CA1327308C - Environmentally compatible pesticides and fire retardants - Google Patents

Abstract

ABSTRACT

There is disclosed an insecticidal composition which is an aqueous solution containing amoniumpentaborate and a mildewcide. A method of controlling degradation of wood by wood boring insects and fungi by the application of the composition is also disclosed.

Description

~ 327308 BACKGROUND OF T~IE INVENTION
, Boron compounds, e.g. boric acid, borax and disodiumoctaborate (TIM-BOR~, U.S. Borax) or their mixtures have been successfully used as pesticides. These chemicals are readily available and are without any serious health hazard to humans and other mammals at levels which are highly toxic to wood boring insects and to some of the decay fungi.
Timber preservation research, using ~oron compounds, dates back to the Forties and as a result, large scale commercial application of diffusion impregnation of timber was developed first in Australia and New Zealand.
(A.N. rhristiansen and E.J. Williams, Australian J. Applied Science, 411-429, 1951; g.M. Harrow, New Zealand J. 5ci.
Tech. B3214), 28-38, 1951; A. McNabb and ~.B~ Taylor, ibid., B35(1~, 113-126, 1953).
A paper by J. Thornton, titled "Boron Preserva-tion of European Timber" (Borax Consolidated Ltd., Borax House, Carlisle Place, London SWl, 1964) reviews the history and technology of boron diffusion into timber.
Boron treatments have been used since about 1982 in the U.S. wood industry. A vacuum and/or pressure dip-diffusion treatment of unseasoned wood with disodium-octaborate solution ~TIM-BOR~) provides excellent protection of wood against wood boring insects (L.H. Williams, .

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~ 327308 Proceedings, Twelfth Annual Hardwood Symposium, Hardwood Research Council, 154 163, 1984).
Other insecticides, such as Lindane ~-hexachlorocyclohexane), polyhalogenated Diels-Alder products: Dieldrin and Aldrin are toxic in humans and represent health hazard in the environment. Thus, environmentally compatible pesticides, such as boron products, are promising replacements for the above listed poisonous, teratogenic, halogenated organic compounds.

SUMMARY OF THE INVENTION
This invention relates to environmentally harmless pesticides: mixtures of ammoniumpentaborate and alkali- and/or alkaline earth metal salt~s) (such as sulfites, sulfates and phosphates) which are useful pesticides against wood boring and other : insects and certain fungi.

Furthermore, this invention describes the reaction between the said mixtures of ammoniumpentaborate and alkali- and/or alkaline earth metal salts and water soluble barium or calcium salts which result in poorly soluble barium- or calciumtriborate and the corresponding barium or calcium salts: sulfite, sulfate and/or hydrophosphate. These -.. ,....... ~
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new barium and calcium salt compositions are also useful , pesticides, fungicides and fire retardants.

