PatentDe  


Dokumentenidentifikation EP0724487 12.07.2007
EP-Veröffentlichungsnummer 0000724487
Titel KONSERVIERUNG VON HOLZ MIT PHENOLFORMALDEHYD RESORCINOLHARZEN
Anmelder Polymer Wood Processors, Inc., Ambler, Pa., US
Erfinder LEWIS, Jean, deceased, US
Vertreter derzeit kein Vertreter bestellt
DE-Aktenzeichen 69434979
Vertragsstaaten DE, ES, FR, GB, IT, NL
Sprache des Dokument EN
EP-Anmeldetag 19.08.1994
EP-Aktenzeichen 949252910
WO-Anmeldetag 19.08.1994
PCT-Aktenzeichen PCT/US94/09337
WO-Veröffentlichungsnummer 1995006524
WO-Veröffentlichungsdatum 09.03.1995
EP-Offenlegungsdatum 07.08.1996
EP date of grant 30.05.2007
Veröffentlichungstag im Patentblatt 12.07.2007
IPC-Hauptklasse B27K 3/15(2006.01)A, F, I, 20051017, B, H, EP
IPC-Nebenklasse C08G 8/24(2006.01)A, L, I, 20051017, B, H, EP   

Beschreibung[en]

The present invention relates to a treating solution for the preservation of wood and other cellulose-based materials. The invention also relates to a method of preparing such treating solution.

This invention relates in particular to the preservation of wood, and includes the chemical compositions used to treat the wood and the process of treating the wood.

The chemical compositions which are described herein are especially well suited for use in the method of US-A- 3,968,276 in which wood to be treated is exposed to a reduced pressure for the purpose of removing moisture and volatiles from the wood, and thereafter impregnating the wood with an aqueous phenol formaldehyde/resorcinol formaldehyde chemical composition as hereinafter described.

Wood is one of the oldest materials known to man. Its ready availability in most parts of the world, coupled with the ease with which it can be cut and fabricated into useful articles, makes it well suited for a variety of applications. However, because wood is a cellulosic material, it is susceptible to decay and deterioration over any extended period of time. As a result, numerous methods have been proposed for treating wood to improve its durability, particularly when used under conditions where the wood is exposed to moisture or biological attack. Applications of wood such as its use in manufacturing railroad ties, utility poles, fence posts, and the like, have created substantial incentives for industry to develop effective and commercially practical methods of treating the wood to extend its useful life (i.e. wood preservation). Various techniques of wood preservation have been used including surface coating, surface treating and pressure penetration of the wood with a variety of chemicals such as creosote, halogenated phenols such as pentachlorophenol and the like.

When halogenated phenols such as pentachlorophenol are used to treat wooden poles (such as utility poles), it is common to dissolve the pentachlorophenol in a hydrocarbon oil, pressure treat the poles, and then evaporate the excess oil. Such a process is relatively expensive, but is justified by the wood preservative properties of the pentachlorophenol.

However, the treated poles tend to "bleed" their treating solution into the surrounding soil when the poles are installed in the ground. This draining or leaching effect is more visible on the sunny side of utility poles which drain or bleed faster because the heat from the sun warms the treating solution and reduces its viscosity.

In an effort to reduce treating costs, water is sometimes substituted for the hydrocarbon oil, and the pentachlorophenol is used in one of its salt forms to provide water solubility. However, this approach has a number of disadvantages and is less preferred than the oil treatment.

Unfortunately, most of the present treating processes (e.g. those using creosote, various copper and mercury compounds, or pentachlorophenol), even when operated under significant pressure conditions, do not result in deep impregnation of the wood. Thus, the wood being treated with any chemical is typically treated to only a shallow depth and, in the case of logs or poles, very often the degree of penetration does not extend throughout all of the soft or sapwood, much less penetrate the heartwood.

However, US-A-3,968,276 discloses a method for treating wood (logs or dimensional lumber), wherein the wood is preserved by impregnating the wood with chemicals which penetrate substantially to the core or center of the wood being treated. In the case of logs or poles, this penetration can be deep within the heartwood and may be substantially complete. discloses enclosing

US-A-3,968,276 discloses enclosing the wood within a chamber, sealing the chamber, evacuating the chamber slowly so that the wood is exposed to a pressure below atmospheric pressure, introducing into the chamber a sufficient amount of an aqueous solution of resin prepolymer to immerse the wood and then maintaining the vacuum over the immersed wood for a period of time both to allow the removal of moisture and volatiles from the wood and to permit the treating solution to enter into the wood. Thereafter, an additional amount of the resin prepolymer solution is introduced into the chamber (if needed) and the pressure on the system is increased to super atmospheric pressure to thereby cause an even deeper penetration of the treating solution into the wood. The vacuum and pressure cycle may be repeated one or more times (e.g. 1 to 30 or more cycles). When the treatment is completed to the desired extent, the treated wood is recovered from the chamber. The process described is extremely effective and achieves substantially greater penetration of the wood than any other commonly practiced treating processes.

Also it is known in the prior art, as disclosed in US-A-4,399,195 and US-A-4,433,031, that one or more known wood preservatives, such as the halogenated phenols, can be introduced deep into the wood being treated and obtain reduced "bleeding" or leaching, by combining the wood preservative with the method of US-A-3,968,276 by using a special class of treating compositions that are water-based or water dilutable which permits the benefits of the aqueous resin prepolymer system of US-A-3,968,276 to be maintained.

Further, US-A-4,399,195 and US-A-4,433,031 disclose that it is possible to accomplish deep penetration with reduced bleeding without encountering any significant amount of "blooming" which is normally associated with aqueous treating solutions of halogenated phenols. This blooming effect is caused by the fact that the aqueous treating solutions are made from salts of halogenated phenols, which dissolve readily in water. Because the salts are water soluble, there is a tendency for the salts to be redissolved by rain water or ground water and to migrate easily to the surface of the treated wood where they crystallize during the subsequent evaporation of the water, causing the "blooming effect".

