PCT [WORLD INTELLECTUAL PROPERTY ORGANIZATION Tmneratons! Butea 6 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (G1) International Patent Classification 6 = COTF 5/04, CO9K 5/00, C10M 139/00 | AL (21) International Publication Number: (43) International Publication Date: WO 97/09332 13 March 1997 (13.0397) (21) International Application Number: PCTISI96/00023 (22) International Filing Date: 4 September 1996 (04.09.96) (20) Priority Data: 9800272 ‘4 September 1995 (040995) SI (70472) Applicant and inventor: CADEZ, Franc (SUST Su entice 23, 1215 Metvode (S). Published ‘With international search report Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt of ‘amendment. (G4) Tite: TRIETHANOLAMINETRIBORATE, A COMPOUND OF BORIC (Ill) ACID AND TRIETHANOLAMINE WITH HIGH CONTENT OF BORATE COMPONENT, HIGHLY SOLUBLE IN WATER AND IN SOME ORGANIC SOLVENTS. G7) Abstract ‘Trethanolaminetrborate solves the problem of low solubility and inclination to crystallisation of the borate component in case of most known technically useful borates. Iti a product ofthe synthesis of boric (I) acd or its anhydride and triethanolamine. It is an ‘exothermic reaction taking place at 114 *C in a covered reactor, that allows for oll eating and is fitted with a thermostat, with thermal protection and with water condenser applied in the following reaction: N(CH:CHOH)3 + 3H3BO3 + N(CHsCH2-O-H2B02)s + 31:0 ‘withanolamine boric acid triethanolamineriborate or. N(CHCH2OH)a + 1,5 B203 + 1,5 Hs0 ~+ N(CH:CH-0-H2B02)s triethanolamine borie acid anhydride triethanolamineriborte. Application: heat transmission agents, working liquids, hydraulic liquids, biocide and ani-tre ‘protection of materialFOR THE PURPOSES OF INFORMATION ONLY Codes used to identify States party tothe PCT on the front pages of pamphlets publishing intemational spplications under the PCT. AM Amenia 6B Usied Kingdon MW Mate AT Asie GE Geogis MX Meo AU Assets GN Gases NE Niger 5 Betas GR Grace NL Neds Bon HU Thogy NO Navway BE Birkin Fino ee NZ NewZolant 2G gain TT haiy PL Pola By Bein Joan Fr Pome BR Bra ke keys RO Ronan BY Belin KG Kymaue RU Ron Feerion cA Cale XP_—_Denocrae Pop's Repuic sD Sud (CF Cent Ata Repaie Koa SE Seas Congo KR Repu of Kore 86 Singer CH Soars KZ Kann SL Shores Che dhe Leck Sk Slonkis CM Cameroon 1K Sita SN Seen Ge Rte SZ Sound 3 Cuhosovala LT Liaia ™ Gut CZ Cah Repatc WD Lasemboug 1G Toe DE Germany Ly tava yTetinn DK Dena MC Meco TT Td ad Tobago HE Eseia MD Repel of Mado UA Ube Spin MG Matagscu UG Ups FL Find ML Mat US Usted Sse of Ames rR Proce MN Mongolia WZ Uelinn GA Gis MR Mourais WN VietNamWO 9709332 PCTISI96/00023, ‘TRIETHANOLAMINETRIBORATE, A COMPOUND OF BORIC (III) ACID AND TRIETHANOLAMINE WITH HIGH CONTENT OF BORATE COMPONENT, HIGHLY SOLUBLE IN WATER AND IN SOME ORGANIC SOLVENTS ‘The invention refers to trethanolaminetriborate - a compound of boric (I) acid and trethenolamine which, compare to other boric acd sls, mixes with water at any ratio and is also well soluble in polar solvents Acconding tothe international patent classification, the petent ranks into C 07 F 5/04 class. ‘The technical problem solved by the invention in question involves greater epplicablity ofthe boc (II) acid in tll technicel branches where the respective application is limited by low solubility and incination to crystallisation, n particular at lower temperatures, which epplies tothe boric (II) acid and to most of ts salts. The compound