CS196157B1 - Organo-silicon ammonium salts of o-hydroxy-benzoic acid and method of making them - Google Patents
Organo-silicon ammonium salts of o-hydroxy-benzoic acid and method of making them Download PDFInfo
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- CS196157B1 CS196157B1 CS610878A CS610878A CS196157B1 CS 196157 B1 CS196157 B1 CS 196157B1 CS 610878 A CS610878 A CS 610878A CS 610878 A CS610878 A CS 610878A CS 196157 B1 CS196157 B1 CS 196157B1
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- salts
- ammonium salts
- organo
- hydroxy
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229910052710 silicon Inorganic materials 0.000 title 1
- 239000010703 silicon Substances 0.000 title 1
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000011152 fibreglass Substances 0.000 description 4
- 229960004592 isopropanol Drugs 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LILIWOQTNCMZSN-UHFFFAOYSA-N N.N[SiH3] Chemical compound N.N[SiH3] LILIWOQTNCMZSN-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 silanes salt Chemical class 0.000 description 2
- HXJZEGBVQCRLOD-UHFFFAOYSA-N 1-triethoxysilylpropan-2-amine Chemical compound CCO[Si](CC(C)N)(OCC)OCC HXJZEGBVQCRLOD-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Description
Vynález sa týká nových organokremicfitých amóniových solí kyseliny o-hydroxybenzoovej a spósobu ich přípravy,The invention relates to novel organosilicon f itých ammonium salts of o-hydroxybenzoic acid and to their preparation.
Arainoalkyltrialkoxysilany sú známe /Walter Noll, Chemie und Technologie der Silicone, Verlag Chemie 1968/ a podobné je známe aj ich použítie ako promótorov adhézie, ktoré bolo popísané už v DE patente č. 1 694 381. Aj keď sa zistilo, že tvorba soli araínosílanov má pre niektoré aplikácie nepriaznivý vplyv na zlepšenie adhézie /Bagda E., Kerner D., Adhíision 5, 1 24 , 1 977/ nedá sa ich vplyv jednoducho eliminovač vyléčením kyselin, z dóvodu stabilizácie systémov, z ktorých sú na povrch skleněných vlákien nanášané. Přípravy solí sa pri přípravě róznych lubrikácíí najčastejšie prevádza za použítía kyseliny chlorovodíkovej alebo kyseliny octovej. DE přihláška č. 2 528 382 rozšiřuje aplikačně použítie amínoalkyltrialkoxysílanov přípravou nových amóniových solí s aromatickými azidosulfonylkarboxylovými kysel i nami. Podobné aj DE přihláška č, 2 452 690 popisuje soli na báze dikarboxylových kyselin a DE patent č. 2 400 039 na báze kyseliny chloroplatičitej.Arainoalkyltrialkoxysilanes are known (Walter Noll, Chemie und Technologie der Silicone, Verlag Chemie 1968) and their use as adhesion promoters is already known, as already described in DE patent no. Although it has been found that the formation of araino silanes salt has an adverse effect on the adhesion enhancement for some applications (Bagda E., Kerner D., Adhision 5, 1 24, 1 977), they cannot simply be eliminated by acid cure, to stabilize the systems from which they are applied to the surface of the glass fibers. The preparation of salts is most often carried out using hydrochloric acid or acetic acid in the preparation of various lubricants. DE application no. No. 2,528,382 extends the application of aminoalkyltrialkoxysilane by the preparation of new ammonium salts with aromatic azidosulfonylcarboxylic acids. Similarly, DE application No. 2,452,690 describes dicarboxylic acid salts and DE patent no. No. 2,400,039 based on chloroplatinic acid.
Vynález popisuje nové organokremičité amóniové soli kyseliny o-hydroxybenzoovej obecného vzorca I v ktorom znamená x celé číslo 0, 1 alebo 2 a R je metyl alebo etyl.The present invention provides novel o-hydroxybenzoic acid organosilicon ammonium salts of formula I wherein x is an integer of 0, 1 or 2 and R is methyl or ethyl.
Tieto nové soli sa pripravujú spósobom podlá vynálezu, ktorého podstatou je, že sa kyselinou o-hydroxybenzoovou pósobl na příslušné amínosilany v prostředí vo vodě rozpustného alkoholu, s výhodou metylalkoholu, etylalkoholu, izopropylalkoholu, pri teplote 0 až 50 °C, s výhodou 15 až 30 °C.The novel salts are prepared according to the process of the invention, which comprises treating o-hydroxybenzoic acid with the corresponding aminosilanes in a water-soluble alcohol, preferably methanol, ethyl alcohol, isopropyl alcohol, at a temperature of 0 to 50 ° C, preferably 15 to 50 ° C. Deň: 29 ° C.
