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    1488160 Polyurethanes and precursor compounds ROHM AND HAAS CO 26 Nov 1974 [14 Dec 1973] 51141/74 Heading C3R [Also in Division C2] An hydroxy (polyalkylenecarbonyloxy)alkylene oxazolidine or oxazine has the formula where R<SP>1</SP> is H, mononuclear aryl, aralkyl or alkyl, R<SP>2</SP> is H or alkyl (both optionally substituted by Ha, C 1-4 alkoxy, OH, amino or NO 2 ) or R 1 and R 2 together complete a C 5 or C 6 cycloalkylene group; R<SP>3</SP> is as R<SP>1</SP> or is cycloalkyl; Y is a straight chain C 2 or C 3 alkylene which may be substituted by alkyl, aralkyl, alkanoyl or aryl; X is a straight chain C 1-4 alkylene group which may have a C 1-6 alkyl side chain; n is at least 4 and z is 1 to 50. It may be prepared by reacting an oxazolidine or oxazine with a lactone in the presence of a transesterification catalyst at 0‹ to 200‹ C. It may be reacted with a polyisocyanate to give a urethane compound where Z is the residue of the isocyanate, m is the valency of Z and p is m-1. Such urethane compounds with additional isocyanate when they do not contain free isocyanate groups are hydrocurable and may be cured in situ on a substrate, e.g. wood, metal, plastic, paper or leather, by exposure to atmospheric moisture.
    公开号:SU862833A3
    申请号:SU742088143
    申请日:1974-12-13
    公开日:1981-09-07
    发明作者:Дэвид Еммонс Вилльям
    申请人:Ром Энд Хаас Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) COMPOSITION FOR COATINGS
    one ,.   The invention relates to the preparation and tfimeni coatings based on isochchanate-containing compounds.  A known composition for a coating that contains a master screen and poly a1d {jlj.  Such a composition has high industrial properties, but is not sufficiently resistant to abrasive wear.  According to the technical essence and achievable effect to. The closest to the proposed composition is a composition for coatings containing organically polyischdaanate and monomeric oxazolidine G21. Such a coating can be cured by air moisture — hydroxyls that react with iscyanate are formed by hydrolysis of oxazolidine.  However, in this case, the abrasive durability of the cover is not enough.  The purpose of the invention. is an increase in abrasion resistance of the coating.  This is achieved by the fact that the composition, including the oxazolidine compound and the polyfunctional (} ian refinement, as the oxazolidine compound contains 3-hydroxy- (oligoalken-bonyloxy) -alkylox. azolidine of total but - ((Hg1n-1o-o, where either 5, - 15, X-alkyl, R-hydrogen or alkyl, at the molar level; oxidation of oxig1 sschidinovogo compound and nzocyanate from 1: 1 to 3: 1) cuff to be used adduct. isocyanate with oxazolidine compound.  Examples of starting isocyanates can be aliphatic diisocyanate with 36 carbon atoms (DDE), 1,6-hexamethylenediamine diisocyanate, 1,8-octamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4-trimethylene diisocyanate, and other aliphatic cyanide diisocyanate, 2,4,4-trimethylene diisocyanate, and other aliphatic cyanide diisocyanate, 1,2,4-trimethylene diisocyanate and other aliphatic cyanide diisocyanate. 3-isocyanatomethyl-3 anatopropyl ether, 5,5-trimethylcyclohexyl isocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate methyl 2,6-diisocyanatocaproate, bis (2-isocyanatoethyl) fumarate, 4 -methyl-1,3-diisocyanatocyclohexane, trans-vinylene and other unsaturated isocyanates, 4,4 m tilenbis (izrtsianato cyclohexane) and other bisizotsianaty, N, N, N-tris (6-izotsianatogoksametilen) -biuret, bis (2-izotsianatoetil) carbonate.  Aromatic isocyanates useful toluenediisocyanate, dianisidine diisocyanate, 4,4-diphenylmethane diisocyanate (IDI), 1-ethoxy-2,4-diizotsianatobeneol, 1-chloro-2, 4-diisocyanato benzene, tris (4-ieotsianatofeiil) -methane, naftalendiizotsianat, 4,4-biphenyl isocyanate, phenylenediisocyanate, 3,3-dimethyl-4, 4-diphenyldiisocyanate, tetrachloro-1,3-phenylene diisocyanate, 2,4, 6-tribrom-1, 3-phenylenediaisisteate oligomei, isocyanate, methacrylate, Id. or polyamines.  The most acceptable are triisocyanat (biuret), 4, 4-methylenebis (cyclohexyl isocyanate), isocyanate OD1, methy lenbis (4-phenylisocyanate), toluylene diiso cyanates, isophorone diisocyanate.  Depending on the molar ratio of both components, they are learned.  