COMPOSITE PRODUCTS

Abstract

A method of manufacturing a composite product, comprising: applying a binder composition, notably in the form of an aqueous solution, to non or loosely assembled matter to provide resinated matter, wherein the binder composition consists of a binder composition prepared by combining reactants comprising at least 50% by dry weight reducing sugar reactant(s) and at least 5% by dry weight nitrogen-containing reactant(s); and arranging the resinated matter to provide loosely arranged resinated matter; and subjecting the loosely arranged resinated matter to heat and/or pressure to cure the binder composition and to form the composite product; wherein the nitrogen-containing reactant(s) comprise TPTA triprimary triamine(s), notably wherein the nitrogen-containing reactant(s) comprise at least 5% by dry weight of TPTA triprimary triamine(s).

Claims

1. (canceled)

2. A method of manufacturing a composite product, comprising: applying a binder composition in the form of an aqueous solution to non or loosely assembled matter to provide resinated matter, wherein the binder composition consists of a binder composition prepared by combining reactants comprising at least 50% by dry weight reducing sugar reactant(s) and at least 5% by dry weight nitrogen-containing reactant(s); and arranging the resinated matter to provide loosely arranged resinated matter; and subjecting the loosely arranged resinated matter to heat and/or pressure to cure the binder composition and to form the composite product; wherein the nitrogen-containing reactant(s) comprise at least 5% by dry weight of TPTA triprimary triamine(s), the TPTA triprimary triamine(s) being organic compound(s) having three and only three amines, each of the amines being primary amines or salts thereof, selected from: a) triprimary triamine(s) having spacer groups between each of the three primary amines which consist of carbon chains; b) triprimary triamine(s) having spacer groups between each of the three primary amines wherein each spacer group has a spacer length which is less than or equal to 12 polyvalent atoms; and c) triprimary triamine(s) having a total number of polyvalent atoms which is less than or equal to 23.

3. A method according to claim 2, wherein the reducing sugar reactant(s) comprise reducing sugar reactant(s) selected from the group consisting of xylose, dextrose, fructose and combinations thereof.

4. A method according to claim 2, wherein the TPTA triprimary triamine(s) consist of triprimary triamine(s) having spacer groups between each of the three primary amines which consist of carbon chains.

5. A method according to claim 2, wherein the nitrogen-containing reactant(s) comprise triprimary triamine(s) selected from the group consisting of triaminodecanes, triaminononanes, triaminooctanes, triaminoheptanes, triaminohexanes, triaminopentanes, and combination thereof.

6. A method according to claim 2, wherein the nitrogen-containing reactant(s) comprise 4-(aminomethyl)-1,8-octanediamine.

7. A method according to claim 2, wherein the binder composition consists of a binder composition prepared by combining reactants consisting of between 60% and 95% by dry weight reducing sugar reactant(s) and between 5% and 40% by dry weight nitrogen-containing reactant(s).

8. A method according to claim 2, wherein the nitrogen-containing reactant(s) comprise at least 95 wt % of TPTA triprimary triamine(s).

9. A method according to claim 2, wherein the nitrogen-containing reactants comprise reactant(s) different from the TPTA triprimary triamine(s) selected from the group consisting of 1,6-diaminohexane, 1,5-diamino-2-methylpentane, and combinations thereof.

10. A method according to claim 2, wherein the nitrogen-containing reactants comprise reactant(s) different from the TPTA triprimary triamine(s) selected from the group consisting of ammonium sulfate, ammonium phosphate, ammonium citrate, and combinations thereof (Previously presented) A method according to claim 2, wherein the aqueous binder composition is prepared by combining all the reducing sugar reactant(s) and all the nitrogen-containing reactant(s) in a single preparation step.

12. A method according to claim 2, wherein the aqueous binder composition is prepared by combining all of the reducing sugar reactant(s) with a first portion of the nitrogen-containing reactant(s) to provide an intermediate binder composition comprising reaction products of the reducing sugar reactant(s) and the first portion of the nitrogen-containing reactant(s), storing the intermediate binder composition; and combining the intermediate binder composition with a second portion of the nitrogen-containing reactant(s) to provide the binder composition.

13. A method according to claim 2, wherein the composite mineral fiber product is a mineral fiber insulation product.

14. A method according to claim 2, wherein the composite mineral fiber product is a mineral fiber veil.

15. A method according to claim 2, wherein, in the form in which it is applied to the non or loosely assembled matter, the binder composition consists essentially of curable reaction product(s) of the reducing sugar reactant(s) and the nitrogen-containing reactant(s).

16. A method according to claim 2, wherein the composite product is a composite mineral fiber product selected from a non-woven veil, glass wool insulation and stone wool insulation and wherein the matter is mineral fibers.

Description

[0128] Examples made on mineral fiber veil are representative of improved properties obtained with TPTA triprimary amine(s) for composite products, notably glass wool insulation and stone wool insulation products.