"~ DETAILED DESCRIPTION OF THE INVENTION

The chemical compositions of matter, described in my U.S. Patent No. 4,514,326, issued April 30, 1985 and their barium and calcium derivatives besides being non-corrosive flame retardants were also found to be excellent pesticides providing several important advantages over other boron products published in the literature.
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The active ingredient present in all of the new compositions is ammoniumpentaborate. Ammoniumpentaborate serves as a precursor of boric acid which is formed during its ingestion by the insects. Boric acid is known to be toxic to insects such as termite,s, powderpost beetles, black carpet beetles, fire ants, carpenter ants, carpenter bees, cockroaches, silver fish, ho~sefly and other insects.
Ammoniumpentaborate and bariumtriborate or calciumtriborate mixed with barium- or calciumsulfite, and/or bariumhydro-phosphate and calciumhydrophosphate are useful pesticides ~2Q a~ainst insects and brown rot fungi. Bariumtriborate and calciumtriborate in an analogous fashion to ammoniumpenta-borate also produces in vivo boric acid in insects.
Boric acid is toxic to insects in very low concentrations (0.05-0.2~) in wood, but its mode of action 2S is unknown. Besides boric acid, ammonia is also liberated 3- ~
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~ from ammoniumpentaborate in the gut of wood decaying .; . . .
insects. Ammonia neutralizes the acidity (PH 5.0-6.0) of the ~
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content of the insect's gut and thus inhibits the activity of cellulase enzyme which is essential for the acid catalyzed hydrolysis of cellulose to glucose in wood boring ~` insects.
Due to the base strength differences between ammonia and sodiumhydroxide, the liberation of boric acid from ammoniumpentaborate is significantly easier than from sodiumborates, such as borax and disodiumoctaborate.
A further advantage of the ammoniumpentaborate compos~tions is their excellent water solubility. Thus, a 60% water solution of ammoniumpentaborate and sodiumhydro-phosphate mixture can be maintained between 30-35C. As a comparison, a 35~ disodiumoctaborate solution needs to be heated at 57C to ~eep the chemical in solution. Both solu-tions contain 41.92~ boric acid equivalent (BAE) content.
further advantage of the ammoniumpentaborate containing compositions is that they are also useful flame reta~dants and antismoldering agents with non-corrosive properties . on the contrary, alkali metal borates applied alone are not useful as flame retardants because they do not undergo thermodissociation as ammoniumpentaborate does. The latter dissociates to ammonia and borontrioxide above 200C.
Borontrioxide forms a glassy flux at higher temperatures and acts as fire retardant. Consequently, my compositions are useful a.s ~' , : ' , : ` ' : 1 32730~
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~ pesticides and flame retardants when applied at an appropriate ..
level in wood materials.
Another important advantage of the ammonium-pentaborate compositions is that they exhibit a higher ,j 5 toxicity in wood against insects than disodiumoctaborate does. Exposure tests were conducted with Formosan subter-ranean termite (Coptotermes formosanus, Shiraki) to banak wood (Virola spp.) by pressure treatment, using a 2% water "~.
-~ solution of ammoniumpentaborate-sodiumsulfate composition.
The test was carried out according to the American Society for Testing Materials Standard Test, D3345-74 IReapproved --. .~
1980). The test clearly proved the high level of toxicity of the pentaborate composition to termites. A nearly total mortality occurred after two weeks while survival exceeded 95% for termites exposed to untreated wood.
A 2% disodiumoctaborate ~TIM-BOR~) or a 2~
pentaborate muxture have marked differences between their boric acid equivalent (BAE) content. Whereas a 2% TIM-BOR~
solution has 2.40 g BAE, a 2% concentration of ammonium-pentaborate-sodiumsulfate solution contains 1.38 g BAE, which corresponds to a 42.7~ lower value. Yet, the lower BAE
level of the ammoniumpentaborate composition shows insecti-~idal and wood penetration characteristics egual to the 42.7~ higher BAE containing TIM-BOR~ solution.

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-CHEMISTRY OF_THE INVENTION

In addition to the ammoniumpentaborate contain-ing compositions, new barium- and calciumborate compositions were also discovered which are potent pesticides and flame retardants. Flame retaraation of these compositions was observed in wood and in synthetic polymers.
It has been found that a water solution of the ammoniumpentaborate-sodiumsulfate and/or sulfite, hydrophos-~,:
phate mixtures upon treatment of water soluble barium salts, such as bariumchloride, bariumacetate, or bariumhydroxyde produce new compositions of matter: bariumtriborate-barium-sulfate, bariumtriborate-bariumsulfite, and/or bariumtri-borate-bariumhydrophosphate. Similar reaction takes place between the above ammoniumpentaborate compositions and water ~15 soluble calcium salts or calciumhydroxyde, yielding calcium-- triborate and the corresponding calcium salts: sulfate, sulfite and/or hydrophosphate.
It was then discovered that the reaction between ammoniumpentaborate and bariumchloride which pro-ceeded first in about 60% yield can be impro~ed to > 90%
~ yield in the presence of appropriate amount of ammonia ¦ ~Eq.l).

