WOOD PRESERVATIVES

Abstract

A method for preserving wood by contacting wood with a composition comprising a polyurethane polymer, non-aqueous solvents, and a wood preservative.

Claims

1. A method for preserving wood; said method comprising contacting wood with a wood treatment composition comprising: (a) a polyurethane polymer synthesized from i) a polyol, and ii) an isocyanate; (b) at least one organic solvent; and (c) at least one wood preservative selected from among halogenated isothiazolinone biocides, halogenated carbamate fungicides and azole fungicides; wherein the polyol comprises from 1 to 5% poly-i-butylene oxide +99 to 95% p-propylene oxide; and

2. The method of claim 1 in which the wood preservative is 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.

3. The method of claim 1 wherein the organic solvent comprises diesel.

4. The method of claim 1 wherein the isocyanate is isophorone diisocyanate.

5. The method of claim 1 wherein the isocyanate is polymeric methylene diphenyl diisocyanate.

6. The method of claim 1 further wherein the polyurethane polymer comprises a capping agent selected from the group consisting of a primary amine having a carbon chain length of ≥C.sub.6, a mono alcohol, and a secondary amine.

7. A wood treatment composition comprising: (a) a polyurethane polymer synthesized from i) a polyol, ii) an isocyanate; and iii) a capping agent (b) at least one organic solvent; and (c) at least one wood preservative selected from among halogenated isothiazolinone biocides, halogenated carbamate fungicides and azole fungicides; wherein the polyol comprises from 1 to 5% poly-i-butylene oxide +99 to 95% p-propylene oxide; and further wherein the capping agent is selected from the group consisting of a primary amine having a carbon chain length of ≥C.sub.6, a mono alcohol, and a secondary amine.

8. The wood treatment composition of claim 7 further wherein the polyurethane polymer comprises a capping agent selected from the group consisting of a primary amine having a carbon chain length of ≥C.sub.6, a mono alcohol, and a secondary amine.

Description

EXAMPLES

Synthesis of Polyurethane Polymers:

[0015] The Following Polyurethanes were synthesized from a bis hydroxy terminated polypropylene oxide (95-99%)/polybutylene oxide (1-5 wt %) mixture and a diisocyanate. 150 mL of anhydrous bis hydroxy terminated polypropylene oxide (95-99%)/polybutylene oxide (1-5 wt %) mixture in aromatic 200 (solvent, 10-30 wt % solution), diisocyanate (2 molar equivalents of isocyanates to hydroxyl groups), was charged with 0.003% of a Tin catalyst (dibutyltin dilaurate) to the reactor. The reactor was heated to 90° C. with overhead stirring. The reaction mixture was held at 90° C. for 1 h.

[0016] In the examples where the polyurethane is capped, the residual isocyanate is measured using Surface SWYPE™ test strips. The reaction product was cooled to room temperature and the capping reagent, mono amine (1 equivalent amine to unreacted isocyanate) was added to cap the remaining isocyanate groups in the reaction mixture. Alternatively, when mono alcohol (1 equivalent hydroxyl to unreacted isocyanate) was used as the capping reagent it was added at 90° C. and reacted for an additional 1 h at 90° C. The reaction is continued at 90 C till no free isocyanate was observed when tested with SWYPE test strips. The polymer solids of the PU solution was estimated from the conversion and the amount of reactants used for the reaction. The polymer solids are calculated as the sum of the reactive components in the synthesis of the polymer.

Procedure to Determine Diesel Compatibility:

[0017] In a clear, 1 oz vial, 0.1 gram of the polymer (on a 100% polymer solids basis) is diluted with 9.9 grams of diesel fuel (weight/weight) to a 1% solution of the polymer. The sample is maintained at room temperature for 48 hours. After 48 hours, the solution is checked for incompatibility, defined as phase separation, precipitation of the polymer as solids, and/or turbidity.