is non-toxical and incombustible. Due to its physical and chemical properties it is widely used in heat transmission media, in metal working liquids, in hydraulic liquids and inthe field of biocide and ant-fire material protection, Its well known that at usual room tenaperature the boric (IH) acd is rather badly soluble, which elso applies to ‘most borates. Due to some of their properties, the boric (II) acid and/or its salts have already been widely used in technique, eg. a8 fimgicids, insecticides, fire extinguishing egents ant-comosion agents; some compounds areWo 97109332 PCT/SI96/00023 eee ee ee ee ‘borates and the boric acid alone can be used independently or in various mixtures. Some of these mixtures have ‘also been patented in various fields of application. Lately the problem of solubility and content of borate in the {field of wood protection has been successfully solved through the application of di-sodium octoborste (1). (Na9BgO13 x4H70). ‘The solubility of this preperation is much higher than the solubility ofthe borio (ID) acid and of most other ‘borates although this property becomes evident only at higher temperatures, At room temperature and even more at lower temperatures their solubility curve approaches the curve of boric acid and of most ofits salts. ‘SOLUBILITY OF BORIC (II) ACID AND THE CORRESPONDING SODIUM SALTS IN WATER - AS A FUNCTION OF TEMPERATURE, EXPRESSED IN MASS PER CENT ‘Temperature (°C) (Compound 20 0 Jo |10 |20 |30 |4 |so |60 |70 |g0 |90 |100 Boricamjacid =o fo 2a [3s ]a7 |62 [8g J10 }130 lise [iat |233 }27,5 B(OH), Sodium borate [0 fo [145 |17,0 |2000 |236 |279 |341 NaBO,x4H,0 Disodium lo Jo |10 ja |25 |38 |59 |95 |160 tetraborate }Na,B,0>x10H,0 Di-sodium lo fo [as 37 [7s |r [229 )264 [289 |39,3 |374 |374 loctoborate LNeByOyxdH0 | — ‘The solubility of boric acid and of some technically most frequently used borates is shown in Figure 1. ‘The invention refers tothe solution ofthe problem of bed solubility of the borate component through application of the product ofthe reaction between the boric (IH) acid and triethanolamine. The synthesis takes place in the reactor thats fitted with a string device and with oil heating at sndard pressure and at 114 °C. The reaction is ‘turbulent end exothermic. Three mols of boric acid react with one mol of triethanolamine as follows: N(CH;CH;OH), + 3H3B03 > N(CH:CH;-O-H,B0) +310 o N(CHgCHOH)3 + 1,5B,03 +1,5H209 N(CH,CH,-O-H;BO,, ‘The product isa clear yellowish, very thick and sticky liquid, The density ofthe final producti 1.330 to 1340 ‘kg/L It mixes with water at any ratio, The water solution has lower viscosity than the concentrate.Wo 97109332 PCT/SI96/00023, 3 ‘The freezing point of the water solution is below the water freezing point. Example of triethanolamineborate synthesis: ‘The following raw-materials are dosed into the reactor of 0.1 m3: + triethanolamine 32.04 kg boro acid 40.00kg ‘Due to foaming only 60 to 70 per cent of reactor volume can be exploited during the reaction, On the water ‘condenser we turn on the cooling water produced during the reaction. We tum on the string device andthe heating, Follows heating of the reactor content to a temperature of 114 °C at which the synthesis lasts for about 40 minutes. Thereafter we tum the heating off The synthesis is over when reaction water stops lowing from the ‘condensation reffigerator. The volume of the reaction water shall equal e east the