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1 3273~
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6 N~4.B508-4H20 + 5 BaX2 3 2 Ammoniumpentaborate-5 Ba(B305)2-4 H20 + lO NH4.x Bariumtriborate .
1 X = Cl, acetate ~Eq.l) ,.,;
- Furthermore, it was found that ammoniumtet~a-borate also produces bariumtriborate when treated with barium salt in a water solution (Eq.2).

6 (NH4)2B407-4 H20 + 4 BaX2 Am~oniumtetraborate 4 Ba(B305)2.4 H20 + 8 NH4.X ~ 4 NH3 + 2 H20 ; Bariumtriborate X = Cl, acetate ~Eq.2) In light of my previous work, these are rather unexpected reactions. It was previously discovered that alkalitetra-borates undergo a three-step transformation in ~he presence of ammonium salts to ammoniumtetraborate, ammoniumtriborate and ammoniumpentaborate ~Eq.3). Furthermore, the intermedi-ates: ammoniumtetraborate and ammoniumtriborate also can be transformed into ammoniumpentaborate in water. However, in the presence of barium or calcium ions the final product of Eq.3, ammoniumpentaborate reverts to the triborate stage which is metastable in its ammonium 6alt form.
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Step 1 15 M2B407.n H20 ~ 15 ~NH4)2 Tetraborate Step 2 4 2 B407-4 H20 + 1~ M2X + n H O
- Ammoniumtetraborate Step 3 `~ ~ NH4 B35 + 10 NH3 ,- 12 NH4.B508.4 H20 + 8 NH3 i~ Ammoniumtriborate Ammoniumpentaborate ~10 (metastable) M = Na, K and/or 1/2 Ca ~; n = O - 10 X = S03, S04 and/or HP04 (Eq.3) Bariumtriborate has been described earlier by A.N. Karibyan et al. (Promst. Arm., 7, 38~39r 1974; Chem.
Abstr. 81, 144792e). They reacted borax wlth bariumchloride in water solution and identified three compounds: bariumtri-borate, bariumtetraborate and BaB6011.6 H20. The new barium-~riborate compositions, however, encompass other barium salts (sulfiteJ sulfate and/or hydrophosphate), as well.
Borate ores, e.q., Gowerit and Nobeleit are calciumtri-borates.
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From the above findings, it was first believed that the ammonium-ion of ammoniumpentaborate or ammonium-tetraborate played a key role in the formation of barium-triborate. Indeed, borax and one mole equivalent amount of ~` barlumchloride provided bariumtetraborate in my hands. It was therefore interesting to find that another sodiumborate:
disodiumoctaborate ~TIM-BOR~) unexpectedly produced barium-~.' ~,, ~ -8-. .

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~ 1 327308 triborate instead of bariumtetraborate in high yield upon bariumchloride treatment (Eq.4).
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~; 6 Na2B8013.4 H20 ~ 8 BaC12 + 4 NH3 + 2 H20 Disodiumoctaborate 8 Ba~B35)2 4 H20 + 12 NaCl + 4 NH4Cl Bariumtriborate (Eq.4) .
Pure bariumtriborate or calciumtriborate also i~ can be manufactured from mixtures of ammoniumpentaborate-sodiumchloride and/or ammoniumpentaborate-sodiumnitrate. The precipitated barium or calciumtriborate can be purified by dissolving the water soluble by-products.

USE AND APPLICATION OF BARIUM- AND CALCIUMBORATE
COMPOSITIONS
It was already discussed above that besides ;15 bariumtriborate, barium-sulfate, -sulfite and/or -hydrophos-phate are also-being generated during the reaction between a mixture of ammoniumpentaborate plus alkali metal-sulfate, -sulfite and/or -hydrophosphate and water soluble barium salts. These new compositions of matter: bariumtriborate plus bariumsulfate, bariumsulfite and/or -hydrophosphate are also useful pesticides. The analogous calcium composi-tions possess similar usefulness.