Calculations of Hansen Solubility Parameters:

[0018] Hansen solubility parameters (HSP) for the various polyurethane end cap segments were computed using HSPiP software (Purchased from https://www.hansen-solubility.com/). Predicted HSPs (using the Y-MB method), namely, the HSP for the dispersion (D), polar (P), and hydrogen bonding (H) contributions (all SP in MPa1/2), the total SP (calculated using the predicted HSP), and “End cap distance from diesel” were computed. According to the HSP theory, the distance between two materials is a measure of the solubility. The smaller the distance the more soluble the fluids are within one another. HSP data for a “diesel” was obtained from the literature (Batista et al. J. Am. Oil Chem. Soc. V92, 95, 2015).

δ.sub.T=√{square root over (δ.sub.D.sup.2+δ.sub.P.sup.2+δ.sub.H.sup.2)}

R.sub.a=√{square root over (4(δ.sub.D1−δ.sub.D2).sup.2+4(δ.sub.P1−δ.sub.P2).sup.2+4(δ.sub.H1−δ.sub.H2).sup.2)}

δ.sub.D1=Dispersive solubility parameter for diesel=14.51
δ.sub.D2=Dispersive solubility parameter for a given end group (δ.sub.D)
δ.sub.P1=Polar solubility parameter for diesel=3.18
δ.sub.P2=Polar solubility parameter for a given end group (δ.sub.P)
δ.sub.H1=H-bonding=Dispersive solubility parameter for diesel=5.97
δ.sub.H2=H-bonding solubility parameter for a given end group (δ.sub.H)

TABLE-US-00001 TABLE 1 Diesel Compatibility of Polyurethane made with 95% p-iPO + 5 wt % piBO and IPDI with various cap segments (MW = 2000 to 4000) Diesel compatibility Calculated Hansen Solubility Parameters (1 wt. %) (MPa.sup.1/2) for End Cap Segment and “End p-iPO Mn = 2000 p-iPO Mn = 4000 Example End Capping Cap” distance from “Diesel” (Ra) EX-1-12; EX-1-12; # Reagent Polyol (bis OH) δ.sub.T δ.sub.D δ.sub.P δ.sub.H Ra Comp 1-5 Comp 1-5 EX-1  Methanol 5 w% p-iBO + 28.4 19.1 16 13.6 17.5 YES YES 95 wt % p-iPO EX-2  1-Butanol 5 wt % p-iBO + 22.7 17.5 10.4 10 10.2 YES YES 95 wt % p-iPO EX-3  1-Pentanol 5 wt % p-iBO + 21.9 17.4 9.5 9.2 9.2 YES YES 95 wt % p-iPO EX-4  1-octanol 5 wt % p-iBO + 19.8 16.9 7.6 6.9 6.6 YES YES 95 wt % p-iPO EX-5  Docosanol 5 wt % p-iBO + 17.1 16.2 4.3 3.4 4.4 YES YES 95 wt % p-iPO EX-6  Dimethylamine 5 wt % p-iBO + 26.1 18.3 14.3 11.9 14.7 YES YES 95 wt % p-iPO EX-7  Dihexylamine 5 wt % p-iBO + 19.7 16.7 8.1 6.6 6.6 YES YES 95 wt % p-iPO EX-8  Didecylamine 5 wt % p-iBO + 18.3 16.4 6.3 5 5 YES YES 95 wt % p-iPO Ex-9  1-hexylamine 5 wt % p-iBO + 22.7 17.5 10.9 9.6 10.4 YES YES 95 wt % p-iPO Ex-10 1-Octylamine 5 wt % p-iBO + 21.9 17.4 9.9 8.8 9.3 YES YES 95 wt % p-iPO EX-11 1-dodecylamine 5 wt % p-iBO + 20 17 8.1 6.8 7 YES YES 95 wt % p-iPO Ex-12 1-Octadecylamine 5 wt % p-iBO + 18.6 16.6 6.5 5.2 5.4 YES YES 95 wt % p-iPO Comp. 1 1-butylamine 5 wt % p-iBO + 25.6 18.1 13.2 12.4 13.9 NO NO 95 wt % p-iPO Comp. 2 1-pentylamine 5 wt % p-iBO + 24.5 17.9 12.2 11.5 12.6 NO NO 95 wt % p-iPO Comp. 3 1-hexylamine 100 wt % p-iPO 22.7 17.5 10.9 9.6 10.4 NO NO Comp. 4 1-Octylamine 100 wt % p-iPO 21.9 17.4 9.9 8.8 9.3 NO NO Comp. 5 1-dodecylamine 100 wt % p-iPO 20 17 8.1 6.8 7 NO NO

