POLYIMINES AND USES THEREOF

Abstract

The present invention relates to a moisture-crosslinkable sealant composition comprising: at least one polyurethane P comprising at least two NCO end functions; at least one polyimine A obtained via a process comprising a step of reaction between at least: a) a (poly)urethane-aldehyde comprising at least 2 aldehyde functions; b) a primary diamine; c) optionally in the presence of a primary monoamine or a monoaldehyde if the —CHO/NH.sub.2 molar ratio is other than 1.

Claims

1-17. (canceled)

18. A moisture-crosslinkable sealant composition comprising: at least one polyurethane P comprising at least two NCO end functions; and at least one polyimine A obtained via a process comprising a step of reaction between at least: a) a (poly)urethane-aldehyde comprising at least 2 aldehyde functions; b) a primary diamine; c) optionally in the presence of a primary monoamine or a monoaldehyde if the —CHO/NH.sub.2 molar ratio is other than 1.

19. The composition as claimed in claim 18, wherein the (poly)urethane-aldehyde a) is obtained by reaction between: at least one polyisocyanate C; and at least one hydroxyaldehyde.

20. The composition as claimed in claim 18, wherein the polyisocyanate C is selected from the group consisting of triisocyanates, diisocyanates and polyurethanes comprising at least two NCO end functions.

21. The composition as claimed in claim 18, wherein the (poly)urethane-aldehyde a) is a (poly)urethane-dialdehyde comprising an allophanate radical.

22. The composition as claimed in claim 18, wherein the polyisocyanate C is the HDI allophanate having the following formula (Y1): ##STR00048##

23. The composition as claimed in claim 18, wherein the polyisocyanate C is a polyurethane comprising at least two NCO end functions which is prepared by a process comprising a polyaddition reaction E1): i. of at least one polyisocyanate; ii. with at least one polyol, in amounts such that the NCO/OH molar ratio (r1) is strictly greater than 1; step E1) using at least one HDI allophanate, having the following formula (Y1): ##STR00049##

24. The composition as claimed in claim 18, wherein the hydroxyaldehydes have one of the following formulae: ##STR00050## ##STR00051## with R.sup.6 and R.sup.7 each representing, independently of one another, a monovalent hydrocarbon radical comprising from 1 to 12 carbon atoms, or R.sup.6 and R.sup.7 together form an aliphatic ring comprising from 4 to 12 carbon atoms, said ring being optionally substituted; R.sup.9 representing a hydrogen, a linear or branched alkyl radical, a cycloalkyl radical, an arylalkyl radical, or an alkoxycarbonyl radical comprising from 1 to 12 carbon atoms; R.sup.b represents H or a linear or branched alkyl radical comprising from 1 to 7 carbon atoms; u represents an integer ranging from 1 to 380; and t represents an integer ranging from 0 to 18. ##STR00052## wherein: t is an integer ranging from 0 to 18; u represents an integer ranging from 1 to 380; and t represents an integer ranging from 0 to 18; and R.sup.b represents H or an alkyl radical ranging from 1 to 7 carbon atoms.

25. The composition as claimed in claim 18, wherein the (poly)urethane-aldehyde a) has one of the following formulae (I) or (II): ##STR00053## wherein: R.sup.a is as defined above; R.sup.d represents the following radical: ##STR00054## wherein i is an integer ranging from 1 to 2, j is an integer ranging from 0 to 9, r is an integer ranging from 1 to 10, R represents a saturated or unsaturated, cyclic or acyclic, linear or branched, hydrocarbon chain comprising from 1 to 20 carbon atoms, and R.sup.3 represents a linear or branched divalent alkylene group having from 2 to 4 carbon atoms; R.sup.4 represents a divalent hydrocarbon radical derived from a polyol by replacement of each of the two hydroxyl groups with a free valency; v is an integer such that the number-average molecular weight of the polyether block of formula —[OR.sup.4].sub.v— ranges from 60 g/mol to 22 000 g/mol; w is an integer such that the number-average molecular weight (Mn) of the (poly)urethane-dialdehyde of formula (I) ranges from 500 g/mol to 22 000 g/mol.

26. The composition as claimed in claim 18, wherein the primary diamine is selected from the group consisting of linear or branched aliphatic amines; aliphatic polyamines; polyetheramines; polyamidoamines; dimer fatty amines; derivatives of diamino acids; amines of the following formula (B): H.sub.2N—CH.sub.2—Z—CH.sub.2—NH.sub.2 wherein Z represents a linear or branched, cyclic, aliphatic or aromatic, saturated or unsaturated divalent hydrocarbon radical, said hydrocarbon radical being optionally interrupted by one or more heteroatoms chosen from —S—, —O— and/or one or more tertiary amine divalent groups —NR′— with R′ representing a linear or branched, saturated or unsaturated alkyl group, comprising 1 to 22 carbon atoms; and mixtures thereof.