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' Furthermore, bariumtriborate and the commingled barium salts ~S04, S03, HP04) or their calcium analogs which have poor water solubilities can be generated in situ on a :

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dry wood surface whieh were previollsly treated with ammoniumpentaborate compositions. The spraying and dipping of ammoniumpentaborate treated wood with ammonia containing bariumchloride or bariumhydroxyde solution instantly forms these sparingly soluble barium salts which act as sealants by , encapsulating the water soluble ammoniumpentaborate composition will act as pesticide and mold resistant and provides protection against leaching out of the insecticidal ammoniumpentaborate from wood. Similar results can be ~- 10 achieved by the analogous calciumtriborate and commingled , calcium sulfate, sulfite and/or hydrophosphate when calciumchloride calciumhydroxide is applied on the ammoniumpentaborate treated wood Alternatively, the m;xture of barium and calcium compositions can be finely milled and used as suspensions in an organic carrier such as light petroleum for pressure-treatment of seasoned wood material.
A1though the heretofore described boron compositions possess some fungicidal activities, nevertheless it is advisable to add appropriate amounts of mildewcides to the boron compositions. As examples one can add methylene bis-~thiocyanate), (Busan~P, ~uckman Laboratories, r~emphis, Tennessee), 3-iodo-2-propynyl butyl carbamate, (Troysan Polyphase~l Troy Chemical Corp., Newark, N.J.), sodium pentachlorophenolate, or propionic acid salts, e.g. NH4-, Na-, Ca-, Ba-, r~g- or N-alkylpyridinium-propionate/s in 0.005-2.0~ add-on level.

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Bariumtriborate containing compositions of this ~ invention are also useful as flame retardants in synthetic i fibers. Bariummetaborate tBaO.B2O3) was reported and patented by German authors as replacements up to 50~ of the expensive antimonytrioxide in polyvinylchloride (PVC) without the loss of its fire resistance (H.P. Skilandat, B.
Taubert, Plaste Kautsch., 1976, 192-197; Chem. Abstr. 85, 6464f and B. Taubert, A. Hopp and H.P~ Skilandat, Ger. P.
(East3 130,025 1976; Chem. Abstr., 91, 76277v).
The newly discovered bariumtriborate containing compositions are also useful for improving the fire retar-dancy of polymers. In my earlier U.S. Patent 4,504,546 (1985) it was pointed out that ammoniumpentaborate is also useful as fire retardant in polymers.
Cellulose, or synthetic fibers were pressure polymerized with phenol-formaldehyde polymer to mats which provide acoustical panels for automotive industry and building industry~ Ammoniumpentaborate compositions used in phenol-formaldehyde polymer have passed the 25 foot tunnel ~ 20 test and were qualified as Class I products.
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The pesticides and flame retardants described can be applied on virgin, processed, reconstituted or recycled, cellulose or cellulose-lignin materials such as timber, railroad ties, plywood, composite wood, wood chips, newsprints and other wood materials; glues, paints and as fire retardants in synthetic polymers.