TABLE-US-00002 TABLE 2 Diesel Compatibility of Polyurethane made with 99% p-iPO + 1 wt % piBO and IPDI with various cap segments (MW = 2000 to 4000) Diesel compatibility Calculated Hansen Solubility Parameters (1 wt. %) (MPa.sup.1/2) for End Cap Segment and “End p-iPO Mn = 2000 p-iPO Mn = 4000 Example End Capping Cap” distance from “Diesel” (Ra) EX-13-24; EX-13-24; # Reagent Polyol (bis OH) δ.sub.T δ.sub.D δ.sub.P δ.sub.H Ra Comp 6-7 Comp 6-7 EX-13 Methanol 1 wt % p-iBO + 28.4 19.1 16 13.6 17.5 YES YES 99 wt % p-iPO EX-14 1-Butanol 1 wt % p-iBO + 22.7 17.5 10.4 10 10.2 YES YES 99 wt % p-iPO EX-15 1-Pexitanol 1 wt % p-iBO + 21.9 1.7.4 9.5 9.2 9.2 YES YES 99 wt % p-iPO EX-16 1-octanol 1 wt % p-iBO + 19.8 16.9 7.6 6.9 6.6 YES YES 99 wt % p-iPO EX-17 Docosanol 1 wt % p-iBO + 17.1 16.2 4.3 3.4 4.4 YES YES 99 wt % p-iPO EX-18 Dimethylamine 1 wt % p-iBO + 26.1 18.3 14.3 11.9 14.7 YES YES 99 wt % p-iPO EX-19 Dihexylamine 1 wt % p-iBO + 19.7 16.7 8.1 6.6 6.6 YES YES 99 wt % p-iPO EX-20 Didecylamine 1 wt % p-iBO + 18.3 16.4 6.3 5 5 YES YES 99 wt % p-iPO Ex-21 1-hexylamine 1 wt % p-iBO + 22.7 17.5 10.9 9.6 10.4 YES YES 99 wt % p-iPO Ex-22 1-Octylamine 1 wt % p-iBO + 21.9 17.4 9.9 8.8 9.3 YES YES 99 wt % p-iPO EX-23 1-dodecylamine 1 wt % p-iBO + 20 17 8.1 6.8 7 YES YES 99 wt % p-iPO Ex-24 1-Octadecylamine 1 wt % p-iBO + 18.6 16.6 6.5 5.2 5.4 YES YES 99 wt % p-iPO Comp.6 1-butylamine 1 wt % p-iBO + 25.6 18.1 13.2 12.4 13.9 NO NO 99 wt % p-iPO Comp.7 1-pentylamine 1 wt % p-iBO + 24.5 17.9 12.2 11.5 12.6 NO NO 99 wt % p-iPO