EXAMPLE 1

Laboratory Indication of Cure Speed with HFCS

[0129] The following binder compositions were prepared by combining a nitrogen containing reactant and a reducing sugar reactant:

TABLE-US-00001 Binder % dry composition nitrogen containing reactant weight Notes 1a AMOD (4-(aminomethyl)-1, 22.5% a TPTA 8-octanediamine triprimary triamine 1b TAPA (tris(3-aminopropyl)amine) 24.0% a triprimary tetramine 1c TAEA (tris(2-aminoethyl)amine) 19.7% a triprimary tetramine
The nitrogen containing reactants of binder compositions 1b and 1c are not TPTA triprimary triamines and thus provide comparative examples. Each of the binder compositions was prepared by combining the nitrogen containing reactant with HFCS 42 (high fructose corn syrup with 42% fructose+52% dextrose+trace quantities of other saccharides) in water to obtain a solution/dispersion containing 1 molar equivalent of triprimary polyamine to 3.31 molar equivalents of reducing sugars. The amounts of triprimary polyamines used in the binder compositions are expressed above and in FIG. 1 as dry weight % (the remaining dry weight being the HFCS 42) and the binder compositions were prepared at 22.5% total solids weight. Each binder composition was formulated to give a primary amine to carbonyl molar ratio on 1:1.105. FIG. 1 shows the light absorbance of leachates from glass fiber filters: drops of the binder compositions were applied to the glass fiber filters which were then were placed in an oven at 107° C. and subsequently removed after set time intervals. Brown polymers were formed on the filters, then dissolved in water and the absorbance of the leachate measured using a spectrophotometer. The evolution of the formation of soluble brown polymers and insoluble polymers provides an initial laboratory indication of curing and cure speed for these type of binders.

[0130] FIG. 1 shows that binder composition 1a using AMOD (4-(aminomethyl)-1,8-octanediamine, a TPTA triprimary triamine) shows a faster curing rate compared to binder composition 1b using TAPA (tris(3-aminopropyl)amine) and binder composition 1c using TAEA (tris(2-aminoethyl)amine) which are both triprimary tetramines.

EXAMPLE 2

[0131] Examples of binder compositions tested on mineral fiber veils are shown in Table 1 with their respective mean dry veil tensile strengths and mean wet tensile strengths.

[0132] In each case, a nitrogen containing reactant comprising a triprimary polyamine was combined with HFCS 42 (high fructose corn syrup with 42% fructose+52% dextrose+trace quantities of other saccharides) in water to obtain a solution/dispersion containing 1 molar equivalent of triprimary polyamine to 3.31 molar equivalent of reducing sugars. The amounts of triprimary polyamines used in the binder compositions are expressed in Table 1 as dry weight %, the remaining dry weight being the HFCS, and the binder compositions were prepared at 2% weight (bake out solids). Once the binder compositions were prepared, they were applied to A4 size glass veil and the glass veils were cured to obtain a quantity of cured binder in the final product of 10% LOI (loss on ignition).

[0133] Measurement of Dry Glass Veil Tensile Strength:

[0134] 8 pieces of cured glass veil with a dimension of 14.8 cm×5.2 cm were cut from the cured A4 size veil and subjected to tensile testing by attaching a 50 Kg load cell using glass veil tensile plates on a testometric machine (TESTOMETRIC M350-10CT). The average of the total force in Newtons of the breaking strength is given in the table below. For the measurement of wet glass veil tensile strength, the veil samples are tested wet after being immersed in water at 80° C. for 10 minutes.

[0135] The column of wet strength % gives the % of mean wet tensile strength with respect to the % mean dry tensile strength.

TABLE-US-00002 TABLE 1 Triprimary Mean Mean polyamine dry tensile wet tensile wet (% dry weight) strength (N) strength (N) strength % TAEA (19.7%) 73.5 25.3 31.7% TAPA (24.0%) 80.9 31.4 38.8% AMOD (22.5%) 75.3 41.4 55.0%

[0136] The results show that all the triprimary polyamines give good dry tensile strengths with TAPA giving a slightly better dry tensile strength compared to AMOD and TAEA. In regard of the wet tensile strengths, AMOD show better results compared to TAPA and TAEA. It is unexpected that the wet strength for AMOD was 55% of the value of the dry tensile strength while for TAPA it was only of 38.8%.

EXAMPLE 3

[0137] Examples of a binder composition for mineral fiber insulation products A binder composition was prepared by combining reactants consisting of 90 parts by weight dextrose monohydrate and 10 parts by dry weight nitrogen-containing reactant where the nitrogen-containing reactant was 4-(aminomethyl)-1,8-octanediamine. This binder composition was suitable for providing appropriate properties when used as a binder composition for mineral wool insulation.

EXAMPLE 4

Examples of Binder Composition for Mineral Fiber Veils are Shown in Table 2

[0138]

TABLE-US-00003 TABLE 2 Test Ref Binder composition (% dry weight) A 77.5% HFCS + 13.5% AMOD + 9% AS B 77.5% HFCS + 9% AMOD + 13.5% AS C 77.5% HFCS + 11.25% AMOD + 11.25% AS D 77.5% HFCS + 22.5% AMOD E 77.5% HFCS + 22.5% AS F 85% HFCS + 10% AMOD + 5% AS with an additional 0.3% silane

[0139] Key: HFCS=high fructose corn syrup; AS=ammonium sulphate; AMOD=4-(aminomethyl)-1,8-octanediamine

[0140] Binder composition E is a comparative example of binder composition with ammonium sulfate (AS).

