HYDROXY AMINO POLYMER AND USE THEREOF IN POLYUREA/POLYURETHANE TISSUE ADHESIVES

Abstract

The present invention relates to a process for producing a hydroxy amino polymer comprising the steps: a) Reaction of an H functional starter compound bearing at least one Zerewitinoff active H atom with an unsaturated, cyclical carboxylic acid anhydride and at least one alkylene oxide compound for obtaining a prepolymer bearing hydroxyl groups, b) Addition of a primary amine and/or of ammonia to the double bond(s) of the prepolymer bearing hydroxyl groups obtained according to step a) for obtaining the hydroxy amino polymer,

wherein the ratio of added amino groups to hydroxyl groups in a hydroxy amino polymer is at least 0.6. Furthermore, the invention relates to a hydroxy amino polymer, which can be achieved according to this process as well as a polyurea/polyurethane system, which contains such a hydroxy amino polymer.

Claims

1.-21. (canceled)

22. A polyurea/polyurethane system comprising an isocyanate functional prepolymer as a component A) obtained by reacting an aliphatic and/or aromatic polyisocyanate A1) with a polyol A2), which may have a number average molecular weight of 400 g/mol and an average OH functionality of 2 to 6, a hydroxy amino polymer as component B), optionally organic fillers, which may have a viscosity measured according to DIN 53019 at 23 C. in the range of 10 to 6000 mPa, as a component C), a reaction product of the isocyanate functional prepolymer according to component A) with hydroxy amino functional compounds according to component B), and/or organic fullers according to component C) potentially as component D), and optionally water and/or a tertiary amine as a component E).

23. The polyurea/polyurethane system according to claim 22, wherein the hydroxy amino polymer is obtained by: a) reacting an H functional starter compound bearing at least one Zerewitinoff active H atom with an unsaturated, cyclical carboxylic acid anhydride and at least one alkylene oxide compound for obtaining a prepolymer bearing hydroxyl groups, b) adding a primary amine and/or an ammonia to the double bond(s) of the prepolymer bearing hydroxyl groups obtained according to step a) for obtaining the hydroxy amino polymer, wherein the ratio of added amino groups to hydroxyl groups in a hydroxy amino polymer is at least 0.6.

24. The polyurea/polyurethane system according to claim 22, wherein the ratio of added amino groups to hydroxyl groups in said hydroxy amino polymer is 0.8 to 2.5, and/or wherein said hydroxy amino polymer has an OH functionality of 1.5 to 6.

25. The polyurea/polyurethane system according to claim 22, wherein said H functional starter compound has 1 to 35 Zerewitinoff active H atoms.

26. The polyurea/polyurethane system according to claim 22, wherein said unsaturated, cyclical carboxylic acid anhydride is selected from the group of unsaturated, cyclical dicarboxylic acid anhydrides, tetrahydrophthalic acid anhydride, and combinations thereof.

27. The polyurea/polyurethane system according to claim 22, wherein said alkylene oxide compound is selected from alkylene oxides with 2 to 24 carbon atoms.

28. The polyurea/polyurethane system according to claim 22, wherein a molar ratio between said alkylene oxide compound and carboxylic acid anhydride is at least 1:1.

29. The polyurea/polyurethane system according to claim 22, wherein said H functional starter compound is first reacted with an initial amount of alkylene oxide compound and then with the unsaturated, cyclical carboxylic acid anhydride and an additional amount of alkylene oxide compound.

30. The polyurea/polyurethane system according to claim 22, wherein the reaction of said H functional starter compound with said unsaturated, cyclical carboxylic acid anhydride and/or the addition of said alkylene oxide compound is performed using a double metal cyanide catalyst (DMC catalyst), wherein said DMC catalyst contains zinc hexacyanocobaltate (III), zinc hexacyanoiridate (III), zinc hexacyanoferrate (III), and/or cobalt (II) hexacyanocobaltate (III).

31. The polyurea/polyurethane system according to claim 22, wherein said H functional starter compound is first reacted with said unsaturated, cyclical carboxylic acid anhydride and subsequently with said alkylene oxide compound or wherein said H functional starter compound is simultaneously reacted with said unsaturated, cyclical carboxylic acid anhydride and said alkylene oxide compound, and/or wherein the process is conducted using an amine catalyst.