US-A-4,399,195 and US-A-4,433,031 disclose manufacturing a water dilutable concentrate or a water-based treating solution which consists essentially of: (a) a halogenated phenol wood preservative such as pentachlorophenol; (b) a phenolic resin prepolymer such as phenol formaldehyde prepolymer ; (c) a coupling or solubilizing agent for enhancing the water compatibility of the concentrate (e.g. methyl alcohol or acetone with or without the addition of a surfactant); and (d) water. Optionally and preferably, the disclosed treating solutions contain organo/metallic salts, especially copper or zinc salts.

In addition, US-A-4,339,195 and US-A-4,433,031 disclose that the ability of the prepolymer to cure rapidly and lock the halogenated phenol deep within the wood can be enhanced by heating the wood at the conclusion of the treatment (e.g. heating the wood with steam) to thereby accelerate the curing of the resin prepolymer.

The term "curing" as used in the previous paragraph is to be differentiated from the term "gelling" as used hereinafter in the present art. Curing refers to the process by which wood preservative stabilizes once impregnated into the wood. Gelling refers to the solidification or semi-solidification of the resins forming the wood preservative during preparation of the wood preservative. Gelling or, more specifically, the time it takes for gelling to occur (gel time testing) is used in the art as an indicator of resin activity and is used to predict and select curing parameters and characteristics of the resins used in the wood preservative solutions.

While the process for treating wood as disclosed in US-A-4,399,195 and US-A-4,433,031 works quite well, the wood treating compositions of the prior art suffer from the limitations of having a limited shelf life, relatively slow curing times and the requirement of significant amounts of heat to effect curing.

It was also known in the prior art to use water soluble phenol formaldehyde resoles as wood preservatives. Such a resole of the prior art typically gels in approximately 10 to 20 minutes at 121°C and has a shelf life of 3 to 6 weeks at 25°C (measured by its ability to remain infinitely water dilutable).

In the adhesive art (glues, etc., an art distinctly different from the wood preservative art, compare JP-A-59/081166 and US-A-4 897 314), it was known that resorcinol formaldehyde resins could be added to or blended with certain water soluble phenol formaldehyde resoles which contain free formaldehyde to react with the resorcinol, wherein the resorcinol functioned to cause more rapid gelling and curing of the adhesive at room temperature. However, the resorcinol formaldehyde modified phenol formaldehyde resins of the adhesive arts were not used as wood preservatives and invariably exhibited a much shorter shelf life than non-blended resins. Further, the resorcinol modified resins of the adhesive arts were designed to fully cure at room temperature, which is not compatible with the wood preservative arts, where the resin must be retained in a liquid state for extended periods both on the shelf and during the impregnation process. While curing at room temperature after the impregnation process is complete may be compatible with the wood preservative arts, premature gelling of the resin solution at room temperature is not. Gelling of the resins in the wood preservative arts is to be avoided because a fully gelled resin cannot impregnate the wood at all, and the large molecules in a partially gelled resin cannot effectively impregnate the minute interstices of the wood and, therefore, cannot penetrate deep into the heartwood, either.

It would be preferred if the known wood preservative resins of the prior art could cure faster and at lower temperatures after impregnation than those presently known in the art, exhibit extended shelf life but without premature gelling. Also, while free or unreacted formaldehyde may be necessary with phenol formaldehyde resins of the prior art for reaction purposes, it would also be preferred if such resins would exhibit an extremely low free formaldehyde content during resin formation, during the impregnation process at the wood impregnation plant, and after the wood is cured and used in its final application, because formaldehyde is toxic and is considered an environmental hazard. Further, it would be preferred if such resins exhibited increased tolerance to the additives which are normally added to these resins to aid in wood preservation and fire retardance.

The object of the present invention is to preserving and/or fire-proofing wood and other cellulose-based material by utilizing specific chemical compositions thus that the utilized treating composition penetrates deeply into the treated material and that "bleeding" of the chemicals and in particular formaldehyde is suppressed effectively.

This object is solved in accordance with the present invention by a treating solution having the features of claim 1, in which solution the overall free formaldehyde concentration is low.

Further features and improvements of the treating solution of the present invention are subject of the dependent claims 2 to 7.

The object of the present invention is also solved by the method of preparing the treating solution having the features of claim 8.

Improvements of this method are subject of the dependent claims 9 and 10.

Furthermore, the object of the present invention is solved by the process of treating wood or other cellulose-based material having the features of claim 11.

An improvement of this process is subject matter of claim 12.

Generally, the present invention is directed to a method of preserving and fire-proofing wood utilizing specific chemical compositions. The present invention is also directed to the chemical compositions. The present invention is also directed to the process of producing the chemical compositions.

More specifically, the present invention is directed to a water-based wood or cellulose treating solution as defined in claim 1 comprising:

  1. a) a phenolic resin prepolymer; and
  2. b) a resorcinol formaldehyde resin prepolymer.

Optionally and preferably, the treating solution also contains additives which aid in wood preservation and fire retardance.

The wood treating solution of the present invention unexpectedly exhibits extended shelf life with reduced premature gelling, faster curing time, lower curing temperatures, lower free formaldehyde content and increased tolerance to the additives which are normally added to treating solutions to aid in wood preservation and fire retardance.

Since resorcinol has far more reactive cites than phenol, more cross linking occurs with the phenol formaldehyde/resorcinol formaldehyde resins of the present invention, than the unmodified phenol formaldehyde resins of the prior art and this additional cross linking will render the phenol formaldehyde/resorcinol formaldehyde treated wood more impervious to water and more chemically stable. The increased chemical stability also reduces the risk of formaldehyde emissions from the treated wood or other cellulosic products.