27. The composition as claimed in claim 18, wherein the —C═N— aldimine function/—NCO function molar ratio may range from 0.50 to 2.0.

28. The composition as claimed in claim 18, wherein it further comprises at least one additive selected from the group consisting of plasticizers, solvents, pigments, adhesion promoters, moisture absorbers, UV stabilizers (or antioxidants), molecular sieves, glitter, fluorescent materials, rheological additives, fillers, and mixtures thereof.

29. A polyimine A obtained via a process comprising a step of reaction between at least: a) a (poly)urethane-aldehyde comprising at least 2 aldehyde functions; b) a primary diamine; c) optionally in the presence of a primary monoamine or a monoaldehyde if the —CHO/NH.sub.2 molar ratio is other than 1; wherein said (poly)urethane-aldehyde a) is a (poly)urethane-dialdehyde comprising an allophanate radical.

30. The polyimine A as claimed in claim 29, wherein the (poly)urethane-dialdehyde is obtained by reaction between: at least one polyisocyanate C comprising at least one allophanate radical; and at least one hydroxyaldehyde.

31. The polyimine A as claimed in claim 30, wherein the (poly)urethane-dialdehyde is obtained by reaction between: at least one polyisocyanate C comprising at least one allophanate radical; and at least one hydroxyaldehyde; in amounts such that the NCO/OH molar ratio (r2) ranges from 0.95 to 1.05.

32. The polyimine as claimed in claim 30, wherein the polyisocyanate C is the HDI allophanate having the following formula (Y1): ##STR00055##

33. The polyimine as claimed in claim 29, wherein the polyisocyanate C is a polyurethane comprising at least two NCO end functions which is prepared by a process comprising a polyaddition reaction E1): i. of at least one polyisocyanate; ii. with at least one polyol, in amounts such that the NCO/OH molar ratio (r1) is strictly greater than 1; step E1) using at least one HDI allophanate, having the following formula (Y1): ##STR00056##

34. The polyimine A as claimed in claim 29, wherein the (poly)urethane-aldehyde a) has one of the following formulae (I) or (II): ##STR00057## wherein: R.sup.a is as defined above; R.sup.d represents the following radical: ##STR00058## wherein i is an integer ranging from 1 to 2, j is an integer ranging from 0 to 9, r is an integer ranging from 1 to 10, R represents a saturated or unsaturated, cyclic or acyclic, linear or branched, hydrocarbon chain comprising from 1 to 20 carbon atoms, and R.sup.3 represents a linear or branched divalent alkylene group having from 2 to 4 carbon atoms; R.sup.4 represents a divalent hydrocarbon radical derived from a polyol by replacement of each of the two hydroxyl groups with a free valency; v is an integer such that the number-average molecular weight of the polyether block of formula —[OR.sup.4].sub.v— ranges from 60 g/mol to 22 000 g/mol; w is an integer such that the number-average molecular weight (Mn) of the (poly)urethane-dialdehyde of formula (I) ranges from 500 g/mol to 22 000 g/mol.

Description

EXAMPLES

[0343] The following ingredients were used: [0344] Tolonate™ X FLO 100 available from Vencorex: allophanate of HDI and of fatty alcohol ethoxylate having a weight content of NCO groups of 12.3±1.0%; [0345] 2,2-dimethyl-3-hydroxypropanal or hydroxypivalaldehyde (CAS number: 597-31-9) available from Biosynth; [0346] 5-(hydroxymethyl)furfural (CAS number: 67-47-0) available from Purac Bioquimica; [0347] Desmophen 4042 BT available from Covestro: PPG triol having a number-average molar mass in the vicinity of 3700 g/mol (OHN=43-46 mg KOH/g); [0348] Voranol 2000 L available from Dow: PPG diol having a number-average molar mass in the vicinity of 2000 g/mol (OHN=53.5-57.5 mg KOH/g); [0349] Voranol 1000 L available from Dow: PPG diol having a number-average molar mass in the vicinity of 1000 g/mol (OHN=106-114 mg KOH/g); [0350] Voranol P 400 available from Dow: PPG diol having a number-average molecular weight in the vicinity of 430 g/mol (OHN=250-270 mg KOH/g); [0351] Desmodur T 100 available from: 2,4′-TDI having a weight content of NCO groups 48.0% by weight; [0352] DOTL available from TIB Chemicals: dioctyltin dilaurate; [0353] xylene available from Sigma-Aldrich; [0354] Jeffamine® D-400 available from Huntsman with a number average molecular weight (Mn) in the vicinity of 450 g/mol (primary alkalinity=4.1-4.7 meq/g).