32. The polyurea/polyurethane system according to claim 22, wherein said hydroxy amino polymer comprises polyester polyol units, polyester-polyether polyol units, and/or polyether polyol units, having a share of oxyethylene units of 40 to 90% by weight, wherein said hydroxy amino polymer preferably has a general formula (I) ##STR00008## wherein starter represents the radical of the H functional starter compound, A represents an aspartate group of the following structure of formulas (IIa) or (IIb) ##STR00009## in which R1 represent hydrogen or an aliphatic, cycloaliphatic or aromatic radical, which may also contain heteroatoms, particularly nitrogen atoms or oxygen atoms as well as hydroxyl groups, R2 and R3 independently represent hydrogen or an aliphatic or aromatic radical and R2 and R3 may also be a component of a cycloaliphatic ring system, R4, R5, R6, and R7 independently represent hydrogen or an aliphatic or aromatic radical and R5 and R6 may also be a component of a cycloaliphatic ring system, 1 corresponds to the number of Zerewitinoff active hydrogen atoms of the H functional starter compound, m, n, and o are independently whole numbers, wherein n, o =0 or >1 and m >1, and n, m are preferably 1 to 430, particularly 2 to 430, preferably 4 to 430, o is preferably 1 to 100, particularly 1 to 50 and preferably 1 to 10, and the ratio of o to 1 in the medium is at least 0.6 and wherein the equivalent molar mass of a structure shown in formula I does not exceed the value of 18900 g/mol.

33. The polyurea/polyurethane system according to claim 22, wherein said polyol A2) contains polyester polyol and/or polyester-polyether polyol and/or polyether polyol.

34. The polyurea/polyurethane system according to claim 22, wherein said prepolymer A) has an average NCO functionality of 1.5 to 6.

35. The polyurea/polyurethane system according to claim 22, wherein a trifunctional polyol is used for producing component A.

36. The polyurea/polyurethane system according to claim 22, wherein said organic fillers of component C) are hydroxy functional compounds.

37. The polyurea/polyurethane system according to claim 22, wherein a component E) contains a tertiary amine of a general formula (IX), ##STR00010## in which R.sub.8,R.sub.9, and R.sub.10 may independently be alkyl or heteroalkyl radicals having heteroatoms in an alkyl chain or at their ends, or R.sub.8 and R.sub.9 can form an aliphatic, unsaturated or aromatic heterocycle together with a nitrogen atom bearing them, which may potentially contain additional heteroatoms.

38. The polyurea/polyurethane system according to claim 22, wherein said tertiary amine is selected from the group consisting of triethanolamine, tetrakis (2-hydroxyethyl) ethylenediamine, N,N-dimethyl-2-(4-methylpiperazine-1-yl)ethanamine, and 2-{[2-(dimethylamino)ethyl] (methyl) amino} ethanol, 3,3,3-(1,3,5-triazinane-1,3,5-triyetris(N,N-dimethyl-propane-1-amine).

39. The polyurea/polyurethane system according to claim 22, wherein said component E) contains 0.2 to 2.0% by weight of water and/or 0.1 to 1.0% by weight of said tertiary amine.

40. A dispensing system having two chambers for the polyurea/polyurethane system according to claim 22, wherein said component A) is contained in one chamber and said component B) and optionally components C), D), and E) of said polyurea/polyurethane system are contained in another chamber.

Description

EXAMPLE 1: PRODUCING A TRIFUNCTIONAL HYDROXY AMINO POLYMER

[0274] 650 g (0.146 mol) of a trifunctional, glycerin-started polyether polyol were presented in a 1 1 laboratory autoclave in a nitrogen atmosphere with an ethylene oxide/propylene oxide ratio of 73/27 (w/w) and OH value=37.9 mg KOH/g (molar mass 4440 g/mol) and then heated to 60 C. At this temperature, 41.8 g (0.426 mol) of maleic acid anhydride and 0.73 g of N-methyldiethanolamine were added and then stirred for 60 minutes at 60 C. Subsequently, it was heated to 90 C.; 77.4 g (1.756 mol) of ethylene oxide were dispensed in the autoclaves at this temperature within 30 minutes and then subsequently reacted at this temperature for 5 hours. Volatile components were baked out in the vacuum at 90 C. for 60 minutes and the reaction was then cooled to room temperature.

[0275] A preliminary product is obtained having an OH value of 35.5 mg KOH/g and an acid value of 0.12 mg KOH/g.