or izotsianatsoderzhzschie 1trodukgy capable of reacting with the movable soedineiishish atom or fully uretanirovannye soy nnvni 3-Hydroxy- (oligogshkilenkarboniloksi) -alkilazopidshn poluchaset reacting hydroxyalkyl 3- Fenokvaeoli in a (GEOK) with a lactone of 5 yLi b carbon atoms in the ring and u and: utatgat catalyst pereet; ia1ash at 5 mol molar from lactone.  The most acceptable mono- and popzl- {lower} - (u) about acton, € -capro lactone, corresponding to oxa actons with the alkoxy group Cj-Cjj. Curing of the composition is due to the moisture of the air (hydroxys of oxazolidine occur) t / HR N: - a-gHgva cv "The amino alcohols react with poly-cyanates to form a three-dimensional 1-film. Curing can be catalyzed by an acid catalyst (Of001-10% by weight of the composition).  in addition, the composition may contain solvents inert to the eo-cyanate and other targeted additives.  The mixture of components in the absence of moisture is stored for a long time and can be used in a single-package container In Gfivodi1 "1X below examples M | and n number average and weight average molecular weights, CPC-gwl-penetration chromatography.  Example 1  Synthesis of 3-oxa (polypentylenecarbonyloxy) -ethyl oxazolidine (M 1240).  A hydroxyethyl oxazolidine (GEO) (1.5 mol, 175.5 g), -caprolactone (3.0 mol, 342) was charged to a flask equipped with a stirrer, a funnel for the introduction of reagents, an agrarian device, a reflux condenser and a device for automatic temperature control. , 0 g) and dibutyltin oxide (, 0.75% on POLIE4IR, 7.73 g).  The contents of the flask are heated to 100 ° C and condensed at this temperature with addition of € 3 (60 mol, 513.0 g) for 60 min.  After the introduction of the reagents is complete, the reaction mixture is maintained for 4 hours to complete the reaction.  In the hot state, 3-hydroxy- (polypentylenecaronyloxy) -ethyl-3-oxazolidine.  () is a liquid, but upon cooling it forms a waxy substance (acids 0.130 m-eq / g, aoJSiHSt 1.38 m-eq / g, 6PC molecular weights: M y 1240,, bg, calculated molecules rs weight 687, equivalent weight in reaction with isocyanate 229 g-SQ).  A. 3- {pxy- (polypentylene carbonyloxy) -ethyl-oxazolidine () (0.01 eka, 2.29 g) was dissolved in xylene (5.3 g) and 001 (0.01 eq, 3.00 was added to the solution). d).  After smashing the ynastin, the yutastin is applied with fuy film with a thickness of 10 kl and allows it to curl at x 4N & t (SL temperature (time to disappear cast 60 minutes, transparent foam, the swelling in 2-ethoxyethyl acetate is insignificant, graphite rigidity). € 6).  B.  3-Focci- (polyphenylphenylphenols) ETlb-oxa-oolidin from рHt "M molecules weighing 1240 (0.01 eq., 2.29 g) is dissolved in xylene (g) and M, m-tris (6- yzocyanathexamethylene) stalk (0.01 eq., 2.50 g).  After mixing, aa &amp; 10m thick film is applied to the glass plate to give it the ability to cure to room temperature (the time until the tackiness disappeared 10 s, the shining film, the swelling in 2-etkkeksat1-1ateta is very small, the rigidity of the grant and).  B. 3-Goxy- (poly-petilencarbonyloxy-ethyl} -oxazole din (0.01 eq, 2.29 g} dissolved in xylene (3.6 g), and 4 4-methylene bis (cyclohexyl isocyanate) was added to the solution 1.31 g).  After mixing, a 10 cm thick wet film is applied to the glass plate and allowed to curl at room temperature (60 minutes of tack-free tackiness, transparent film, swelling in 2-ethoxyethyl acetate, very little graphite hardness F}.  G.  3-Soxy- (polypentylenecarbonkoxy) -ethyl-oxazolidine (0.64 mol, 443.0 g) is heated to and then 4,4-methylenebis (cyclohex isocyanate) (0.32 mol, 83.8 g) is added.  Due to the exothermic nature of the reaction, the mixture is heated to.  and then cooled, with stirring, to for 30 minutes.  At room temperature, this isocyanate is mixed with a bisoxazolidine hf product, resulting in a waxy product (calculated molecular weight 1636, 409 g-hectare for reaction with isocyanate).  The product obtained is mixed with xylene and various di- and polyisocyanates to obtain 3-p-Exoxy (by pentenylenecarbonyloxy) -ethyl-oxazolidine (1.50 mol, 1030.5 g) cures in moisture in the presence of moisture (1.50 mol, 1030.5 g) RSD (0.75 mol, 450 g) is added.  Due to the exothermic xaipaxTepa reaction, the mixture is heated to 9 ° C, after which, with stirring for 30 missions, it is cooled to.   