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;' The following examples are given as illustra-tions of the present invention but are not to be considered as limiting the same.
Example 1 A well-stirred mixture of 73.5 kg borax penta-hydrate and 33.4 kg ammoniumsulfate in 45 1 of water was heated to its boiling point. After 30 1 of water, ~arrying : the liberated ammonia was distilled off, about 95 1 of hot syrup remained in the reaction vessel. A hot spray-drying or flaking resulted in a solid mixture of ammoniumpentaborate and sodiumsulfate. One recrystallization of the crude product yielded pure ammoniumpentaborate.
Example 2 Following the procedure of Example 1, but substituting ammoniumsulfate with ammoniumsulfite or ~15 diammoniumhydrophosphate or alternately with ammonia gas, plus sulfurdioxi~e, or ammonia gas and phosphoric acid ammoniumpentaborate and sodiumsulfite or ammoniumpentaborate and disodiumhydrophosphate were obtained.
Thus, 48.6 ml concentrated ammoniumhydroxide (28~ NH3 content), representing 136 g ammonia ~8 mole) was diluted by 600 ml water and within 10 min 560 ml ~920 g) phosphoric acid (85~) ~8 mole) diluted by 600 ml water was added to ~he stirred mixture. The temperature of the reaction mixture rose to 80C. Then, to the stirred, hot `, i~

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mixture 2330.4 g (8 mole) borax .S H2O was added at once, which cooled the temperature to 52C. The clear mixture was then stirred and the excess of ammonia was distilled off with the help of an additional 4 1 water. The residual thick ,~ 5 syrup was then diluted by water up to 4720 ml which yielded a clear, colorless solution containing 59.2% tweight/
~-~; volume) solid content. The solution contained 36.5%
ammoniumpentaborate (41.92% BAE). Its specific gravity is ~ 1.33/32C. The solution's PH is between 7-8 and is ready ;~ 10 for dip-diffusion of timber. The solution remains clear at 35C.
Example 3 The composition of Example 1 can be manufac-~ tured by the following alternate technology. One mole amount ;; 15 of alkali and/or alkaline earth metal tetraborate is trans-formed in a hot solution with the help of one mole equiva-. lent of sulfuric acid and with a minimum amount of 0.8 mole ammonia into ammoniumpentaborate and the corresponding metal sulfate.
~-~ 20 Thus, a solution of 48.6 ml concentrated ammoniumhydroxyde (0.8 mole) in 200 ml water, or 13.6 g (0.8 .~
mole) ammonia in 240 ml water was treated with 98 g (53.3 ml) concentrated sulfuric acid while the temperature rose .
over 70C. ~Alternately, ammonia can be added to sulfuric acid.) The hot solution was then treated in one batch with 291.3 g (1 mole) borax and with the help of a short heating a clear solution was obtained. During this process a rapid -l3 ~:`
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1 3273a8 and a practically quantitative transformation of the tetra- -borate to ammonium pentaborate occurred. The hot, clear solu~ion contains about 70~ solid and can be directiy applied as fire retardant and/or pesticide.
S From the reaction mixture ammoniumpentaborate crystallized at room temperature. One recrystallization from water provided pure ammoniumpentaborate ( ~KmBax 3400l 3240 (broad), 1650, 1430, 1350, 1250, 1100, 1030, 920, 780, and 690 cm 1).
Alternately, the hot reaction mixture can be evaporated or spray-dried to a mixture of solid ammonium-~. .
pentaborate and sodiumsulfate. During the removal of water less than 5% of the applied ammonia was distilled off.
Example 4 ~; 15 Following the procedure of Example 3, but sub-stituting sulfuric acid with sulfurous acid (SO2 in water) , or phosphoric acid, mixtures of ammoniumpentaborate and alkali and/or alkaline earth metal sulfites or hydrophos-phates were obtained.
Example 5 ~ Ammoniumpentaborate (16.3 g) was dissolved in Elj 50 ml water, containing 0.7 g ammonia. The clear solution was treated with 12.2 g bariumchloride dissolved in 30 ml water. The two solutions instantly produced bariumtriborate as a fine crystalline precipitate which after drying weighed 19.? g (90.9% yield). Theor. yield is 21.67 g.
~Km~r 3520, 3400 ~broad), 1630 tsmall), 1450 (shoulder), 1365 , , . . .