calculated volume, in our case 11.61 dm3, The finished product weighs 60.43 kg SOLUBILITY OF BORIC (II) ACID AND THE CORRESPONDING SODIUM SALTS IN WATER AS COMPARED TO THE SOLUBILITY OF TRIETHANOLAMINETRIBORATE - AS A FUNCTION OF ‘TEMPERATURE, EXPRESSED IN MASS PER CENT ‘Temperature (°C) Compound -m|-0]o }10 }20 |30 [4 }s0 | 60 | 70 | a0 | 90 | 100 Borie (If) acid 0 jo jm jas [47 ja [se [mp |B | iB | Bm | Bs | Zs B(OH): ‘Sodium borate Oo [0 |S | mp | m | 26 | mp | w NaBO,x4H,0 ‘Disodium o |o |p [us | 2 |B | |95 | + NaBOpx10H,0 Disodium coctoborate 0 jo Jip | a7 |B | Bi | 2p | a4 | BD | BB | MA | TA = NeBj0ye4H,0 ‘Triethanolaminetribo ‘mp | sono | ono | cmp | mp | imap | snp | smnp | smo | mp | imo ite N(CH) HBO), ‘The solubility of trethanolaminetiborate as compared to that of bore acid and of some other borates is shown in Figure 2wo 97709332 PCTISI96/00023 4 ‘VISCOSITY OF TRIETHANOLAMINETRIBORATE WATER SOLUTION AT VARIOUS, CONCENTRATIONS (mm2/s) ‘Temperature (°C) wc j10 | |30 |4 |s0 [6 |7 |80 |90 | 100 1% [55 |4 | [30 [26 [is fi2 3% |7s |s7 ja ja [3s {3 | [13 0% m jes |ss jas ja fas 27 fis 8% us jes |e 47 [a [3s f27 [2s ja 100% 502 ‘The viscosity of trethanolaminetriborate water solution as function of temperature and concentration is shown in Figure 3‘WO 97/09332 PCTISI96/00023, PATENT CLAIMS 1. The chemical compound withthe chemical name triethanol-arminetriborate characterised tn that ACH_CH,OH,BO, its formula runs N ->CH)CH OH) NCH,CH,OH2B0, that 100g oftrethanolaminetrborate in concentrated form contains the equivalent of 11.74 of boron (B) and/or 66.19 g of boric (Il) acid and that at room temperature itis «highly viscous clear yellowish liquid with 1.3300 to 1.3400 kl density, 2. The synthesis procedure for production of trethanolaminetriborate ‘characterised tn that ‘the first output raw-material is triethanolamine and the second being boric (I) acid (7a) ot its anhydride (7b), reciprocally reacting exothermally at 114 °C in the reactor, that allows for ol heating and that is covered, fied ‘with a thermostat, with thermal protection, with a water cooled condenser for reaction water and with a string device, following the reaction: N(CH,CH;0H)3 + 3H3BO3 > N(CH,CH;-O-H,BO); +310 : eee a ot N(CHCH)OH)3 +1,5B,03 +1,5H,O> N(CH,CH,-O-H,BO))s ‘triethanolamine boric acid anhydride triethanolaminetriborate 3. The chemical compound trethanolaminetriborate aocording to the claim no. 1 ‘characterized in that itis designed for application as the main component or as additive to heat transmission agents. 4. The chemical compound triethanolaminetiborate according tothe claim no. 1 ‘characterized in that itis designed for application asthe min component or as additive to processing iquids used at cutting, grinding and reshaping procedures, ‘5. The chemical compound triethanclaminetiborate according tothe claim no. 1 Characterized tn that itis designed for application as the main component or as additive to hydraulic liquids.