Further still, the cross linking of the phenol formaldehyde/resorcinol formaldehyde resins of the present invention provides more bonding with the cellulose, which in turn entraps in the treated wood the water soluble additives which enhance wood preservation and fire retardance, even after the treated wood is cured. These water soluble additives can penetrate deeply into the heartwood for greater protection of the wood. In contrast, for example, the prior art copper compounds were typically not water soluble but were emulsified in water, and these large emulsified copper molecules could only impregnate the wood superficially, i.e. approximately 0,00635 to 0,0127 m (0,25-0,5 inches), as opposed to penetrating deep into the heartwood.

In particular, the present invention is directed to aqueous resin solutions for treating wood and the use of such solutions to treat wood (both dried wood and green wood), and the resulting treated wood products.

In the following discussion, the term "treating solution" refers to the aqueous resin solution comprising a phenolic resin prepolymer and a resorcinol formaldehyde resin prepolymer. When wood preserving compounds (such as copper-based compounds) are added to the aqueous resin solution, the resulting compound is referred to as a wood preservative solution. When fire retarding compounds (such as diammonium phosphates) are added to the aqueous resin solution, the resulting compound is referred to as a fire retarding solution. When both wood preserving compounds and fire retarding compounds are added to the aqueous resin solution, the resulting compound is referred to as a wood preserving/fire retarding solution.

In the wood preserving and fire proofing industry, it is commonly the case that a resins manufacturer will manufacture the basic resin treating solution and provide that solution to a wood treating plant or facility which will then add the wood preserving and/or fireproofing compounds during the wood impregnation process.

For convenience, it is sometimes convenient to make the treating solution of the present invention in two steps, the first step being the preparation of water-dilutable concentrate or syrup, and the second step consisting of diluting the concentrate with water to achieve a desired concentration of active ingredients.

The treating solution of the present invention contains from 8% to 30% by weight of an aqueous phenolic resin prepolymer, 0.8% to 7% by weight resorcinol formaldehyde resin prepolymer, and 64% to 91% by weight of water. By comparison, the water dilutable concentrate or syrup generally contains from 40% to 60% by weight of the phenolic resin prepolymer, 4% to 12% by weight resorcinol formaldehyde resin, and 28% to 56% by weight of water.

Unless otherwise indicated, all percentages set forth herein refer to weight.

FORMATION OF THE AQUEOUS PHENOLIC RESIN PREPOLYMER

While the phenolic resin prepolymer component of the aqueous resin treating solution of the present invention includes other phenolic derivatives and other formaldehyde derivatives, the preferred phenolic resin prepolymer is a phenol formaldehyde resin prepolymer and is formulated beginning with the phenol in its liquid state.

Formaldehyde is added to the molten phenol in a mole ratio of approximately 1.0 to 2.75 moles per mole of phenol. Exceeding the upper limit causes excessive amounts of free formaldehyde, while going below the lower limit results in a resin solution incapable of effective cross linking. Either liquid solutions of formaldehyde or formaldehyde prills can be used with the present invention. Typically, paraformaldehyde prills are added to the phenol and melted in the reaction vessel. Paraformaldehyde prills are preferred because they eliminate the need to remove excess water from the resin after it has been produced. There is little or no reaction between the molten phenol and formaldehyde until a reaction catalyst is added. The catalyst typically causes a strong exothermic reaction.

Catalysts compatible with the present invention include alkaline earth hydroxides and carbonates, including sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, barium carbonate and calcium carbonate. Sodium hydroxide is the preferred reaction catalyst and is added to the reaction vessel preferably as a 50% solution in water within the range of 0.02 to 0.12 moles per mole of phenol. Exceeding the upper limit causes an excessively exothermic reaction while going below the lower limit will excessively slow the rate of reaction and cause incomplete curing. Water is added to temper the exothermic reaction.

The above components, phenol, formaldehyde, sodium hydroxide and water, are reacted between 50° C to 100° C for approximately 0.5 to 6 hours, preferably at about 65° C for 2 to 4 hours, and subsequently adjusted with water to a non-volatile (or solids content) of 50% to 70%.

The phenolic resin prepolymer is a clear to amber colored water soluble liquid. Low viscosity aqueous phenolic resin prepolymers are preferred for ease of use. Such prepolymers typically have molecular weights of less than 1000.

FORMATION OF THE RESORCINOL FORMALDEHYDE RESIN PREPOLYMER

The second component of the present invention, the resorcinol formaldehyde resin prepolymer, is formulated beginning with the resorcinol.

Formaldehyde is added to the resorcinol in a mole ratio not exceeding 0.70 moles per mole of resorcinol. The mole ratio of resorcinol to formaldehyde is important in the present invention. The mole ratio is selected to ensure an excess of resorcinol in the resorcinol formaldehyde resin prepolymer. The excess of resorcinol in turn ensures that there are no aldehyde radicals present in the resorcinol formaldehyde resin prepolymer. The absence of aldehyde radicals ensures that the resorcinol formaldehyde resin prepolymer can be readily handled and can be controllably reacted with the residual formaldehyde in the aqueous phenolic resin prepolymer when the two prepolymers of the treating solution of the present invention (aqueous phenolic resin prepolymer and resorcinol formaldehyde resin prepolymer) are blended together as discussed below. Exceeding the upper limit of this mole ratio will also result in an undesirable premature solidification of the resorcinol formaldehyde resin prepolymer.

Either liquid solutions of formaldehyde or formaldehyde prills can be used with the present invention. Typically, paraformaldehyde prills are added to the resorcinol and melted in the reaction vessel. Paraformaldehyde prills are preferred because they eliminate the need to remove excess water from the resin after it has been produced. There is little or no reaction between the resorcinol and formaldehyde until a reaction catalyst is added. The catalyst typically causes a strong exothermic reaction.