Example 1—Synthesis of Urethane-Dialdehyde Based on NCO-Terminated Allophanate/2,2-dimethyl-3-hydroxypropanal U1

[0355] The following urethane-dialdehyde was synthesized according to the procedure described in U.S. Pat. No. 3,392,148 or JP 2015,064,998 by reacting 1 mol of Tolonate X-FLO 100 having an NCO weight content of 12.3% (polyisocyanate C) with 2 mol of 2,2-dimethyl-3-hydroxypropanal. The following urethane-dialdehyde U1 is obtained quantitatively, having a molar mass of 884 g/mol and 2.26 meq/g of aldehyde function.

##STR00045##

Example 2—Synthesis of Urethane-Dialdehyde Based on NCO-Terminated Allophanate/5-(hydroxymethyl)furfural U2

[0356] The following urethane-dialdehyde U2 was synthesized according to the procedure described in U.S. Pat. No. 3,392,148 or JP 2015,064,998 by reacting 1 mol of Tolonate X-FLO 100 having an NCO weight content of 12.3% (polyisocyanate C) with 2 mol of 5-(hydroxymethyl)furfural (NCO/OH molar ratio=1). The urethane-dialdehyde U2 is obtained quantitatively, having a molar mass of 933 g/mol and 2.14 meq/g of aldehyde function.

##STR00046##

Example 3—Synthesis of Polyurethane-Dialdehyde Based on NCO-Terminated Polyurethane/5-(hydroxymethyl)furfural U3

[0357] The polyurethane-dialdehyde U3 was synthesized in 2 steps.

Step 1—Synthesis of the Terminated NCO-Terminated Polyurethane

[0358] An NCO-terminated polyurethane was prepared by mixing the ingredients indicated in the table below at a temperature below or equal to 95° C. under anhydrous conditions. The amounts indicated in the table below are expressed as percentages by weight relative to the total weight of the NCO-terminated polyurethane solution.

TABLE-US-00001 Ingredients PPG diol having a number-average molar mass of 25.1 430 g/mol: Voranol P 400 Allophanate of HDI and of fatty alcohol ethoxylate 59.7 (% NCO = 12.3% by weight): Tolonate ™ X-FLO 100 Catalyst (DOTL) 0.012 Toluene 15.2 NCO/OH molar ratio 1.5 Final % by weight of NCO 3.0

[0359] In the above table, the final % by weight of NCO corresponds to the amount of NCO functions in the NCO-terminated polyurethane solution at the end of the polyurethane preparation reaction, expressed relative to the total weight of the NCO-terminated polyurethane solution.

Step 2—Synthesis of the Polyurethane-Dialdehyde

[0360] The polyurethane-dialdehyde U3 was synthesized quantitatively according to the procedure described in U.S. Pat. No. 3,392,148 by reacting 1 mol of the NCO-terminated polyurethane from step 1 with 2 mol of 5-(hydroxymethyl)furfural (NCO/OH molar ratio=1). The polyurethane-dialdehyde U3 is obtained quantitatively, having a molar mass of 3092 g/mol and 0.65 meq/g of aldehyde function.

##STR00047##

Example 4—Synthesis of the Polyimines

[0361] In a reactor equipped with a stirrer and a Dean-Stark apparatus, 1 mol of (poly)urethane-dialdehyde (example 1, 2 or 3), 1 mmol of formic acid and then the primary diamine (e.g. Jeffamine® D-400 available from Huntsman) in an amount such that the —CHO/—NH.sub.2 molar ratio >1 makes it possible to obtain a polyimine having a desired number-average molecular weight (Mn), are dissolved in 500 ml of toluene under an inert atmosphere (nitrogen). The mixture is heated and maintained at reflux for around 6 hours until no more water is removed by azeotropic distillation, and then the toluene is removed by distillation under reduced pressure (1 mmHg). The polyimines (11), (12) and (13) are obtained with a quantitative yield. Depending on the viscosity of the polyimines obtained, it is possible to dilute the polyimines in xylene to a solids content of 85%.