At room temperature, this iso-cyanate, combined with the bisoxaeol product, forms a waxy substance (calculated molecular weight 1976, 494 g-eq for reaction with isocyanates).  The resulting product (0.01 eq., 4.94 g) is dissolved in xylene (7.5 g) and K, M N-TPHC (6-isocyanatohexamethylene) -buret is added to the solution.  After 1 tablet, a 10-note wet film is applied to the glass plate.  and give her the opportunity to curl off (time to disappear from type 15 min, transparent film, the swelling in 2-ethoxyethyl is insignificant).  PRIME 2.  Synthesis of 3-Oasoi - (polypentylenecarboxyloxy) -ethyl-oxazolidine (M 1590).  A GEOC (0.4 mol, 46.8 g) 6 -cagfolactone (2 mol, 364.8 g) and a flask are placed in a flask, supplied with a stirrer with a stirrer for introducing reagents, a non-burning device, a reflux condenser and a device for automatic temperature control. (1.0% for polyester, 4.14 g) The mixture is heated to 100 ° C and maintained at this temperature for 260 minutes while the E-caprolacTdH reacts.  In the hot state, the product obtained is liquid, but upon cooling a waxy substance is formed (acids 0.091 m-eq / g, atmaA.  .  0.936 mEq / g, GPS molecular weights, М „980, 1.62, calculation.  The molecular weight is 1030, equivalent to Bed in reaction with isocyanate (M4 343). .  A. 3-Goxy- (polypentylenecarbonyloxy) -ethyl-oxazolidine (M 1590) (0.01 eq., 3.43 g) is dissolved in xylene (6.4 g) and DDA (0.01 eq, 3.00) is added. d) After mixing, a film with a thickness of 10 mils is applied to the glass plate and allowed to curl at room temperature (60 minutes tacky, turbid film, slight swelling in 2-ethoxyethyl acetate, graphite hardness Sb).  B.  3-Soxy- (polypentylenecarbonyloxy) -ethyl7-oxazolidine () (0.01 eq., 3.43 g was dissolved in xylol (5.0 g) and N. was added. N, m-tris (6-isocyanatohexamethylene -biuret (0.01 eq, 2.50 g).  After mixing, a 10 mil thick wet film is applied to the glass plate and the dactiT is able to curl at room temperature (10 minutes until the tackle disappears, transparent film, the swelling in 2-ethoxy ethyl acetate is very slight, graphite hardness F).  B. (ps 1pentylenecarbonyloxy) -ethyl-oxazolidine (M ".  1590) (0.01 eq., 3.43 g) was dissolved in xylene (4.7 g) and 4,4-methylenebis (cyclohexyl isocyanate) (0.01 eq., 1.31 g) was added.  After mixing, a wet film of 10 mils is applied to the glass plate and allowed to curl at room temperature (time to tack free 120 minutes, transparent film, swelling in 2-ethoxyethyl acetate, very little hardness of graphite III).  G.  3-fOKCH - (polypentylenecarbonyl) xy-ethyl} -oxazolidine (M (1590) (0.01 eq., 3.43 g) is dissolved in xylene (4.4 g) and toluene diisocyanate is added.  After mixing, a 10 mil thick film is applied to the glass plate and allowed to curl at room temperature (60 minutes tack-free tack, transparent film, swelling in 2-ethoxyethyl acetate. Ate is insignificant).  Example 3  Synthesis of 3-goxy- (polypentylenecarbonyloxy) -ethyl-oxazolidine ().  In a flask equipped with a stirrer 14, a funnel for the introduction of reagents, a heater, a condenser and a device for automatic temperature control, a GEOC (6.09 mol, 105, Зг), € -caprolactone (1.8 mol, 205f2 g) is placed and BunSnO (0.75% on polyester, 3.49 g).  The flask is heated to and kept at this temperature while -caprolactone (7.2 mol, 820.8 g) is added during the bumin.  The contents of the flask are filled with bh to complete the reaction.  In the hot state, the hydroxy- (polypentylenecarbonylxy) -ethyloxazolidine obtained is both liquid, but when cooled, a waxy substance is obtained (the calculated molecular weight is 1257, the equivalent weight in the reaction with eo-cyanato is 419 g-eq).  3-R-hydroxy-polypentylenecarbonyl-1-oxy-ethyl-oxazolidine (0.42 mol, 531.9 g) is heated to a BFB, and then 4, 4-methylene bis (cyclohexyl isocyanate) (0.21 mol, 55.0 g) is added.  For the expense of. heat of reaction; the mixture is heated to, after which it is kept at this temperature for 3 hours to complete the reaction.  At room temperature, the product is a waxy substance (calculated molecular weight 2776, 694 g-eq for reaction with isocyanate).  P p and measures 4.  Synthesis of 3-goxy- (by pentenylenecarbonyloxy) -ethyl} -oxazo d | 1den ().  In a flask equipped with a stirrer, water for the introduction of reagents, a heater, a reflux condenser and a device for automatic re-heating of the temperature, a GEOC (0.60 mol, 70.2 g), B-caprolactone (1.2 mol, 136.8 t) and Bu / jSnO (0.75% of the total amount of polyester, 8.22 g).  