Pretože voda je najčastejším riedidlom pri príprave róznych lubrikácíí, nemá technický význam příprava krystalických solí, ale roztokov, ktoré sa s vodou miešajú, pretože přípravu solí vo vodě nie je možné prevádzať, z dóvodu malej rozpustnosti samotnej o-hydroxybenzoovej kyseliny vo vodě .Since water is the most common diluent in the preparation of various lubricants, the preparation of crystalline salts is not of technical importance, but solutions that are mixed with water because the preparation of salts in water cannot be converted because of the low solubility of o-hydroxybenzoic acid itself in water.
Pri Štúdiu vlastností róznych solí na báze aminosílanov s minerálnymi a organickými kyselinami ako promótorov adhézie medzi skleněným vláknom a epoxidovou živicou sme zistili, že uvedené soli výrazné zlepšujú mechanické vlastnosti epoxidových sklolaminátov pri porovnaní s běžnými aminosilanmi, použitými pri ich príprave.In a study of the properties of different amino-based salts of mineral and organic acids as promoters of adhesion between glass fiber and epoxy resin, we have found that these salts significantly improve the mechanical properties of epoxy fiberglass compared to conventional aminosilanes used in their preparation.
Vynález je ďalej objasněný formou príkla· dov .The invention is further elucidated by way of example.
Příklad 1Example 1
2(C2H4NH)x(CH2)3Si(OR)3] 2 (C 2 H 4 NH) x (CH 2 ) 3 Si (OR) 3 ]
Příprava soli vzorcaPreparation of salt of formula
OH (^Ο^-COO h[nH2(CH2)3Sí(OC2H5)3JOH (? -? - COO h [n H 2 (CH 2 ) 3 Si (OC 2 H 5 ) 3 )
961 57 /1/, sa prevádzala v banke s míešadlom a oddělovací* lievikom.961 57 (1), was transferred to a flask with a stirrer and a separatory funnel.
Násada:handle:
44,3 g/0,2 mól/ Jf-aminopropy 1 tri etoxysilanu 27,6 g/0,2 mól/ o-hydroxybenzoovej kyseliny 71,9 g izo-propylalkoholu44.3 g (0.2 mol) of N-aminopropyl 1-ethoxy-silane 27.6 g (0.2 mol) of o-hydroxybenzoic acid 71.9 g of isopropyl alcohol
Do baňky sa vložila kyselina, alkohol a za miešania sa pomaly po kvapkách v priebehu 15 minút přidal silan. Reakčným teplom sa obsah baňky vyhriel na 35 až 40 °C. Amóniová sol sa uskladnila pri teplote -5 °C. Rryštalizácia neprebehla ani po 2 týzdňoch, čo umožňuje výhodné soli skladovat vo formě roztokov. Vodné roztoky solí sú čiré a stabilně· Rozpuštěním vo vodě sa připravil roztok obsahujúci 0,5 Z hmot. soli, ktorý sa použil na úpravu skleněných vlákien. Týmto roztokom sa upravili vlákna priamo pri ich výrobě z platinovej pece. Opravené skleněné vlákna z E-skla o hrúbke 13 mikrónov vo formě kokónov sa nechali cca 24 h volné predsušit a po tejto době sa dosušili pri 125 °C 4 h. Skleněné pramene sa použili ako výstuž epoxídovej živice na báze 2,2-bis/p-hydroxyfenyl/propanu a epichlórhydrinu s obsahom 0,50 ekvivalentov epoxy/100 g, vytvrdenej za použitia tvrdidla na báze dietyléntriamínu. Vyhodnocovanie sklolaminátov sa prevádzalo skúškou pevnosti na ohyb podlá ČSN 640 607 a umele stárnutie 2 h varom vo vodě. Podobným sposobom sa připravil 0,5 Z hmot. roztok základného aminosilanu vo vodě, t.j. jp-aminopropyltrietoxysilanu, ktorým sa rovnako upravilo a vyhodnotilo skleněné vlákno v epoxídovej živici. DosiahnutéAcid, alcohol was added to the flask and silane was slowly added dropwise over 15 minutes with stirring. The flask contents were heated to 35-40 ° C by reaction heat. The ammonium salt was stored at -5 ° C. Crystallization did not take place after 2 weeks, which makes it possible to store the preferred salts in the form of solutions. Aqueous solutions of salts are clear and stable. Dissolve in water to prepare a solution containing 0.5 wt. salt used to treat the glass fibers. This solution treated the fibers directly in their production from a platinum furnace. The repaired 13 micron thick E-glass fibers in the form of cocoons were allowed to pre-dry for about 24 hours and then dried at 125 ° C for 4 hours. Glass strands were used as reinforcement of epoxy resin based on 2,2-bis (p-hydroxyphenyl) propane and epichlorohydrin containing 0.50 equivalents epoxy / 100 g, cured using a diethylenetriamine hardener. Evaluation of fiberglass was performed by bending strength test according to ČSN 640 607 and artificial aging by boiling in water for 2 h. In a similar manner, 0.5 wt. a solution of the basic aminosilane in water, i. β-aminopropyltriethoxysilane, which also treated and evaluated the glass fiber in the epoxy resin. achievements
Do baňky sa vložila kyselina a 40 g alkoholu. Z oddelovacieho lievika sa za intenzívneho miešania po kvapkách přidal roztok sílánu v- zbytku alkoholu tak, aby teplota neprestúpila 50 °C, /20 minút/. Kvarternizácia je kvantitativná a sol je neobmedzene rozpustná vo vodě. Vlastnosti epoxidového sklolaminátu sa vyhodnotili rovnakým sposobom ako v příklade 1 a sú uvedené v tabulke.The flask was charged with acid and 40 g of alcohol. From the separatory funnel, a silane-alcohol solution was added dropwise with vigorous stirring so that the temperature did not exceed 50 ° C (20 minutes). The quaternization is quantitative and the salt is freely soluble in water. The properties of the epoxy fiberglass were evaluated in the same manner as in Example 1 and are shown in the table.