[0362] A —CHO/—NH.sub.2 molar ratio of 1.1 was used for the synthesis of the polyimines. The characteristics of the polyimines obtained have been grouped together in the following table:

TABLE-US-00002 I1 I2 I3 (poly)urethane-dialdehyde Example 1 Example 2 Example 3 Number-average molecular 2773 2881 7630 weight (Mn) in g/mol Content of C = N functions 1.44 1.39 0.52 in meq/g

Example 5: Application Test

Preparation of the NCO-Terminated Polyurethane P1

[0363] The non-limiting example of NCO-terminated polyurethane P used in the reference example outside the invention (without aldimine) and in examples C1 to C3 according to the invention (with aldimines according to the invention) was prepared by mixing the ingredients indicated in the following table at a temperature below or equal to 95° C. under anhydrous conditions. The amounts indicated in the table below are expressed as percentages by weight relative to the total weight of the polyurethane composition of each of the examples.

TABLE-US-00003 Ingredients P1 PPG triol having a number-average molar mass of 3700 38.3 g/mol (OHN = 44.5 mg KOH/g): Desmophen 4042 BT PPG diol having a number-average molar mass of 2000 36.9 g/mol: Voranol 2000 L 2,4′-TDI (% NCO ≥ 48.0% by weight): Desdomur T 100 9.6 Catalyst (DOTL) 0.012 Xylene 15.2 NCO/OH molar ratio 1.6 Final % by weight of NCO 1.8

[0364] In the above table, the final % by weight of NCO corresponds to the amount of NCO functions in the polyurethane solution P1 at the end of the polyurethane preparation reaction, expressed relative to the total weight of the polyurethane solution.

Preparation of Sealant Compositions

[0365] Sealant compositions were then formulated from the NCO-terminated polyurethane P1 prepared in accordance with the above process.

[0366] The reference sealant composition outside the invention (without aldimine) and the sealant compositions C1 to C3 according to the invention (with polyimines according to the invention) have been reported in the following table:

TABLE-US-00004 Reference C1 C2 C3 Prepolymer (P1) 19.40 17.31 17.11 17.11 Mesamoll: CAS 91082-17-6 16.90 15.27 15.27 5.22 Gel Paste CAS 77703-56-1 12.33 12.34 12.34 12.34 available from SIKA (dibutyl-4-4′- methylenedi(phenyl)urea) DIDP: diisodecyl phthalate 2.10 — — — PTSI: p-toluenesulfonyl 0.40 0.40 0.40 0.40 isocyanate IPDI 0.40 0.40 0.40 0.40 XDI 0.20 0.20 0.20 0.20 Silquest A-187 0.17 0.17 0.17 0.17 (MOMENTIVE) Tinuvin B 75 (BASF) 0.14 0.14 0.14 0.14 Xylene 1.90 1.90 1.90 1.90 PVC (Solvin 373 MC) 15.60 15.61 15.61 15.61 OMYA BSH 25.00 25.01 25.01 25.01 TiO.sub.2 4.90 4.90 4.90 4.90 Aerosil R 202 0.51 0.51 0.51 0.51 Polyimine I1 5.74 Polyimine I2 5.94 Polyimine I3 15.89 Salicylic acid 0.10 0.20 0.20 Tin catalyst 0.05 — — —

[0367] The above sealant compositions formulated from the NCO-terminated polyurethane (P1) and aldimines according to the invention compared to the reference sealant composition were characterized and the results reported in the table below:

TABLE-US-00005 Reference C1 C2 C3 Skinning time (min) 7 h 90 min 90 min 2 h Extrusion (g/min) at t.sup.0 250 300 300 200 Boeing test 0 0 0 0 Elongation at break- 500 550 550 700 Dumbbell (%) 100% Modulus- 0.55 0.58 0.55 0.50 Dumbbell (MPa) Max. modulus (MPa) 0.80 1.00 1.00 0.75 7-day stability OK OK OK OK Extrusion at t.sup.0 + 3 210 250 250 170 weeks at 40° C. (g/min) Bubbling Yes No No No

Characterization:

[0368] the skinning time was measured according to the standard ISO 291 at 23° C. and 50% relative humidity, [0369] the extrusion corresponds to the amount, in grams, of sealant which was able to be extruded per minute, under a pressure of the piston of 3 bar at 23° C. [0370] the 100% modulus - dumbbell was measured according to the NF ISO 37 standard (March 2012) with dumbbell test specimens, [0371] the max. modulus was measured according to the ISO 8339 standard, [0372] the elongation at break—dumbbell was measured according to the NF ISO 37 standard (March 2012) with dumbbell test specimens, [0373] the creep resistance has been checked according to the ASTM D2202 standard known as the “Boeing Test”. [0374] the extrusion of the sealant compositions is carried out through a 4-mm diameter extrusion nozzle under a pressure of 3 bar at 23° C. and constant humidity at the end of mixing) (t.sup.0) and 3 weeks at 40° C. after the end of mixing (t.sup.0+3 weeks) to assess their viscosity.