[0276] Michael Addition of Pentylamine:

[0277] 0.65 g (3 equivalents) of pentylamine was added to 11.85 g of the preliminary product. The reaction mixture was stirred for 6 hours at 60 C. in the heating block. Potentially surplus amine was then removed in the high-vacuum.

[0278] The following amines were reacted nnalogouslv:

TABLE-US-00001 TABLE 1 Weight of the Hydroxy amino Amine for Michael addition amine sample polymer N-pentylamine 0.63 g 2 N-propylamine 0.44 g 3 N-butylamine 0.54 g 4 N-hexylamine 0.76 g 5 N-decylamine 1.16 g 6 3-Methoxypropane-1-amine 0.66 g 7 Cyclopentylamine 0.63 g 8 2-(morpholine-4-yl)ethanamine 0.96 g 9

[0279] The compounds listed in Table 1 are hydroxy amino polymers pursuant to the invention. They will be reacted with a trifunctional NCO-terminated prepolymer in the following. The production of the trifunctional NCO-terminated prepolymer is performed as follows:

[0280] Production of a Trifunctional NCO-Terminated Prepolymer

[0281] 465 g of HDI and 2.35 g of benzoyl chloride were presented in a 1 1 four-neck flask. 931.8 g of a trifunctional polyether of a molar mass of 4500, started on glycerin and an ethylene oxide content of 71% and a propylene oxide content of 29%, respectively related to the overall alkylene oxide content, were added within 2 hours at 80 C. and subsequently stirred for 1 hour. The surplus HDI was then distilled off through thin film distillation at 130 C. and 0.13 mbar. 980 g (71%) of the prepolymer is obtained with an NCO content of 2.37% and a viscosity of 4500 mPa/23 C. The residual monomer content was <0.03% HDI.

[0282] Tissue Adhesive

[0283] 2.08 g (1 equivalent) of hydroxy amino polymer 2 were added to 2 g of the trifunctional NCO-terminated prepolymer and stirred well in a cup for 20 seconds. A thin layer of the polyurea/polyurethane system was then directly applied to the muscle tissue to be bonded. The time during which the adhesive system still had a low viscosity was determined as the processing time, such that it could be applied to the tissue without difficulty.

[0284] The time, after which the polyurea/polyurethane system was no longer tacky (tack free time) was measured through bonding tests with a glass rod. In doing so, the glass rod was touched to the layer from the polyurea/polyurethane system. If it no longer remained bonded, the system was considered to be tack free. In addition, the bonding strength was determined, in which the ends of two pieces of muscle tissue (1=4 cm, h=0.3 cm, b=1 cm) were coated with the polyurea/polyurethane system 1 cm apart and adhered in an overlapping manner. The bonding strength of the polyurea/polyurethane system was respectively tested through tension.

[0285] The reaction of the NCO-terminated prepolymer with hydroxy amino polymers from Table 1:

TABLE-US-00002 TABLE 2 Hardening Hydroxy amino product Processing Tack free Adhesive polymer number time time strength N-pentylamine/(2) 2a 1 min. 3 min. ++ 30 seconds N-propylamine/(3) 3a 1 min. 3 min. + 20 seconds N-butylamine/(4) 4a 1 min. 3 min. ++ 30 seconds N-hexylamine/(5) 5a 1 min. 3 min. ++ 10 seconds 30 seconds N-decylamine/(6) 6a 1 min. 3 min. ++ 20 seconds 30 seconds 3-methoxypropane- 7a 1 min. 4 min. + 1-amine/(7) 10 seconds Cyclopentylamine/(8) 8a 1 min. 6 min. o 40 seconds 2-(morpholine-4-yl) 9a 1 min. 7 min. + ethanamine/(9)

[0286] The exothermic reaction of the hardening was between 23 and 25 C.

[0287] Determining the Biodegradability

[0288] The adhesive was applied to a tube (diameter: 0.5 cm, length: 2 cm) for hardening. The resulting 2.7 g heavy test sample was agitated in 10 ml of buffer solution (pH: 7.4, Aldrich: P-5368) at 60 C. or 37 C. in an agitation incubator with 150 RPM until the material was completely dissolved, i.e. without residuum.

[0289] All samples were fully degraded after 4 days at 60 C.

[0290] Measurement of Cytotoxicity of 2a

[0291] The hardened adhesive was tested for cytotoxicity according to ISO 10993-5:2009 with L 929 cells. The material proved to be non-cytotoxic.