The stockpile is heated to 100 ° C and maintained at this temperature while e-caprolactoids (7.8 mol, 889.2 g) are introduced for 60 No. 1H.  After the introduction of caprolactone is complete, the reaction mixture tetrasphere is maintained at 10 hours for 6 hours for the reaction.  In the hot state, the product obtained is itself liquid, but when it is cooled, a waxy substance is formed (acids 0.09 meq / g 0.523 mVeq, Gnc molecular weights: Mu257p, M 16 90,52, calculated molecules The average weight is 1827, the equivalent weight in reaction with isocyanate is 609 gavey).  BUT. 3-Goxi- (polypentylenecarbonyloxy) -ethylZ-oxa-oolidine (0.01 eq., 6.09 g) is dissolved in xylene (9.0 g and DDE (0.01 gsp, 3.00 g) is added.  After mixing, a wet film 10 Ml l thick is applied to the glass plate and allowed to curl at room temperature (the time until disappearance of NLH 90 NWH, turbid film, swelling in 2-ethoxyethylether is reduced — with glass peeling off, graphite rigidity . 6 C).  B.  Eisoxazoidin 3-goxy- (polypentylenecarbonyloxy) ethyl 3-oxa-el-dine (0.01 eq., 6.09 g) is dissolved in xylene (8. 6 g) and M, H, H-bis are added to the solution (b-cyocyanatohexasteylene -biuret (0.01 eq., 2.50 g. After mixing, a 10 mn tolcine raw film is applied to the glass plate and allowed The slide is called at room temperature (the time until the disappearance of the tackiness is 15 minutes, a transparent film, the swelling in 2-ethoxy ethyl acetate is very slight, the hardness of graphite is 6B), B.  3-Goxy- (polypentylenecarbonyloxy) -ethyl3-oxazolidine (0.01 eq., 6.09 g) is dissolved in xylene (7.0 g) and toluene diisocyanate (0.01 eq, 0.9 g) is added.  After mixing, a 10-mil-thick wet film is applied to the glass plate and allowed to curl at room temperature (60 minutes of tack-free tackiness, turbid film, slight swelling in 2-ethoxy ethyl acetate).  G.  3- Oxy- (polypentylenecarbonyloxy) -ethyl-oxazolidine (O,. 28 masses, 515.4 r) j is heated to 80 ° C and 4,4-methylenebis (cyclohexyl isocyanate) (0.14 mol, 36.7 g) is added.  The mixture is heated exothermically to 92 ° C and maintained at 95-100 ° C for 30 minutes until the reaction is complete.  At room temperature, this isocyanate combined with bisoxazolidine forms a waxy substance (calculated molecular weight 3916, equivalent weight in reaction with the isocyanate of 979 g-eq).  This product is mixed with xylene and various di- and polyisocyanates and the preparation of vulcanizing in the presence of moisture coatings.  PRI im p 5.  Synthesis of 3-goxy- (polypentylenecarbonyloxy) -ethyl7 -2-isopropyloxazoliphyl ().  In a flask equipped with a stirrer, a funnel for the introduction of reagents, a heater, a reflux condenser and a device for automatic temperature control, 2-isopropyl-1-hydroxyethyl-oxazolidine (IPOK) is placed in the form of an 82.3% solution in xylene (1.50 kül, 289.8 g) and BurtSnO (0.25% of the total amount of polyester, 2.73 g).  The contents of the flask are heated to 125 ° C and 6-caprolactone (7.5 mol, 855.0 g) is introduced in 60 minutes.  After the introduction of the latter is complete, the reaction mixture is maintained for 2 hours until completion of the reaction.  The resulting product, 3- {pxy- (polypentylenecarbonyloxy) -ethyl -2-isopropyloxazolidine (), in the heated state is well form, a waxy substance is formed when cooled to room temperature (calculated weight {1st weight 730, dry residue 95 , 2%, equivalent weight in reaction with isocyanate 255).  BUT.  3-Grksi- (polypentylenecarbonylrksi) -ethid3-2-isopropyl oxazolidine () (0.01 eq., 2.55 g) is dissolved in xylene (5.1 g) and M, N, m-bks (6 -isocyanatohexamethylene) -biuret (0.01 sqv, 2.50 g).  After mixing, a 10-mi-thick wet film is applied to the glass plate and is given the opportunity to curl an ovat at room temperature (60 minutes of tack-free tackiness, a transparent film, the swelling in 2-ethoxy ethyl acetate is very low, the hardness of graphite F).  B.  3-Goxy- (polypentylenecarbonyl oxy) -ethyl -2-isopropyl oxazolidine (M 730) (0.01 eq., 2.55 g) is dissolved in xylene (3.9 g) and 4,4-methylenebis cyclohexyl isocyanate is added to the solution (0.01 eq, 1.31 g).  