Catalysts compatible with the present invention include alkaline earth hydroxides and carbonates, including sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, barium carbonate and calcium carbonate. Sodium hydroxide is the preferred reaction catalyst and is added to the reaction vessel within the range of 0.02% to 0.12% moles per mole of resorcinol, about 0.045 moles being preferred by weight.

Water is added to temper the exothermic reaction.

The above components, the resorcinol, formaldehyde, sodium hydroxide and water are reacted to completion at a temperature of approximately 50°C to 100°C for a period of from 0.5 to 6 hours, preferably at 65°C for 2 hours and adjusted to a 50% to 75% solids content and, more preferably, to a 60% solids content. The resorcinol formaldehyde resin prepolymer used in the present invention is an aqueous dark red liquid and is reactive in the presence of formaldehyde or formaldehyde donors.

FORMATION OF THE TREATING SOLUTION OF THE PRESENT INVENTION

The phenolic resin prepolymer is then blended with the resorcinol formaldehyde resin prepolymer to yield the treating solution of the present invention. Preferably, the resorcinol formaldehyde resin prepolymer is added in a ratio of 10% to 30% by weight of the phenolic resin prepolymer, more preferably 16% to 20%. The two components are simply blended, and no heat is applied at this point. Exceeding the upper limit of this weight percent may result in an unstable compound, while going below the lower limit of this weight percent may cause an unreactive system. Surprisingly, the treating solution of the present invention exhibits considerably longer shelf life than blends known in the art as discussed in detail below. Typically, the treating solution of the present invention will be manufactured to this point by a resins manufacturer, who will then ship the treating solution to a wood preservation plant, where the solids content of the treating solution is adjusted to 8% to 36%.

It has been found with the present invention that the addition of approximately 2 to 6 parts by weight of hexamethylene tetramine to 100 parts of the treating solution of the present invention further accelerates the gel time and cure rate, but at the expense of storage life. It is believed that at elevated temperatures, the hexamethylene tetramine decomposes to produce ammonia and formaldehyde, which also act to accelerate the reaction. It is not known why the addition of hexamethylene tetramine shortens shelf life.

IMPREGNATION OF WOOD WITH THE TREATING SOLUTION OF THE PRESENT INVENTION

In treating wood, the treating solution of the present invention will be prepared as described above, at an appropriate solids content level (i.e. the appropriate level of dilution) and the wood will be impregnated by methods known in the art, particularly the method taught by US-A-3,968,276, which will typically include the following steps:

  1. 1. Wood to be treated is selected for treatment. The wood will be debarked and usually precut (e.g. dimension lumber) or pre-shaped (e.g. poles or fence posts). It may be green or air-dried or force dried and will often be in the form of poles or dimensional lumber. The ability to treat green wood (e.g. wood containing a significant amount of natural moisture) is an important advantage of the present process.
  2. 2. The wood to be treated is placed in an evacuation zone and exposed to pressures which are below atmospheric pressure (e.g. at a vacuum of at least 0,508 m (20 inches) of mercury, preferably at least 0,66 m (26 inches) of mercury) for a time sufficient to remove moisture and other volatiles from the wood. Vacuums of at least 0,7112 m (28 inches) of mercury are preferred. This reduced pressure is usually achieved slowly over a period of from 10 to 120 minutes (preferably 15 to 60 minutes).
  3. 3. The wood is then immersed in or flooded with the treating solution of the present invention while still under reduced pressure. During this phase of the treating, additional water and volatiles escape from the wood, and the treating solution begins to penetrate into the wood.
  4. 4. The pressure within the treating chamber or zone is then gradually increased to a level above atmospheric pressure (e.g. often to a level of 0,172-3,45 MPa gauge (25 psig-500 psig), preferably 0,345-2,41 MPa gauge (50 to 350 psig) to thereby increase the penetration of the wood by the treating solution. Typically, this step is continued until the treating solution has substantially completely penetrated into the heartwood, although the process could of course be stopped short of that point if a lesser treatment is desired.
  5. 5. To further improve and enhance the depth and quality of penetration of the treating solution into the wood, the vacuum and pressure cycle can be repeated as many times as desired (e.g. 2 to 25 or more cycles). When the process is cycled in this fashion, it is helpful if the maximum pressure during each cycle is increased each time by, for example, 0,0689-0,689 MPa gauge (10-100 psig) above the maximum pressure of the previous cycle (usually a pressure increase of 25% to 100% over the previous pressure). This appears to prevent the rupture and collapse of the wood cells near the surface of the wood.
  6. 6. Recovering the treated wood from the treating chamber.

Note that the vacuum and pressure phases of the treating cycle should be achieved gradually to avoid destruction of the cell walls of the wood. Thus, while speed is important for commercial purposes, too rapid a change in the pressure can be harmful. Consequently, the optimum cycle rates, pressure and vacuum should be determined for each set of operating conditions to be used (e.g. size, shape and type of wood to be treated; composition of the treating compositions, temperature, etc.)

Since it is the intention of the present invention to cause or permit the treating solution to cure after it has penetrated deep within the wood, the conditions of treating should be made so as to permit easy penetration of the wood followed by a rather rapid curing of the treating solution after penetration. It has been discovered that one very convenient method of accelerating the curing of the treating solution after the treating solution has deeply penetrated into the wood is to heat the treated wood. Although this heating can be accomplished in a variety of ways, the direct application of steam to the treated wood is preferred. This method requires no special chemicals and avoids the problems of premature curing that are sometimes associated with the use of catalysts. Moreover, the use of steam is convenient, economical, environmentally acceptable and does not cause any cleanup problems. One of the advantages of the present invention is that less heat and time is required to effect curing. The amount of heat and time will vary with the cross section of wood and the type of wood being cured.

