissolved components in the composition;

-1-30% by weight of an alkanolamine or mixture of alkanolamines, calculated on the amount of dissolved ingredients in the composition; and

-optionally, 1-30 wt% of an alkaline agent, based on the amount of dissolved ingredients in the composition.

Alternatively, as noted above, when the basic agent is ammonia, the bisphosphonate may be introduced, or at least partially introduced, in the form of a bisphosphonate. Thus, according to some embodiments of the invention, the composition comprises:

0.1 to 70% by weight, preferably 1.0 to 60% by weight, for example 20 to 50% by weight, of 1-hydroxyethane 1, 1-diphosphonic acid or a mixture of 1-hydroxyethane 1, 1-diphosphonic acid and other bisphosphonic acids or bisphosphonates and/or other organic phosphonates in the form of an alkaline agent salt, for example an ammonia salt, based on the amount of dissolved components in the composition; and

-1-30% by weight of alkanolamine or mixture of alkanolamines, calculated on the amount of dissolved ingredients in the composition.

The addition of ammonia as an alkaline agent in the form of a bisphosphonate reduces the amount of free ammonia in the final solution, thereby reducing the odor of ammonia and preventing discoloration of the solution.

According to some preferred embodiments of the invention, the alkanolamine is selected from the group consisting of amines represented by formula I,

NR¹R²R³formula I

Wherein R is¹，R²And R³Independently selected from hydrogen and having 1 to 6 carbon atomsOptionally substituted with at least one substituent selected from at least one of hydroxyl, monoalkanolamine, dialkanolamine and trialkanolamine, such as monoalkanolamine, dialkanolamine, trialkanolamine and C₁-C₆An alkanolamine.

For example, the alkanolamine may be selected from one or more of monoethanolamine, monoisopropanolamine, mono-sec-butanolamine, diethanolamine, diisopropanolamine, di-sec-butanolamine, triethanolamine and triisopropanolamine.

According to other embodiments of the invention, the alkanolamine is selected from alkylalkanolamines, such as C_1-6alkyl-C_1-6Alkanolamines, preferably selected from one or more of methylethanolamine, butylethanolamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine and ethyldiethanolamine.

The alkanolamine may also comprise a mixture of alkanolamine and alkylalkanolamine.

While typical basic alkanolamines can adjust the pH of the composition, the composition typically contains a separate or second basic agent in addition to the bisphosphonate component and the alkanolamine.

According to some embodiments of the invention, the alkaline agent is selected from inorganic hydroxides and carbonates, for example hydroxides of alkali metals and alkaline earth metals, carbonates of alkali metals and alkaline earth metals, ammonia, ammonium hydroxide and mixtures thereof. Preferably aqueous ammonia.

According to some embodiments of the invention, the alkaline agent is chosen from aqueous ammonia, the mass fraction of which is between 1 and 25%, for example between 10 and 25%. Preferably, saturated aqueous ammonia is used. According to some embodiments of the invention, ammonia is used at a pH of at least about 8.5, for example 9 to 13.

If inorganic hydroxides or carbonates are used, it is preferred to use a calcium-free component, since calcium ions can form insoluble complexes with bisphosphonates. Typically the alkaline agent should be present in an amount sufficient to adjust the pH of an aqueous solution of 1-hydroxyethane 1, 1-diphosphonic acid and alkanolamine to a value of from 3.0 to 9.0, for example from 4.5 to 8.0, preferably from 4.0 to 7.0, most preferably from 5.0 to 6.0.

According to some embodiments of the invention, the alkaline agent is present in an amount of 0.1 to 40% by weight of the solution, in particular 1 to 30% by weight of the solution.

According to some embodiments of the invention, the pH of the composition is in the range of 4.0 to 7.0, most preferably in the range of 5.0 to 6.5, such as 5.2 to 6.0.

In view of the above, according to a preferred embodiment of the present invention, the alkaline agent comprises ammonia, the bisphosphonate component comprises 1-hydroxyethane 1, 1-diphosphonic acid, and the alkanolamine comprises monoethanolamine or triethanolamine or a mixture thereof.