After mixing, a 10-mil-thick wet film is applied to the glass plate and allowed to curl at room temperature (120 minutes of tack-free tackiness, transparent film, slight swelling in 2-ethyl acetate, graphite hardness F).  In 3-goxy- (polypentylenecarbonyloxy) -ethyl-iopropyloxazolidine (M, 730) (0.716 mol, 547.5 g), it is heated until then 4,4-methylenebis (cyclohexyl-.  isocyanate) (O, 358 mol, 93.8 g).  The mixture is heated before and then allowed to cool until stirred.  within 30 min.  At room temperature, this isocyanate, combined with bisoxazolidine, is a waxy substance (calculated molecular weight 1720, dry residue 96.0%, equivalent weight in reaction with isocyanates 448). To obtain coatings that cure in the presence of moisture coatings and adhesives, the resulting product mixed with xylene and various di- and polyisocyanates.  G.  3-Goxy- (polypentylenecarbonyloxy) -ethyl -2-isopropyl-oxazolidine () (0.75 mol, 573, 8 g) is heated to 80 ° C and then N, N, N-bis (6- isocyanatecocke len) -bearer (0.25 mbp, 188.0 g).  The mixture is heated exotherms to 103 s, after which it is kept under stirring for 30 minutes.  At ksmnat temperatures, this product, in combination with the bisoxazolidine polyester, slowly forms a waxy substance (calculated molecular weight 1834, dry residue 90.3%, equivalent weight in reaction with isocyanate 508 gEqv). Dp of curing in the presence of moisture coatings, this product is mixed with xylene and different from di- and poly-isocyanates.  Example  - Synthesis of 3-hydroxy- (polypentyleicarbonyloxy) -ethyl-2-isopropyl oxazolidine ().  In a flask equipped with a stirrer, a funnel for the introduction of reagents, a heater, a reflux condenser, and a device for automatic temperature control, IPOK (0.40 mol, 78.1 g), 6-caprolactone (3.2 mol, 364, 8 g) and (1% polyester, 4.14 g).  The mixture is heated to 100 ° C and maintained at it for 8 hours  In the hot state, the product obtained is liquid, but upon cooling a waxy substance is formed (calculated molecular weight 1072, dry residue 96.7%, equivalent weight in reaction with isocyanate 369).  A. 3- Hydroxy- (polypentylenecarbonyloxy) -ethyl -2-isopropyl oxazolidine (0.01 eq., 3.69 g) is dissolved in xi, lola (6.7 g) and DC is added (0.01 eq., 3.00 d).  After mixing, a 10 mils crude film is applied to the glass plate and allowed to curl at cs 1 at room temperature (time to tack free from the coating is 240 minutes, transparent film, moderate swelling in 2-ethoxyethyl acetate, graphite i hardness.  6B).  B.  3-Hydroxy- (polypentylenecarbonyloxy) -ethyl -2-isopropyl oxazolidine () (0.01 eq., 3.69 g) is dissolved in xylene / 6.2 g) and N, N, n-bis (6 -isocyanatohexamethylene) biuret (0.01 eq., 2.50 g).  After mixing, a wet film with a thickness of Yumil is applied to the glass plate and allowed to curl at room temperature (time to tack-free for 30 minutes, transparent film, swelling in 2-ethoxy ethyl acetate very little, hardness of graphite F).  B, 3-Goxy- (polypentylenecarbonyloxy) -ethyl -2-isopropyloxazolidine.  () (0.01 eq, 3.69 g) was dissolved in xylene (5.0 g) and 4,4-methylenebis (cyclohexyl isocyanate) was added (. 0.01 eq, 1.31 g).  After mixing, a 10 mils thick film is applied to the glass plate and allows it to cure to room temperature (time to tack free 120 minutes, clear film / swelling in 2-ethoxy ethyl acetate, graphite hardness F).  G.  3- Goxy- (polypentylenecarbonyloxy) -ethylZ-2-isopropyl oxazolidine (M.  1072) (0.01 eq., 3.69 g) was dissolved in xylene (4.6 g) and toluene diisocyanate (OrOl eq, 0.9 g) was added.  After mixing, a 10-mm-thick wet film is applied to the glass plate and allowed to curl at room temperature (30 minutes, transparent film, slight swelling of 2-ethoxyethylene in the tack-free layer).  Example 7  3- Hydroxy- (popibuty Lencarbonyloxy) ethyl-2-isopropyl oxazolidine ().  AT. A flask equipped with a stirrer, a wick for introducing reagents, a heater, a reflux condenser with a device for automatic temperature control is placed with IPOK (0.20 mol, 39.6 g) and (0.25% for polyester, 0.92 g).  The flask is heated to and injected over 60 times with solution of -caprolactone (2.6 mol, 296.4 g) and valerolactone (0.4 mol, 40.0 g).  When the introduction of the reagents is complete, the contents of the stake would be kept for 90 minutes at 125 ° C until the reaction is complete.  The coyab is cooled to 100 s, and then 4,4-methylenebis (cyclohexyliso-adanate (0.10 mol, 26.2 g) is introduced into it).  