FORMATION OF WOOD PRESERVATIVE SOLUTIONS AND/OR FIRE RETARDANT SOLUTIONS

If desired, the treating solution of the present invention and the concentrates thereof may contain other ingredients such as fire retardant chemicals, dyes or colorants, catalysts, various biocides and other chemicals (e.g. borax, which serves as a buffer or stabilizer). The presence of wood preservatives such as organo-metallic compounds is optional but preferred. Compounds of zinc and copper are particularly desirable. Suitable organo/metallic compounds include zinc naphthenate, copper naphthenate and copper-8-quinolinolate. The treating solution of the present invention has been successfully tested with the addition of water soluble copper (cupric) salts such as copper gluconate and copper triethanolamine, which function to enhance the wood preservative functions of the treating solution. The treating solution of the present invention has also been successfully tested with the addition of diammonium phosphate, which acts as a fire retardant.

The treating solution of the present invention is also useful in the preservation and fire-proofing of other cellulose fiber-based products, in phenol formaldehyde resin-sized woven and non-woven products, in fiberglass thermal insulation and in pultruded products.

ADVANTAGES OF THE PRESENT INVENTION INCLUDE:

  1. 1. a faster gel time (reduced 10 to 25 times at 121°C over prior art compositions from about 9-20 minutes to instantaneous gelling in the examples discussed below), which results in faster curing times, which in turn permits more quality management by allowing full curing at the wood treating plant as opposed to the end user's location--thus eliminating the effect on curing of unpredictable variables such as seasonal effects, geographic effect, etc. at the end user's site;
  2. 2. curable at significantly lower temperatures, which in turn lowers the cost of curing;
  3. 3. longer shelf life (extended from about 3-6 weeks to about 20 weeks or more, as shown in the examples discussed below);
  4. 4. much lower "free formaldehyde" content (reduced from a range of about 0.6-3.9% to a range of about 0.1-0.2% as shown in the examples discussed below), which reduces emissions of formaldehyde during "B-staging" and curing cycles and is preferred from an environmental standpoint as free formaldehyde is an environmental hazard;
  5. 5. increased tolerance to the additives which are normally added to these resoles to aid in wood preservation (e.g. copper-based additives) and fire retardance (e.g. diammonium phosphate).

The present invention will by further understood by reference to the following Examples.

Examples 1 and 2 FORMATION OF AQUEOUS PHENOLIC RESIN PREPOLYMERS

First, two phenol-formaldehyde resins (designated "A" and "B" respectively) were formulated as follows: Ex 1 Ex 2 Phenol-Formaldehyde Resin A Resin B Phenol 100 moles 100 moles 91% Paraformaldehyde 130 moles 250 moles Water 200 moles 200 moles 50% Sodium Hydroxide 4.5 moles 10.5 moles

Resin A was reacted for 2 hours at 65°C and adjusted with water to a non-volatile (or solids) content of 63%.

Resin B was reacted for 3.5 hours at 60°C and adjusted with water to a non-volatile (or solids)content of 63%.

Example 3 FORMATION OF AQUEOUS RESORCINOL FORMALDEHYDE RESIN PREPOLYMER

A resorcinol-formaldehyde resin prepolymer (designated hereinafter "C"), was formulated comprised of the following: Ex 3 Resorcinol-Formaldehyde Resin C Resorcinol 100 moles 91% Paraformaldehyde 50 moles Water 210 moles 50% Sodium Hydroxide 4.5 moles

Resin C was reacted to completion at a temperature of 85°C and adjusted to a 75% solids content by vacuum distillation. Resin C is reactive in the presence of formaldehyde or formaldehyde donors.

Examples 4 and 5 FORMATION OF THE TREATING SOLUTION OF THE PRESENT INVENTION

Approximately 15 parts by weight of Resin C was added each to Resins A and B, resulting in Example 4 (Resin AC) and Example 5 (Resin BC). A comparison of the properties of Resins A, B, AC and BC appears below: Ex. 1 Ex. 2 Ex. 4 Ex. 5 Property Resin A Resin B Resin AC Resin BC Non-volatile content 63% 63% 63% 63% Viscosity 180 cps 120 cps 250 cps 150 cps pH 9.0 9.0 8.8 8.8 Sunshine Gel Time @ 121°C 20 min. 9 min. 13 min. Instantly @ 107°C 58 min. 28 min. 36 min. 1.6 min. Water Tolerance infinite infinite infinite infinite Free Formald. 0.6% 3.9% 0.2% 0.1% Storage life [1] 28 days 40 days >140 days >90 days
1. Storage life of the resins were measured by loss of water tolerance from infinite to less than 1000% when stored at 25°C. Resins AC and BC remained at infinite water tolerance at the last reported test date.

Examples 6 and 7 ADDITION OF HEXAMETHYLENE TETRAMINE TO THE TREATING SOLUTION OF THE PRESENT INVENTION

A treating solution was formulated according to Examples 4 and 5. To each solution was added three parts by weight of hexamethylene tetramine, resulting in treating solutions Example 6 (Resin ACH) and Example 7 (Resin BCH). A comparison of the properties of Examples 6 and 7 appears below: Ex. 6 Ex.7 Property Resin ACH Resin BCH Non-volatile content 63% 20% Viscosity 230 cps 20 cps PH 8.8 8.7 Sunshine Gel Time @ 121°C -- -- @ 107°C 6.1 min. -- Water Tolerance infinite infinite Free Formaldehyde 0% 0% Storage life [1] 2 days 17 days

Examples 6 and 7 remained stable with the subsequent addition of water soluble copper (cupric) salts such as copper gluconate and copper triethanolamine. The addition of diammonium phosphate to Example 6 was well tolerated, but, for reasons not known, was not well tolerated by Example 7.