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` -14-, (very strong), 1190 (small) 1130 (~mall), 1020 (very strong), 930 tsmall), 885 (medium), 815 (medium), 795 (small), 740 (medium), 685 (medium) cm Analysis for BA(B3O5)2.4 H20:
5Bacalc'd 31-63% BCalc~d 14.93%
Bafound 31-85~ Bf~Und: 14.69%
Solubility in water: 0.39%/20C
Bariumtriborate was found to be stable at 300C/3 hours.
10Example 6 Followinq the procedure of Example 5, but , substituting ammoniumpentaborate with 5.26 g (0.02 mole) ammoniumtetraborate which upon reacting with 4.88 g (0.02 mole) bariumchloride provided bariumtriborate in good yield.
The composition was proven by barium and,,boron analyses (determined as boric acid) and IR spectrum.
Example 7 , Following the procedure of Example 5, but substituting a~moniumpentaborate with a solution of 8.24 g ~' 20 ~0.02 mole) disodiumoctaborate in 30 ml water and 6.51 g (0.026 mole) bariumchloride in lS ml water 10.3 g ~89.1%~
bariumtriborate was obtained. The IR spectrum and elemental analysis verified the composition.
' Example 8 Follo~ing the procedure of Example 5, but substitute ammoniumpentaborate with 5.82 g (0.02 mole) borax pentahydrate and using 3.08 g (0.0126 mole3 bariumchloride , ~ .

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in a total of 33 ml boiling water (1 hr), 4.1 g bariumtetra-~;~ borate was isolated. The analysis for BaB4O7.4 H2O showed a B/Ba ratio of 4.01:1. IR spectrum showed ~max 3400 ~broad), 1640 (medium), 1420 (shoulder), 1340 (broad, very strong), 1000 (broad, very strong), 730 (weak), 690 (weak) ~; cm Example 9 A mixture of ammoniumpentaborate and sodium-sulfate, or -sulfite and/or -hydrophosphate was rendered to 10 about PH8 by ammoniumhydroxide and treated with barium-chloride solution. Alternately, bariumhydroxyde can be used without the application of ammoniumhydroxyde. White precipi-tate was formed spontaneously: bariumtriborate mixed with bariumsulfate, or bariumsulfite and/or bariumhydrophosphate and was isolated by filtration in nearly quantitative yield.
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The filtered, washed micro-crystalline white powder contains no ammonium ion and has a low water solubility.
Thus, a mixture of 10.82 g ammoniumpentaborate-sodiumsulfate of Example 1 was dissolved in 50 ml hot water.
The solution was rendered alkaline by ammoniumhydroxide ~p~8) and treated with 12.2 g bariumchloride solution dissolved in 30 ml water. The microcrystalline precipitate:
bariumtriborate-bariumsulfate weighed 15.7 g (yield 100%).
Its water solubility is ~1.0%/20C.
Example 10 Following the procedure of Example 2 or 3, but using ammoniumchloride or ammoniumnitrate, or alternately -l6 ;, .