‘WO 97/09332 PCTISI96/00023, 6 6. The chemical compound trsthanclaminetrborate according to the claim no, 1 characterized tn that itis designed for application as the msin component ores additive to biocide and anti-fre protection agentsWO 97/09332 PCTISI96/00023, 12 » NaxBsO1SAEDD ” » & ss 2» Nerorx1080 OHS 10 20-10 0 10 2 30 40 SO 60 70 80 90 100 ‘Temperature (degreesC) Figure 1wo 97709332 PCTISI96/00023, 20-10 0 610 20 630 «40 «650 60 «670 «680 «690 100 Figure 2 1000 100% == r , 68% 50% 1% 33% 10 ° 2 0 60 80 10 120 ‘Temperature (degreesC) Figure 3INTERNATIONAL SEARCH REPORT (acme Pu./SI 96/08823, 7 ASSIFTCATIO OF UBIECT MATTE Teee "Cave /oa EdaK5/a0-——c10M139/00 Acorn oIntraional Patent Clasifctin (IP) ort bth atonal lasieaton and PC ine ‘FIELDS SEARCHED ‘Wii documeton ached” (ascaion nem falowed by Gamieaton BRON) IPC'6 CO7F CO9K C1OM ‘Decarenaton arte ober Gan em dvinenaon oe Fah a ach GOREN uae ne Bae Har leone ata tas conned Gung We nemnOonal Se (eae OT aa We an Whee rae, Sear we we) {C:DOCUMENTS CONSIDERED TO BE RELEVANT CCvgory” | Gaten of document, with nation, whee appropiate, of the evant pasage Relean o euim No PAX CHEMICAL ABSTRACTS, vol. 125, no. 10, 1,2,4,6 2 September 1996 Colunbus, Ohio, US; abstract no. 119071, AND VARIOUS AMINOALCOHOLS* xp002022013 see abstract PAX & 0. MATER. SCI. LETT. vol. 15, no. 3, 1996, pages 1111-1114, WATANABE, S. ET AL.: "CHARACTERISTIC PROPERTIES OF CUTTING FLUID ADDITIVES DERIVED FROM THE PRODUCTS OF BORIC ACID 1,2,4,6 K] Forte docu area i he eoannuston of box C. DC] Pate ay members are ied in anne 7 Spec cagones of ied Sonam? “A” docament eninge genera ate fe a whic snot Ceondered ob St pateaar reetance “Bearer document bu pueden or afer the inteatonl “ing Ste “Lr document bic may teow outs on pony ims or “whch i ced to exalt ie puiaton date of sna ‘Sten or oer peal esa ar specie) “0” duet rigor in, eaten “P* document plied por oh nations ling date bt tier hn ep te ned T lner doce pushed ate the teraons ling dae ‘pao dando cote spent ‘ied endewand te prince oe ery verge “XC docaretof paral reevanc; the dame invention ‘Shot be coated ove or snag be comace [var sn imenve pwn he dae ken alone “Y* docmen of parle relevance; the daimed tenon ‘Sanat ankadeed tae in vente ap when he ‘car emis hone or more ele ssh ce Sopa es common Song aura ae aes "AY document enter ofthe me pat faruly Da oar saa angio oe aan a Dao align a 3 January 1997 28,01 97 Nine td lng rar Be BA Raa lier rope Put Oi, 8 Patan 2 FEL ey 35 68 epo ‘ Faetai%) 30308 Rinkel, L aon TEA se ma a page 1 of 2INTERNATIONAL SEARCH REPORT Tmuratonal Applicaton No PL. /S1_ 96/0023 €iCarinaca) DOCUMENTS CONSIDERED TO BE RELEVANT ‘Chabon of same wih EGCG, WE SPH ODE FT POTS A CHEMICAL ABSTRACTS, vol. 94, no. 4, 26 January 1981 Columbus, Ohio, US; abstract no. 17989t, SUGA, K. ET AL.: "SYNTHESIS OF WATER SOLUBLE CUTTING FLUIDS" xp902622014 see abstract & KANKYO KAGAKU KENKYU HOKOKU (CHIBA DAIGAKU) , 1979, page 17 CHEMICAL ABSTRACTS, vol. 117, no. 4, 27 duly 1992 Columbus, Ohio, US; abstract no. 28859V, BAZHANOV, S.V. ET AL.: "TRANSPARENT FIRE-PROTECTIVE WOOD COATING" xp002022015 see abstract & SU 1 659 443 A (BAZHANOV, S.V. ET AL.) 30 June 1991 iS ee eo (NATSON, H.J.) 29 February 972 see the whole document DE 27 48 212 A (UNILEVER N.V.) 11 May 1978 see the whole document 1,3 1,3 1,6 1,6 1,5 Faes POTN sours aoa ss aT) page 2 of 2INTERNATIONAL SEARCH REPORT fasion on pt aly meee ‘onratonal Appleanen No Pu./ST 96/8023 DE-A-2748212 Fan PCTASATO pnt oman ay BT 11-05-78 LU-A- tent document Publiation| Pater family Publication ited in search report, ‘due ‘embers ‘dae US-A-3645901, 29-02-72 NONE: 1590445 362854 25-06-81 513867 08-01-81 3005277 03-05-79 860375 02-05-78 1092037 23-12-80 630407 15-06-82 2369339 26-05-78 1295228 26-12-85 53056204 22-05-78 60018718 11-05-85 78423 (12-07-78 NL-A,B,C 7711924 03-05-78 SE-B- SE-A> 425669 25-10-82 7712283 «1-05-78