Due to the heat of reaction, the mixture is heated to 113 ° C, after which it is cooled for 30 minutes with a remixed wire to 100 ° C.  At an extractive temperature, this isodianate combined with oxazole, the pyrite product is a waxy vest &amp; o (calculated molecular weight 3945, dry residue 98.3%, effective weight in reaction with compaction 1005).  To obtain vulcanized in the presence of moisture, the product obtained was obtained by the product &amp; azeaate with xylene and DIFFERRED TO POLYISOTHYANTS.  BUT.  3- (E-hydroxidm cipher) -tep agidro-1, 3-oxazine-F to a glass reactor, having been removed from the cell.  with a thermometer L coidvatators 4 with a water trap, mark DI- (3-rHJEa} C4CCHnpO Q J}) - aMItH (3.0 MOL 399 g) and toluene (SOtO g).  Paraformaldegkd is weighed out (3.15 mol, purity of 90%, 105g and priVA 1/3 inlet7 c. amine solution.  By the way. the mixture is mixed with n ttaipeeeoT up to 9 0 С, while at the same time abba pp slowly the rest of the quantity of formaldehyde. guide that takes 70 min.  The mtnttAv reaction mixture with the oe / paswo fridge and extract after 4 hours o &amp; itee the amount of suction of water is 63%.   Chaan under reduced pressure.  Balance pv | Gon Utah is shaky with aatcyytM, and pesynbTa is what I get j-if Yves hydroxypropy -tragide-1,3 oxva, “6.  1H1fovulki9ukma1 with koktoeshsh 3 - 1 Oksk- (sex p9NIU ato (9eLo n oks} -prrsh | l -tetras to 1, 3-oksaeiiya to N, N, gG-tris (6-iso1-pantograph "x8 m and vi -biureta.  6 flask, equipped with Mamalkha, aaron for introduction | eagento, by the heater, the reverse Jaslo and the test and the device for automatic temperature, are e- (-hydroxypropyl) -tetrahydide o-1,3-ox ZIN (0.9 mol, 130.5 g), C - caprolone (1.8 mol, 205.2 g) and (0.75% polyester, 8.6 g).  With the flask, my flasks are heated to and alive at this temperature, T-caprolactone is added for 60 min; (7.2 mol, 820.8 g).  At the end of the administration of caprolactone, the contents of the coy are kept at 100 ° C for 6 hours before verification of the reaction.  The resulting 3-foxy- (pipylene-ene-6-oxyloxy) -propyl-7-tetrahydro-1, 3-oxazine is a liquid in the heated state, but upon cooling, a waxy mixture is formed (the calculated molecular weight is 1285, the equivalent weight in the reaction with isocyanate is 426 g-equivalent ).  In order to obtain a vulcanized material in the presence of moisture, the potential formation product is smeared with xylene.  Pr im e p9.  VisOxazine Zroxy- (polypentylenecarboxyloxy) propyl J -tetrahydro-1, 3-oxazine.  3-Grksi- (polypentylenecarbonyloxy) -npojiiuij-tetrahydro-1,3-oxazine 10, A2 mol, 539.6 g) is melted and heated until 4, 4-methylene bis (cyclohexyl isocyanate) (6.21 mol, 55.0 g).  The mixture is heated by the heat of reaction until, after which it is kept for 30 minutes at the end of the reaction. At a temperature of this temperature, this isocyanate, in combination with bis (tetrahydro-1, 3-rxazinsm), represents a waxy BentecTBo (calculated molecular weight).  weight 2832, equivalent weight per unit with isocyanate 708 haq).  In preparing for the vulcanization of the coatings in the presence of moisture coatings, this product is moistened with various di- and polyisocyanate.  As a result of treatment with 2-R (hydroxy) -ethyloxazolidine (1 mol) €.  by caprolactone in the presence of a catalyst, a correspondingly substituted 2-K-hydroxo- (polypentyleicarbovloxy} -ethyloxaolidine) is obtained, which reacts with isocyanates to form a coating.  In tab.  Table 1 shows the values of the substituents, the number of caprolactoids, the amount and type of catalyst, the temperature of the reaction time and the use of xyrocytes, as well as the molecules of the first and equivalent weights.  In this case, the following terms were used: I - d diacine based benzine with 36 atoms lost; II- 4,4-methyleibis (cyclohexylisocyanate); W - metmlenbis (4-phenyl isocyanate); IV - toluvlene diisocyanate; V «3-of schianatrmethyl-3,5,5-trimethyldncrhoxylisocyanate, Vi - H, I6is (6-nocycanohexame. Tilei) biuret; GEOC - gi-foxyethyloxazolidine, IPOK - 2-isopropylhydroxyethyloxaololidine t OK - oxazolidine; Vie, (iaiat.  .  In tab.  2 shows the properties of the compositions when using hydroxyoxazolidine functional compounds, and table.  3 - results
    obtained using Seisoxazolidine compounds.