Example 6, containing copper triethanolamine and diammonium phosphate, when impregnated in a cellulose substrate reached a full cure in 3-4 hours at 80°C. This wood preservative solution was stable for 2 days at 20-25°C.


Anspruch[de]
Behandlungslösung, die für die Konservierung von Holz und anderen auf Zellulose basierenden Materialien durch tiefes Eindringen in das Material geeignet ist, umfassend: a) 8 bis 30 Gew.-% eines Phenolharzvorpolymers, das Formaldehyd in einem Molverhältnis von ungefähr 1,0 bis 2,75 Mol pro Mol Phenol enthält; b) 0,8 bis 7 Gew.-% eines Resorcin-Formaldehydharzvorpolymers, das Resorcin enthält, das mit Formaldehyd reaktiv ist, in einem Molverhältnis von nicht mehr als 0,70 Mol pro Mol Resorcin,

und
c) 64 bis 91 Gew.-% Wasser, wobei die Behandlungslösung einen Gehalt an freiem Formaldehyd von weniger als oder gleich 0,2 % aufweist.
Behandlungslösung nach Anspruch 1, wobei das Phenolharzvorpolymer Phenol-Formaldehydharzvorpolymer ist. Behandlungslösung nach Anspruch 1 oder 2, wobei das Phenolharzvorpolymer in einem Verhältnis von 16 bis 20 Gew.-% vorhanden ist. Behandlungslösung nach einem der Ansprüche 1 bis 3, des Weiteren enthaltend metallorganische, Holz konservierende Verbindungen. Behandlungslösung nach Anspruch 4, wobei die metallorganischen, Holz konservierenden Verbindungen aus der Gruppe ausgewählt werden, die Kupfergluconat und Kupfertriethanolamin umfasst. Behandlungslösung nach Anspruch 1 oder 5, die des Weiteren feuerhemmende Verbindungen auf Diammoniumbasis umfasst. Behandlungslösung nach Anspruch 6, wobei die feuerhemmende Verbindung auf Diammoniumbasis Diammoniumphosphat ist. Verfahren zur Zubereitung einer Behandlungslösung nach einem der Ansprüche Ansprüche 1 bis 7, die für die Konservierung von Holz und anderen auf Zellulose basierenden Materialien durch tiefes Eindringen in das Material geeignet ist, wobei das Verfahren umfasst: a) einen ersten Schritt des Hinzufügens von Phenol in ein erstes Reaktionsgefäß; b) einen zweiten Schritt des Hinzufügens von Formaldehyd in das erste Reaktionsgefäß in einem Molverhältnis von ungefähr 1,0 bis 2,75 Mol pro Mol Phenol; c) einen dritten Schritt des Hinzufügens eines Katalysators zu dem ersten Reaktionsgefäß in einem Molverhältnis von 0,02 bis 1,2 Mol pro Mol Phenol, wobei der Katalysator aus der Gruppe ausgewählt wird, die aus den Erdalkalihydroxiden und Erdalkalicarbonaten besteht; d) einen vierten Schritt des Hinzufügens von Wasser in das erste Reaktionsgefäß; e) einen fünften Schritt des Umsetzens des Inhalts des ersten Reaktionsgefäßes für ungefähr 0,5 bis 6 Stunden bei einer Reaktionstemperatur von 50°C bis 100°C, um das Phenolharzvorpolymer zu bilden; f) einen sechsten Schritt des Einstellens des Feststoffgehalts des Gehalts des Phenolharzvorpolymer mit Wasser auf ungefähr 50 bis 70 Gew.-%; g) einen siebten Schritt des Hinzufügens von Resorcin in ein zweites Reaktionsgefäß; h) einen achten Schritt des Hinzufügens von Formaldehyd in das zweite Reaktionsgefäß in einem Molverhältnis von nicht mehr als 0,70 Mol pro Mol Resorcin; i) einen neunten Schritt des Hinzufügens eines Katalysators zu dem zweiten Reaktionsgefäß in einem Molverhältnis von 0,02 bis 1,2 Mol pro Mol Resorcin, wobei der Katalysator aus der Gruppe ausgewählt wird, die aus den Erdalkalihydroxiden und Erdalkalicarbonaten besteht; j) einen zehnten Schritt des Hinzufügens von Wasser in das zweite Reaktionsgefäß; k) einen elften Schritt des Umsetzens des Inhalts des zweiten Reaktionsgefäßes für ungefähr 0,5 bis 6 Stunden bei einer Reaktionstemperatur von 50°C bis 100°C, um das Resorcin-Formaldehydharzvorpolymer zu bilden; l) einen zwölften Schritt des Einstellens des Feststoffgehalts des Gehalts des Resorcin-Formaldehydharzvorpolymers mit Wasser auf ungefähr 50 bis 75 Gew.-%; und m) einen dreizehnten Schritt des Vermischens des Phenolharzvorpolymers mit dem Resorcin-Formaldehydharzvorpolymer und Wasser, wobei das Resorcin-Formaldehydharzvorpolymer in einem Verhältnis von ungefähr 10 bis 30 Gew.-% des Phenolharzvorpolymers vorhanden ist, um die Behandlungslösung zu bilden. Verfahren nach Anspruch 8, des Weiteren umfassend den Schritt des Hinzufügens von metallorganischen, Holz konservierenden Verbindungen. Verfahren nach Anspruch 8 oder 9, des Weiteren umfassend den Schritt des Hinzufügens von feuerhemmenden Verbindungen auf Diammoniumbasis. Verfahren zur Behandlung von Holz zu seiner Konservierung durch tiefes Eindringen einer Behandlungslösung nach irgendeinem der Ansprüche 1 bis 7, wobei das Verfahren die Schritte umfasst: a) Platzieren des zu behandelnden Holzes in eine Evakuierungszone und das Holz Drücken unterhalb des Atmophärendrucks für eine Zeit Aussetzen, die ausreicht, um Feuchtigkeit und andere flüchtige Stoffe aus dem Holz zu entfernen; b) Tauchen des Holzes in die auf Wasser basierende Behandlungslösung, die Phenolharzvorpolymer, Resorcin-Formaldehydharzvorpolymer und Wasser enthält, unter dem reduzierten Druck; c) das Holz in der Behandlungslösung unter dem reduzierten Druck getaucht halten, bis die Lösung in das Holz eingedrungen ist; d) Erhöhung des Drucks über der Flüssigkeit auf einen Druck oberhalb des Atmosphärendrucks, um dadurch die Durchdringung des Holzes durch die Behandlungslösung zu steigern;