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` -` 1 327308 ammonia and hydrogenchloride or nitric acid instead of ! ammoniumsulfite or hydrophosphate, a mixture of ammonium-pentaborate and sodiumchloride or sodiumnitrate was obtained.
Example ll Following the procedure of Example 9, but sub-!, ~ stituting ammoniumpentaborate and sodiumsulfate, sodium-i sulfite and/or sodiumphosphate with ammoniumpentaborate and sodiumchloride or sodiumnitrate, a mixture of bariumborate and bariumchloride or bariumnitrate was formed. The latter by-products can be removed by water, yielding pure barium-i triborate.
; Example 12 Eollowlng the procedure of Example 9, but ~; lS substituting bariumchloride or bariumhydroxyde with soluble calcium salts, such as calciumchloride or alternately with calciumhydroxyde, a mixture of calciumtriborate and the corresponding poorly soluble calcium-sulfate, -sulfite and/or -hydrophosphate were obtained.
Example 13 Following the procedure of Example 5, but substituting bariumchloride with calciumchloride or calcium-hydroxyde, calciumtriborate was obtained.
, Example 14 Followin~ the procedure of Example 10 and treating its product with calciumchloride, calciumtriborate and calciumnitrate was formed. The latter and the commingled , ~ .
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calciumchloride by~products were readily dissolved in water and pure calciumtriborate was isolated by filtration.
Example 15 Unseasoned banak wood pieces were vacuum and/or : 5 pressure treated with 2% ammoniumpentaborate-sodiumsulfate or ammoniumpentaborate-sodiumhydrophosphate solutions. For about six weeks, while the diffusion process of the chemi-cals took place, the wood samples were wrapped into plastic sheets and protected from drying. Termite treatments of the , wood samples, carried out according to the ASTM Standard Test, D3345-74 have shown a total mortality of termites between 2 and 4 weeks with a small weight loss of wood.
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Control studies on untreated wood showed a >95~ survival of termites.
Adding ~usan~ or Troysan~ mildewcide to the above ammoniumpentaborate-salt mixture secures wood against insects and fungi.
Exampl~ 16 Vnseagoned or seasoned hickory wood blocks (l.Sx2x6~) were dipped for about 30 seconds into S9.2%
ammoniumpentaborate-sodiumhydrophosphate solution of Exam-ple 2 and dried at room temperature. Then a spray with ammonia containing bariumchloride formed a white bariumtri-borate-bariumhydrophosphate protective coating on the wood surface. Wood samples resisted ignition four times longer (132 seconds) than the untreated wood blocks which bursted into flame within 25-30 seconds. Flame height of the Bunsen . .

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-` 1 3273~8 burner was 3" and the tip of the flame reached the wood surface. A cross section of the treated wood has shown only about 2 mm ammoniumpentaborate penetration. Longer diffusion time of the boron containing chemicals secures complete fire retardation, as well as protection against pests.
Bariumtriborate, bariumtetraborate or calcium-triborate containing diet fed to termites showed comparable toxicity with ammoniumpentaborate.
Example 17 Cotton, nylon, polyester, rayon or other poly-meric fibers were treated and heat polymerized under pressure with a finely ground mixture of the phenol-formal-dehyde polymer precursors and 15-30% ammoniumpentaborate-sodiumsulfate of Examples 1 or 3. The porous, compacted materials passed the 25 foot tunnel test representing Class I products as acoustical mats for building industry and sound proofing fire walls for the automotive industry.
Example 18 Ammoniumtetraborate ~ammoniumbiborate~ was refluxed in water while ammonia evolution was observed.
After 30-120 minutes of reflux the solvent was removed and the crystalline residue was found to be ammoniumpentaborate.
Example 19 A mixture o ammoniumpentaborate ~0.01-5.0%) and a mildewcide, such as Busan~, Troysan~ or sodium penta-chlorophenolate ~0.01-2.0%) in water solution was sprayed on or dip-diffused into wood. Wood boring insects, such as :
~` termites and lyctid beetles, as well as wood deca~ fungi were controlled by the above mixture.
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Claims (8)

1. An insecticidal composition comprising an aqueous solution containing an insecticidally effective amount of from 0.01-5.0% of ammonium pentaborate and from 0.01-2.0% of a mildewcide.

2. The composition of claim 1 wherein the mildewcide is methylene bis-(thiocyanate), 3-iodo-2 propynyl butyl carbamate, sodium pentachloro -phenolate, or a propionic acid salt.

3. The insecticidal composition of claim 1 wherein the insect is a wood boring insect.

4. The composition of claim 2 wherein the insect is a wood boring insect.

5. The composition of claim 3 wherein the wood boring insects are termites.

6. The composition of claim 4 wherein the wood boring insects are termites.

7. A method of controlling degradation of wood by wood boring insects and fungi which comprises applying the composition of claim 1 to wood by spraying or dip-diffusion.

8. The method of claim 7 wherein the wood boring insects are termites.