As mentioned above, according to some embodiments of the present invention, 20 to 90 wt%, for example 30 to 80 wt% of the bisphosphonate component is added in the form of an ammonium salt, which is mixed with the alkanolamine and optionally water, the pH of the aqueous solution being in the above-mentioned range of 4.0 to 7.0, preferably in the range of 5.0 to 6.5, for example 5.2 to 6.2.

According to some embodiments of the invention, the composition of any of the above embodiments has good stability and typically can be extended in shelf life by at least 6 months, or even longer.

The compositions of the present invention may be formulated according to various methods of use. According to some embodiments of the invention, the water content of the aqueous composition may be adjusted to a value of 35 wt% or higher, typically up to 95 wt%. This allows compositions to be obtained which are easy to use by simple spraying or other surface treatment techniques, such as roller coating. According to further embodiments of the present invention, the water content of the aqueous composition may be adjusted to be below 40 wt.%, preferably below 35 wt.%, for example 10-35 wt.%.

Other components may be added to the composition, for example retention aids and/or water-adding agents may be added. Suitable retention aids may be fatty acids, polymers (e.g. starch, cellulose or derivatives thereof), chitosan and silicon compounds. Hydrophobing agents include resins and their derivatives, surface sizes such as Alkyl Ketene Dimer (AKD) or Alkenyl Succinic Acid (ASA), tall oil and its derivatives. AKD, ASA and/or tall oil and derivatives thereof are preferably used as water-adding agent, preferably in an amount of 0.01 to 5.0 wt.%.

According to other embodiments of the present invention, the composition comprises a surfactant capable of reducing the surface tension of the liquid, making it easier to spread the liquid, while also reducing the interfacial tension between the two liquids. Surfactants can be classified according to the charge groups present in the surfactant head. Nonionic surfactants have no charged group in their head. The head of the ionic surfactant carries a net charge. If the charge is negative, the surfactant is more specifically referred to as an anionic surfactant. If the charge is positive, it is referred to as a cationic surfactant. If the head of the surfactant carries two oppositely charged groups, it is referred to as a zwitterionic surfactant.

According to some embodiments of the invention, the composition further comprises an additional flame retardant, such as one of ammonium phosphate, borate and boric acid and mixtures thereof or iron phosphate.

In another embodiment which may be combined, for example, with the previous, the composition comprises a complexing agent, preferably selected from one or more of ethylenediamine succinic acid, iminodisuccinic acid, N-bis- [2- (1, 2-dicarboxyethoxy) -ethyl ] -aspartic acid, ethylenediamine tetraacetic acid and diethylenetriamine pentaacetic acid.

According to some embodiments of the invention, the composition consists of only the aforementioned three components, the alkaline agent, the 1-hydroxyethane 1, 1-diphosphonic acid and the alkanolamine, all of which are soluble or at least dispersible in water.

An important advantage of embodiments of the present invention is that the composition is free or nearly free of ammonia fumes and odors. According to some embodiments of the invention, the composition has an ammonia release rate that is less than 0.03mg/M given by the M1 classification handbook, Version22.1.2015, and the Building materials Chemical and Sensory Testing Protocol (M1 classification and Protocol for Chemical and Sensory Testing of Building materials, Version22.1.2015)²h。

The compositions of the present invention may be prepared by mixing HEDP with an alkanolamine or mixture of alkanolamines and optionally a basic agent such as aqueous ammonia.

According to some embodiments of the invention, the method of producing the flame retardant composition comprises mixing the following components to obtain a composition having a pH between 3 and 9, such as 4 to 7,

-10 to 60 parts by weight, for example 30 to 50 parts by weight of HEDP;

-1 to 10 parts by weight of an alkanolamine or mixtures thereof, said alkanolamine being added in free form;

-optionally 0.1 to 40 parts by weight of an alkaline agent, preferably an aqueous solution of an alkaline agent, such as aqueous ammonia or an aqueous solution of an alkali or alkaline earth metal hydroxide or carbonate; and

-optionally, water.