TABLE-US-00003 TABLE 3 Diesel Compatibility of Polyurethane made with 95% p-iPO + 5 wt % piBO and MDI with various cap segments (MW = 2000 to 4000) Diesel compatibility Calculated Hansen Solubility Parameters (1 wt. %) (MPa.sup.1/2) for End Cap Segment and “End p-iPO Mn = 2000 p-iPO Mn = 4000 Example End Capping Cap” distance from “Diesel” (Ra) EX-25-30; EX-25-30; # Reagent Polyol (bis OH) δ.sub.T δ.sub.D δ.sub.P δ.sub.H Ra Comp 8 Comp 8 EX-25 Methanol 5 wt % p-iBO + 28.4 19.1 16 13.6 17.5 YES YES 95 wt % p-iPO EX-26 Docosanol 5 wt % p-iBO + 17.1 16.2 4.3 3.4 4.4 YES YES 95 wt % p-iPO EX-27 Dimethylamine 5 wt % p-iBO + 26.1 18.3 14.3 11.9 14.7 YES YES 95 wt % p-iPO EX-28 Didecylamine 5 wt % p-iBO + 18.3 16.4 6.3 5 5 YES YES 95 wt % p-iPO Ex-29 1-hexylamine 5 wt % p-iBO + 22.7 17.5 10.9 9.6 10.4 YES YES 95 wt % p-iPO Ex-30 1-Octadecylamine 5 wt % p-iBO + 18.6 16.6 6.5 5.2 5.4 YES YES 95 wt % p-iPO Comp. 8 1-pentylamine 5 wt % p-iBO + 24.5 17.9 12.2 11.5 12.6 NO NO 95 wt % p-iPO

TABLE-US-00004 TABLE 4 Diesel Compatibility of Polyurethane made with 99% p-iPO + 1 wt % piBO and MDI with various cap segments (MW = 2000 to 4000) Diesel compatibility Calculated Hansen Solubility Parameters (1 wt. %) (MPa.sup.1/2) for End Cap Segment and “End p-iPO Mn = 2000 p-iPO Mn = 4000 Example End Capping Cap” distance from “Diesel” (Ra) EX-31-36; EX-31-36; # Reagent Polyol (bis OH) δ.sub.T δ.sub.D δ.sub.P δ.sub.H Ra Comp 9 Comp 9 EX-31 Methanol 1 wt % p-iBO + 28.4 19.1 16 13.6 17.5 YES YES 99 wt % p-iPO EX-32 Docosanol l wt % p-iBO + 17.1 16.2 4.3 3.4 4.4 YES YES 99 wt % p-iPO EX-33 Dimethylamine 1 wt % p-iBO + 26.1 18.3 14.3 11.9 14.7 YES YES 99 wt % p-iPO EX-34 Didecylamine 1 wt % p-iBO + 18.3 16.4 6.3 5 5 YES YES 99 wt % p-iPO Ex-35 1-hexylamine 1 wt % p-iBO + 22.7 17.5 10.9 9.6 10.4 YES YES 99 wt % p-iPO Ex-36 1-Octadecylarnine 1 wt % p-iBO + 18.6 16.6 6.5 5.2 5.4 YES YES 99 wt % p-iPO Comp. 9 1-pentylamine 1 wt % p-iBO + 24.5 17.9 12.2 11.5 12.6 NO NO 99 wt % p-iPO

TABLE-US-00005 TABLE 5 Diesel Compatibility of Polyurethane made with 95% or 99% p-iPO + 1 or 5 wt % piBO and IPDI or MDI with No cap segments (MW = 2000 to 4000) Diesel compatibility (1 wt %) p-iPO p-iPO (NCO/OH Mn = 2000 Mn = 4000 Example molar Polyol EX 37-42; EX 37-42; # ratio) NCO (bis OH) Comp 10-11 Comp 10-11 EX-37 0.1 IPDI 5 wt % p-iBO + YES YES 95 wt % p-iPO EX-38 0.8 IPDI 5 wt % p-iBO + YES YES 95 wt % p-iPO EX-39 0.1 MDI 5 wt % p-iBO + YES YES 95 wt % p-iPO EX-40 0.8 MDI 5 wt % p-iBO + YES YES 95 wt % p-iPO Ex-41 0.1 IPDI 1 wt % p-iBO + YES YES 99 wt % p-iPO Ex-42 0.8 IPDI 1 wt % p-iBO + YES YES 99 wt % p-iPO Comp. 10 0.1 MDI 1 wt % p-iBO + YES YES 99 wt % p-iPO Comp. 11 0.8 MDI 1 wt % p-iBO + YES YES 99 wt % p-iPO