und
e) Herausholen des behandelten Holzes.
Verfahren nach Anspruch 11, bei dem das zu behandelnde Holz erwärmt wird, um das Härten der Behandlungslösung zu beschleunigen.
Anspruch[en]
Treating solution suitable for the preservation of wood and other cellulose-based materials by deep penetration into the material, comprising: a) 8% to 30% by weight of a phenolic resin prepolymer which contains formaldehyde in a mole ratio of approximately 1,0 to 2,75 moles per mole of phenol; b) 0,8% to 7% by weight of a resorcinol formaldehyde resin prepolymer which contains resorcinol that is reactive with formaldehyde in a mole ratio not exceeding 0,70 moles per mole of resorcinol,

and
c) 64% to 91% by weight of water, the treating solution having a free formaldehyde content of less than or equal to 0,2%.
Treating solution of claim 1, wherein the phenolic resin prepolymer is phenol formaldehyde resin prepolymer, Treating solution of claim 1 or 2, wherein the phenolic resin prepolymer is present in a ratio of 16% to 20% by weight. Treating solution of one of claims 1 to 3, further comprising organo-metallic wood preserving compounds. Treating solution of claim 4, wherein the organo-metallic wood preserving compounds are selected from the group comprising copper gluconate and copper triethanolamine. Treating solution of claim 1 or 5, further comprising diammonium-based fire retardant compounds. Treating solution of claim 6, wherein the diammonium-based fire retardant compound is diammonium phosphate. Method of preparing a treating solution as claimed In one of claims 1 to 7 suitable for the preservation of wood and other cellulose-based materials by deep penetration Into the material, said method comprising: a) a first step of adding phenol to a first reaction vessel; b) a second step of adding formaldehyde to said first reaction vessel in a mole ratio of approximately 1,0 to 2,75 moles per mole of phenol; c) a third step of adding a catalyst to said first reaction vessel in a mole ratio of 0.02 to 1,2 moles per mole of phenol, wherein said catalyst Is selected from the group consisting of alkaline earth hydroxides and alkaline earth carbonates; d) a fourth step of adding water to said first reaction vessel; e) a fifth step of reacting the contents of said first reaction vessel for approximately 0,5 to 6 hours at a reaction temperature of 50° C to 100° C to form the phenolic resin prepolymer; f) a sixth step of adjusting the solids content of the contents of said phenolic resin prepolymer with water to about 50% to 70% by weight; g) a seventh step of adding resorcinol to a second reaction vessel; h) an eighth step of adding formaldehyde to said second reaction vessel in a mole ratio not exceeding 0,70 moles per mole of resorcinol; i) a ninth step of adding a catalyst to said second reaction vessel in a mole ratio of 0,02 to 1,2 moles per mole of resorcinol, wherein said catalyse is selected from the group consisting of alkaline earth hydroxides and alkaline earth carbonates; j) a tenth step of adding water to said second reaction vessel; k) an eleventh step of reacting the contents of said second reaction vessel for approximately 0,5 to 6 hours at a reaction temperature of 50° C to 100° C to form the resorcinol formaldehyde resin prepolymer; l) a twelfth step of adjusting the solids content of the contents of said resorcinol formaldehyde resin prepolymer with water to about 50% to 75% by weight;

and
m) a thirteenth step of blending said phenolic resin prepolymer with said resorcinol formaldehyde resin prepolymer and water, wherein said resorcinol formaldehyde resin prepolymer is present in a ratio of about 10% to 30% by weight of said phenolic resin prepolymer to form said treating solution.
Method of claim 8, further comprising the step of adding organo-metallic wood preserving compounds. Method of claim 8 or 9, further comprising the step of adding diammonium-based fire retardant compounds. Process of treating wood for its preservation by deep penetration of a treating solution as claimed in any one of claims 1 to 7, said process comprising the steps of: a) placing the wood to be treated in an evacuation zone and exposing the wood to pressures below atmospheric pressure for a time sufficient to remove moisture and other volatiles from the wood; b) Immersing the wood under said reduced pressure In the water-based treating solution comprising phenolic resin prepolymer, resorcinol formaldehyde resin prepolymer, and water; c) maintaining the wood immersed in the treating solution under said reduced pressure until the solution has penetrated into the wood; d) Increasing the pressure above the liquid to a pressure above atmospheric pressure to thereby Increase the penetration of the wood by said treating solution;

and
e) recovering the treated wood.
Process of claim 11, in which the wood to be treated is heated to accelerate the curing of said treating solution.
Anspruch[fr]
Solution de traitement convenant à la préservation du bois et d'autres matériaux à base de cellulose par pénétration profonde dans le matériau, comprenant : a) 8% à 30% en poids d'un prépolymère de type résine phénolique qui contient du formaldéhyde dans un rapport molaire d'environ 1,0 à 2,75 moles par mole de phénol ; b) 0,8% à 7% en poids d'un prépolymère de type résine résorcinol formaldéhyde qui contient du résorcinol qui est réactif avec le formaldéhyde dans un rapport molaire ne dépassant pas 0,70 mole par mole de résorcinol,