According to further embodiments of the present invention, the method of producing a flame retardant composition for treating wood products comprises mixing components comprising an aqueous solution of a reaction product or mixture of bisphosphonic acids and alkanolamines, and optionally an alkaline agent, to obtain a composition having a pH of between 3 and 9,

10 to 60 parts by weight, for example 30 to 50 parts by weight, of a bisphosphonic acid;

-1 to 10 parts by weight of an alkanolamine or mixtures thereof, said alkanolamine being added in free form;

-optionally 0.1 to 40 parts by weight of an alkaline agent; and

-water.

The mixing of the components is carried out at a temperature of 10-100 ℃, preferably below 100 ℃, more preferably around 10-60 ℃.

Typically, the water content of the composition may be up to 60% of the total weight of the composition. The added ingredients typically comprise water, but additional water is added to achieve a predetermined solid matter content, for example, 50% or more by total weight of the composition.

According to some embodiments of the method of the present invention, the total amount of base equivalents of alkanolamine and alkaline agent is at least 50% of the acid equivalents of HEDP or other bisphosphonic acids. In other words, a sufficient amount of amine and any alkaline agent is added to adjust the pH of the solution such that the pH of the solution is above the pKa values of the first and second acid groups of HEDP or other bisphosphonic acids.

According to some embodiments of the present invention, a composition of interest is obtained by mixing 35 to 40 parts by weight of HEDP, wherein the HEDP is provided in the form of an aqueous solution, 4 to 8 parts by weight of an alkanolamine selected from the group consisting of monoethanolamine, monoisopropanolamine, monobutanolamine, diethanolamine, diisopropanolamine, didecanolamine, triethanolamine, and triisopropanolamine, and mixtures thereof, and 2 to 10 parts by weight of aqueous ammonia. Further, 0.1 to 5 parts by weight of an ionic surfactant, optionally provided in the form of an aqueous solution, is optionally incorporated. If necessary, water is added.

Embodiments described herein also include methods of treating wood products to impart flame retardancy thereto, the method comprising contacting the wood product with a composition according to any of the embodiments described above.

Applying 10-500g/m on the wood product by surface treatment²For example, 100-300g/m²The flame retardant composition of (1). The amount of the flame retardant composition is 10-200kg/m during pressure impregnation³E.g. 25-100kg/m³。

The use of the composition can be carried out by known methods. According to some embodiments of the invention, the composition is applied to the wood product by spraying or rolling. According to further embodiments of the present invention, the composition may be applied by pressure impregnation in combination with the foregoing. According to some embodiments of the invention, the wood product is contacted with the composition by immersing the wood product in the aqueous composition.

The invention makes it possible to treat wood-based materials in a simple and economical manner, which treatment can easily be included in other steps of existing wood treatment. The treatment process may be performed as one step in a continuous multi-step production line of wood or wood products. The composition according to the invention is also convenient to handle, since it does not emit strong irritating odours, such as ammonia. Hereinafter, examples of the method will be given to show how the treatment composition is used for the treatment of wood and how the treatment is integrated into a wood processing line of a wood processing plant for wood processing.

1) Pressure impregnation

The traditional method of injecting large quantities of impregnation substances into the wood provides the most efficient treatment through different steps (underpressure and overpressure, high temperature). In this way, optimum permeability properties can be achieved, and wood can usually be impregnated onto the core material. The composition according to the invention has very good permeability and can reduce the negative/overpressure used in conventional CCA impregnation, thus improving the cost-effectiveness of the process. At the same time, it is possible to pressure impregnate finer particle sizes of wood, such as spruce, with the compositions of the invention, which is not possible with the substances conventionally used.

2) Soaking and dipping

The compositions of the present invention are permeable well and in some cases, immersion alone is also feasible. The process is simple but requires a separate immersion tank and is carried out batchwise as is pressure impregnation.

3) Spraying or rolling

For example, the composition of the present invention may be sprayed or roll-coated onto the surface of wood along with the shaved wood.

4) Painting or other surface treatment routes

The compositions of the present invention may also be added to wood in conjunction with paint or other surface treatment routes. In the paint feed tank, the solution can be dipped into the wood board by a separate paint unit at an overpressure or a negative pressure on the wood board. Depending on the pressure and the speed of the pipeline, good permeability and thus good shooting properties can be achieved by this method.