[0141] Binder composition D showed a higher dry tensile strength than binder composition E. Each of binder compositions A, B and C showed a higher dry tensile strength than binder compositions D.

[0142] Binder composition F showed a particularly good wet tensile strength; it is currently believed that the silane additive contributes significantly to this good wet tensile strength.

EXAMPLE 5

[0143] Examples of binder composition tested on mineral fiber veils are shown in Table 3 with the respective mean dry veil tensile strengths:

[0144] In each test, the nitrogen-containing reactant(s) were mixed with glucose in water. The amounts of the reactants used in the binder compositions are expressed in Table 3 as dry weight % and the binder compositions were prepared at 2% solids weight (bake out solids). Once the binder compositions were prepared, they were applied to glass veil which were cured to obtain a quantity of cured binder in the cured veil of 10% LOI (loss on ignition). The dry tensile strength is measured in the same way as described in example 2.

TABLE-US-00004 TABLE 3 Mean dry tensile Test Ref Binder composition (% dry weight) strength (N) G (comparative) 85% Glu + 15% DAP 76.5 H (comparative) 85% Glu + 15% AS 73.5 I (comparative) 85% Glu + 15% TriCA 93.0 J 85% Glu + 15% AMOD 81.0 K 85% Glu + 5% AMOD + 10% DAP 80.0 L 85% Glu + 7.5% AMOD + 7.5% DAP 80.2 M 85% Glu + 10% AMOD + 5% DAP 82.4 N 85% Glu + 5% AMOD + 10% AS 84.7 O 85% Glu + 7.5% AMOD + 7.5% AS 90.0 P 85% Glu + 10% AMOD + 5% AS 88.6 Q 85% Glu + 5% AMOD + 10% TriCa 88.0 R 85% Glu + 7.5% AMOD + 7.5% TriCA 91.4 S 85% Glu + 10% AMOD + 5% TriCA 87.9

[0145] Key: Glu=glucose; AS=ammonium sulphate; DAP=diammonium phosphate; TriCA=triammonium citrate; AMOD=4-(aminomethyl)-1,8-octanediamine

[0146] Binder compositions G, H and I are comparative examples of binder compositions with respectively only diammonium phosphate (DAP), ammonium sulfate (AS), and triammonium citrate (TriCa) as nitrogen-containing reactant. Binder composition J is a binder composition wherein the nitrogen-containing reactant consists of AMOD.

[0147] In examples K, L and M, the nitrogen-containing reactants consist of AMOD and DAP in different proportions. Examples J, K, L and M shows that similar levels of dry tensile strength are achieved for each of these binder compositions.

[0148] In examples N, O and P, the nitrogen-containing reactants consist of AMOD and AS in different proportions. The binder compositions N, O and P present higher dry tensile strengths compared to the result obtained with the binder composition J. Binder composition O seems to present an optimum result compared to binder compositions N and P. It is believed that there is a synergistic effect of the presence of AS and AMOD as the nitrogen-containing reactants.

[0149] FIG. 3 illustrates a TPTA triprimary triamine having three primary amines A, B, D with spacer groups which consist of carbon chains between each of its three primary amines. Each carbon atom is numbered to facilitate the explanation below.

[0150] The spacer group between primary amines A and B: [0151] has a spacer length of 7, ie carbon atoms 1, 2, 3, 4, 5, 6, 7 which together form the shortest chain of covalently bonded polyvalent atoms between primary amines A and B (the carbon atoms of the two branched chains 8, 9 and 10, 11 do not form part of the spacer length; [0152] has 11 polyvalent atoms, ie carbon atoms 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11(the carbon atoms 12, 13, 14, 15, 16 do not form part of the spacer group between A and B as they form a chain which connects the third primary amine D to the molecule).

[0153] The spacer group between primary amines A and D: [0154] has a spacer length of 10, ie carbon atoms 1, 2, 3, 4, 5, 12, 13, 14, 15, 16; [0155] has 14 polyvalent atoms, ie carbon atoms 1, 2, 3, 4, 5, 8, 9, 10, 11, 12, 13, 14, 15, 16.

[0156] The spacer group between primary amines B and D: [0157] has a spacer length of 8, ie carbon atoms 7, 6, 5, 12, 13, 14, 15, 16; [0158] has 10 polyvalent atoms, ie carbon atoms 7, 6, 5, 12, 13, 14, 15, 16, 10, 11 (the chain of carbon atoms 4, 3, 2, 1, 8, 9 does not form part of the spacer group between B and D as this form a chain which connects the other primary amine A to the molecule.

[0159] The total number of polyvalent atoms in the molecule is 19, i.e. carbon atoms 1 to 16 and the 3 nitrogen atoms of the 3 primary amines A, B and D.