Promotor adhézieAdhesion promoter
Obsah skla /Z hmot./Glass content / Weight /
Medza pevnosti v ohybe /MPa/ aminosilan amóniová solFlexural strength (MPa) aminosilane ammonium salt
66,766.7
66,2 za sucha66.2 dry
150150
280 po vare280 after boiling
068068
230230
Příklad 3Example 3
Příprava soli vzorcaPreparation of salt of formula
OH ^O^-COO [h NH2C2H4NH(CK2)3Sí(OCH3)3JOH 4 O 4 -COO [h NH 2 C 2 H 4 NH (CK 2 ) 3 Si (OCH 3 ) 3 J
Příprava soli vzorcaPreparation of salt of formula
Násada:handle:
38,9 g /0,2 mól/-//^-aminoetyl/aminopropyltrimetoxysílánu38.9 g (0.2 mol) of N- (4-aminoethyl) aminopropyltrimethoxysilane
27,6 g /0,2 mól/ o-hydroxybenzoovej kyseliny27.6 g (0.2 mol) o-hydroxybenzoic acid
66,5 g /izo-propylalkoholu66.5 g / iso-propyl alcohol
Do baňky sa vložila kyselina, alkohol a ponořila sa do Dewarovej nádoby s ladom.The flask was charged with acid, alcohol and immersed in a Dewar flask with ice.
Po ochladení na 0 °C sa pomaly za miešania přidal sílán tak, aby teplota neprestúpila 10 °C. Po přidaní celkového množstva sílánu sa roztok koncentrácie 0,5 Z hmotnostných solí vo vodě- použil na úpravu skleněných vlákien. Vyhodnocovanie epoxidového sklolaminátu sa previedlo rovnakým sposobom ako v příklade 1 a vlastnosti ,οη θθ <g>-COO H [nH2C2H4NHC2H4NH(CH2)3Sí(OCH3)3]After cooling to 0 ° C, silane was added slowly with stirring so that the temperature did not exceed 10 ° C. After addition of the total amount of silane, a solution of 0.5% by weight of salts in water was used to treat the glass fibers. Evaluation of the epoxy fiberglass was carried out in the same manner as in Example 1 and the properties, οη θθ <g> -COO H [nH 2 C 2 H 4 NHC 2 H 4 NH (CH 2 ) 3 Si (OCH 3 ) 3 ]
Násada:handle:
g/0,2 mól/ N-/^—etyléndiaminoetyl/^'-aminopropy1trimetoxysilanug (0.2 mol) N - [(4-ethylenediaminoethyl)] - (4'-aminopropyltrimethoxysilane)
27,6 g/0,2 mól/ o-hydroxybenzoovej kyseliny27.6 g (0.2 mol) o-hydroxybenzoic acid
60*6 g izo-propylalkoholu60 * 6 g of isopropyl alcohol
PREDMETSUBJECT
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS610878A CS196157B1 (en) | 1978-09-22 | 1978-09-22 | Organo-silicon ammonium salts of o-hydroxy-benzoic acid and method of making them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS610878A CS196157B1 (en) | 1978-09-22 | 1978-09-22 | Organo-silicon ammonium salts of o-hydroxy-benzoic acid and method of making them |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS196157B1 true CS196157B1 (en) | 1980-03-31 |
Family
ID=5407348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS610878A CS196157B1 (en) | 1978-09-22 | 1978-09-22 | Organo-silicon ammonium salts of o-hydroxy-benzoic acid and method of making them |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS196157B1 (en) |
-
1978
- 1978-09-22 CS CS610878A patent/CS196157B1/en unknown
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