Prior to wood treatment, the treatment composition may be diluted with water to a concentration suitable for treatment.

As previously mentioned, the water concentration may vary in the particular method of use. Thus, for pressure impregnation, compositions having a water content of up to 95% by mass can generally be used; the preferred water mass concentration is about 60-90%. Similarly, for spraying or rolling, a composition comprising a major part of water by mass is generally used, for example 55-90% by mass. For impregnation, the water content is generally less than 80% by mass, for example 10-70%, or 20-60%.

The composition may be absorbed through the thickness of the wood to be treated, or from the surface to a certain depth, by dipping, soaking, spraying, evaporating (atomizing), or brushing. Due to the various alternatives, the treatment can be carried out at a suitable moment in other processes of the wood, for example in the final drying of the wood. The physical properties of the composition, such as viscosity, can be adjusted according to the type and purpose of the treatment.

It should be noted that, according to some embodiments of the present invention, retention and fire performance are improved by increasing the temperature of the solution and/or the concentration of the flame retardant solution.

Impregnation of wood with cell wall penetrating substances depends on diffusion at the wood cell level. The diffusion rate depends on the diffusion coefficient, temperature and concentration of the chemical species. The interior of the woody cell walls is maximally accessible when the wood is in a swollen state, which is most easily achieved by water saturation of the material.

There are no permanent capillaries in the cell wall. When water desorbs during drying, the microfibrils in the cell wall move together (shrink). After rewetting, the microfibers separate again (swell), but since water occupies all the spaces between the microfibers, the microfibers do not necessarily move to the same position as before.

According to a first embodiment of the invention, dried wood or wooden material is contacted with a composition according to any one of the above embodiments. It has been found that dried wood or wooden material is a suitable material if the chemicals need to impregnate a large part of the wood.

However, if diffusion of chemical substances into the wooden cell wall is required, it is important that the cell wall contains water. Thus, according to a second embodiment of the invention, wet wood is contacted with a composition according to any of the embodiments above. The term "wet wood" refers to wood having a moisture content of greater than 2 wt.%, preferably greater than 20 wt.%. According to some embodiments of the invention, the raw wood is contacted with a composition according to any of the above embodiments.

Prior to use, the composition may be mixed with a glue for bonding two or more wood layers together to form a multilayer structure.

Generally, the compositions are used to improve the performance of wood products.

In the present invention, the term "wood product" refers to any structure or product comprising wood, for example wood in the form of mechanically produced block structures, layers, chips or strands, which are used as such or can be shaped into a secondary structure, which comprises inter alia layers (veneers), chips or strands bonded together.

According to some embodiments of the present invention, the wood products contacted with the compositions of the present invention may be selected from wood and engineered wood products and multi-layer wood products and boards, examples including cross-laminated wood, laminated veneer wood, wood-plastic composites and plywood, and other man-made boards, such as particle board, fiber board (including medium and high density fiberboard) and oriented strand board.

Furthermore, the compositions and methods of the present invention can be used to treat acoustical panels that are at least partially composed of wood material, for example, in the form of fibrillated fibers. The fibrillated fibers may be obtained from recycled wood fibers.

The compositions and methods of the present invention may also be used to modify materials comprising cellulose-based substances, such as cellulose derivatives. Thus, the compositions of the present invention may be mixed with carboxymethylcellulose to form compositions that may be used as adhesives for paper products such as wallpaper, paperboard products such as corrugated board, and multi-ply wood products such as panels and paperboard. Modified cellulose derivatives are generally useful as viscosity modifiers and thickeners.

The wood treatment agent of the present invention is useful for protecting wood from one or both of several harmful environmental factors. The harmful factors mainly include invasion of wood, size change or comprehensive influence of environment by insects such as mold, rot, blue spot, termite and the like besides fire.

The compositions can be adjusted according to the respective protection and priority required. Preferably, a composition is provided that has sufficient activity against several different detrimental environmental effects simultaneously.