    Oxazolidine- (6-caprolactone) -isocyanate gndovulkaniyuyuces compositions are characterized by a high content of dry residue, the duration of storage of resins, which are crosslinked in the presence of atmospheric moisture with the formation of beautiful durable, resistant to mechanical damage to the coatings, as evidenced by viscosity data, time of disappearance of paint and film-forming properties of polymers.
    The increased stability of the solution without an increase in the time to disappearance of the casting is observed in the case of bixoxazolidinomash (for example, in combination with the isocyanate) smop, anseloid results are observed when using di- and triisocyanates;
    The insal rigidity of graphite is in the range of 6B (coarsely soft) to 5B, 4B, 3V, 2B, B, HB, H, 2H, 3N, 4n, 5I, bN, and 9H (the hardest). The end of the grafit is honed on sandpaper to a flat surface. Graphite is positioned at an angle of 45 relative to the test surface, and then it is guided along.
    five
    n
    but
    H
    15
    n 5
    at
    n CH (CH-j) 2
    5 8
    CH (GH) f
    sn (sn)
    15
    CH (CH3), 1
    15
    sn (sn)
    15
    CH (CH), j
    15
    sn (sn) 2
    15 ch (cl) e
    15
    SI (sn ,,),
    15
    nosti as a nanosecond one, the characteristic is accepted as the value of the toughest graphite that does not destroy the film.
    The viscosity of Taru Kara-Khol Dta is a viscosity based on a comparison of 5 two rising bubbles. The test specimen is placed in a standard capillary viscometer. Then the sample qravnivayut with a number of standard liquids, indicated in the table in letters. The viscosity of the sample is designated as the value of the standard that has the same lifting speed as the bleach solution. The standard scale is limited to values from A-6 (the very low viscosity itself) to Z-10 (the highest is 1cc).
     comparing the abrasive resistance of Ggfdner compr ons1 based on highly oxidized oxazolidine versus bis f2- (2-isopropyl oxazolidine 1) - &amp; tyl | -adylatom reveals a pore with more cycles of stranium (for example, 200 and 100, respectively). coating composition
    Recommended for use in the electronic and chemical industry and in the construction industry.
    . -.
    table
    1468 1404
    1380
    1394
    1465
    635 V
    1 A-2 A-2 A-2 A-1 B60
    5 / GEOK
    1 A-2 A-1A-1 A-1 C 60
    8 / GEOK 1 C D E - -90 15 / GEOK
    4A 5 / IPOK A-ZA-3 A-3 A-3 A-3 240
    5A 8 / IPOK A-2 A-2 A-2 A-2 A-2 240
    5A 5 / GEOK U1 S W "- -10
    8 / GEOK
    U1TXso
    15 / GEOK
    U1e-U1DDE
    5 / IPOK
    U1MRR
    8 / IPOK
    Continued table. one
    - Unknowingly ./. Positive
    - -L6B
    Abbe
    partial and partial detachment
    - Strong 6B
    Moderate 6V
    Very non-H significant
    And -
    F
    also
    fi
    16V F
     "
    E o
    ".
    . -
    F S W NaOMe is used as a catalysts. Okhaeolidine- (e-skak) olaktok) iso-ccanate polymers (1 eq of polyester) 1 eq of isocyanate, applied from xylene with a dry residue of 50%)
    11A 9 / GEOK
    权利要求:
    Claims (2)
    [1]
    I A-4 A-2 B D 12A 8 / GEOK VI A - g
    13A 5 / GEOK
    II A-ZA-ZA-3 - A-3 The viscosity of the solution is determined {) from in 30 minutes after immersion in the atura rate. 24 h
    Continuation of table 2
    Very moderate
    is bad
    four; Zrazra-Unsigned / .6В
    real
    60 Same Very Minor F tubes in a nitrogen atmosphere. 2-hydroxyethyl acetate at room oxazolidine- (€ -caprolactone) - isocyanate polyester / 1 eq of cyanate supported from
    geok Solutions Through 30 temperature. Formula of the invention 1. Composition for coatings, including an oxazolidine compound and a polyfunctional isosdate, characterized in that, in order to increase the abrasive resistance of the coating, as an oxazolidine compound, it contains a 3-hydroxy- (oligoalkylenecarbonyloxy) alkyloxazolidine radical 9l where n - 4 or 5, Z - 5 - 15,
    45 Proerach- Moderate, fioe was placed in the viscometer tube under a nitrogen atmosphere. min after immersion in 2-hydroxyethyl acetate at room temperature Polymers (1 eq of mixed xylene with a dry residue X is alkyl, R is hydrogen or alkyl, with a ratio of oxazolidinO Btro compound and isocyanate from lijl to 3 J1).