et
c) 64% à 91 % en poids d'eau, la solution de traitement ayant une teneur en formaldéhyde libre inférieure ou égale à 0,2%.
Solution de traitement selon la revendication 1, dans laquelle le prépolymère de type résine phénolique est un prépolymère de type résine phénol formaldéhyde. Solution de traitement selon la revendication 1 ou 2, dans laquelle le prépolymère de type résine phénolique est présent dans une proportion de 16% à 20% en poids. Solution de traitement selon l'une des revendications 1 à 3, comprenant en outre des composés de préservation du bois organométalliques. Solution de traitement selon la revendication 4, dans laquelle les composés de préservation du bois organométalliques sont choisis dans le groupe comprenant le gluconate de cuivre et la triéthanolamine de cuivre. Solution de traitement selon la revendication 1 ou 5, comprenant en outre des composés ignifugeants à base de diammonium. Solution de traitement selon la revendication 6, dans laquelle le composé ignifugeant à base de diammonium est le phosphate de diammonium. Procédé de préparation d'une solution de traitement selon l'une des revendications 1 à 7 convenant à la préservation du bois et d'autres matériaux à base de cellulose par pénétration profonde dans le matériau, ledit procédé comprenant : a) une première étape qui consiste à ajouter du phénol dans un premier réacteur; b) une deuxième étape qui consiste à ajouter du formaldéhyde dans ledit premier réacteur, dans un rapport molaire d'environ 1,0 à 2,75 moles par mole de phénol ; c) une troisième étape qui consiste à ajouter un catalyseur dans ledit premier réacteur dans un rapport molaire de 0,02 à 1,2 mole par mole de phénol, ledit catalyseur étant choisi dans le groupe constitué par les hydroxydes alcalino-terreux et les carbonates alcalino-terreux ; d) une quatrième étape qui consiste à ajouter de l'eau dans ledit premier réacteur ; e) une cinquième étape qui consiste à faire réagir le contenu dudit premier réacteur pendant à peu près 0,5 à 6 heures à une température réactionnelle de 50°C à 100°C pour former le prépolymère de type résine phénolique ; f) une sixième étape qui consiste à ajuster la teneur en matières solides du contenu dudit prépolymère de type résine phénolique avec de l'eau à raison d'environ 50% à 70% en poids ; g) une septième étape qui consiste à ajouter du résorcinol dans un deuxième réacteur ; h) une huitième étape qui consiste à ajouter du formaldéhyde dans ledit deuxième réacteur, dans un rapport molaire ne dépassant pas 0,70 mole par mole de résorcinol ; i) une neuvième étape qui consiste à ajouter un catalyseur dans ledit deuxième réacteur dans un rapport molaire de 0,02 à 1,2 mole par mole de résorcinol, ledit catalyseur étant choisi dans le groupe constitué par les hydroxydes alcalino-terreux et les carbonates alcalino-terreux ; j) une dixième étape qui consiste à ajouter de l'eau dans ledit deuxième réacteur ; k) une onzième étape qui consiste à faire réagir le contenu dudit deuxième réacteur pendant à peu près 0,5 à 6 heures à une température réactionnelle de 50°C à 100°C pour former le prépolymère de type résine résorcinol formaldéhyde ; l) une douzième étape qui consiste à ajuster la teneur en matières solides du contenu dudit prépolymère de type résine résorcinol formaldéhyde avec de l'eau à environ 50% à 75% en poids ;

et
m) une treizième étape qui consiste à mélanger ledit prépolymère de type résine phénolique avec ledit prépolymère de type résine résorcinol formaldéhyde et de l'eau, ledit prépolymère de type résine résorcinol formaldéhyde étant présent dans une proportion d'environ 10% à 30% en poids dudit prépolymère de type résine phénolique, pour former ladite solution de traitement.
Procédé selon la revendication 8, comprenant en outre l'étape qui consiste à ajouter des composés de préservation du bois organométalliques. Procédé selon la revendication 8 ou 9, comprenant en outre l'étape qui consiste à ajouter des composés ignifugeants à base de diammonium. Procédé de traitement du bois pour sa préservation par pénétration profonde d'une solution de traitement selon l'une quelconque des revendications 1 à 7, ledit procédé comprenant les étapes suivantes : a) placer le bois à traiter dans une zone de dépressurisation et exposer le bois à des pressions inférieures à la pression atmosphérique pendant suffisamment longtemps pour éliminer du bois l'humidité et les autres matières volatiles ; b) immerger le bois sous ladite pression réduite dans la solution de traitement à base d'eau comprenant un prépolymère de type résine phénolique, un prépolymère de type résine résorcinol formaldéhyde et de l'eau ; c) maintenir le bois immergé dans la solution de traitement sous ladite pression réduite jusqu'à ce que la solution ait pénétré dans le bois ; d) augmenter la pression au-dessus du liquide jusqu'à une pression supérieure la pression atmosphérique pour augmenter la pénétration de ladite solution de traitement dans le bois ;

et
e) récupérer le bois traité.
Procédé selon la revendication 11, dans lequel le bois à traiter est chauffé pour accélérer la réticulation de ladite solution de traitement.






IPC
A Täglicher Lebensbedarf
B Arbeitsverfahren; Transportieren
C Chemie; Hüttenwesen
D Textilien; Papier
E Bauwesen; Erdbohren; Bergbau
F Maschinenbau; Beleuchtung; Heizung; Waffen; Sprengen
G Physik
H Elektrotechnik

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