    [2]
    2. The composition for coatings according to claim 1, distinguished by the fact that, as a polyfunctional isocyanate, it contains an adduct of an isocyanate with an oxazolidine compound. Sources of information that are taken into account in the examination 1. US patent HI 3532661 / .kl. 260-77.S, publ. 1970. 2 Accepted for Greatness of the Great Britain 1301403, cl. C 3 R, publ. 1972 (prototype).
    类似技术:
    公开号 | 公开日 | 专利标题
    US3743626A|1973-07-03|Hydrocurable oxazolidine-isocyanate compositions
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    US4474933A|1984-10-02|Crosslinking resin mixtures
    US4046744A|1977-09-06|Thermosetting coatings based on ketoxime-blocked isocyanates and oxazolidines
    US3012991A|1961-12-12|Chemical reactions
    US4101527A|1978-07-18|Moisture curing polymers prepared from polyfunctional isocyanates and a dioxazabicyclo octane
    US3281378A|1966-10-25|Diisocyanato substituted aliphatic carboxylic acid ester urethane reaction products
    SU862833A3|1981-09-07|Composition for coatings
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    US2855421A|1958-10-07|Polyisocyanates and method of preparing polyisocyanates
    US4032686A|1977-06-28|Articles coated with a cured composition of hydroxy|alkyleneoxazolidine and a polyisocyanate
    US4024117A|1977-05-17|Hydrocurable compositions of hydroxy|-alkyleneoxazolidine and an isocyanate
    US3054755A|1962-09-18|Polyurethane plastics
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    WO1983000328A1|1983-02-03|Solid blocked cross-linking agents based on |,4-cyclohexane bis|
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    US3937716A|1976-02-10|Oxazolidine derivatives
    AU611706B2|1991-06-20|Storage-stable hydrocurable oxazolidine-isocyanate compositions
    US3941753A|1976-03-02|Prepolymers of polyisocyanates with hydroxy-enamines or hydroxy-ketimines
    WO1992013907A1|1992-08-20|Thermally stable curable hindered isocyanate-oxazolidine composition
    US2797232A|1957-06-25|Hidden polyisocyanates
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    同族专利:
    公开号 | 公开日
    IL46230D0|1975-03-13|
    IL46230A|1978-08-31|
    IT1027684B|1978-12-20|
    ES450993A1|1977-08-16|
    JPS558017B2|1980-03-01|
    FR2283184A1|1976-03-26|
    FR2288756A1|1976-05-21|
    SE7415558L|1975-06-16|
    CH572950A5|1976-02-27|
    AU7582774A|1976-05-27|
    FR2288756B1|1978-02-03|
    DK652174A|1975-08-18|
    US3912691A|1975-10-14|
    ZA747675B|1976-01-28|
    GB1488160A|1977-10-05|
    DE2458588A1|1975-06-19|
    BE823338A|1975-06-13|
    ES432941A1|1977-07-01|
    CA1061349A|1979-08-28|
    JPS5089385A|1975-07-17|
    NL7416317A|1975-06-17|
    SE7806024L|1978-05-25|
    FR2283184B1|1977-11-10|
    SE7806025L|1978-05-25|
    ES450994A1|1977-08-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3743626A|1968-10-18|1973-07-03|Rohm & Haas|Hydrocurable oxazolidine-isocyanate compositions|DE2446438C2|1974-09-28|1985-04-11|Bayer Ag, 5090 Leverkusen|Process for the preparation of urethanes containing oxazolidine groups and their use|
    US4046744A|1976-07-28|1977-09-06|Rohm And Haas Company|Thermosetting coatings based on ketoxime-blocked isocyanates and oxazolidines|
    DE2922176C3|1979-05-31|1995-11-09|Akzo Gmbh|Water-curable polyisocyanate or polyepoxide mixtures|
    DE3019356A1|1980-05-21|1981-11-26|Sika AG, vorm. Kaspar Winkler & Co., 8048 Zürich|NEW ADIMIN AND OXAZOLIDING GROUPS OF COMPOUNDS AND METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS HARDENERS FOR POLYISOCYANATES|
    US4471102A|1983-11-04|1984-09-11|Textron, Inc.|Storage stable one component urethane compounds and method for making and using same|
    US4677208A|1985-08-12|1987-06-30|Akzona Incorporated|Manufacture of oxazolidines by the alkoxylation of imines|
    US4859743A|1988-06-22|1989-08-22|Ppg Industries, Inc.|Urethane component for high solids coating compositions|
    US5506328A|1993-05-24|1996-04-09|Olin Corporation|Low VOC, moisture curable, two-component coating compositions based on organic polyisocyanates|
    DE4327853A1|1993-08-19|1995-02-23|Bayer Ag|Process for the production of coatings|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US425007A|US3912691A|1973-12-14|1973-12-14|Hydrocurable compositions of hydroxy -alkyleneoxazolidine and an isocyanate|
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