# Patent

## Title
Pumpable shelf-stable suspension of fibers in an organic phase

## Abstract

A pumpable shelf-stable suspension of fibers in an organic phase comprising 1.0-60 wt % of fibers and 0.01-10 wt % of a disubstituted urea is proposed as well as a method using the disubstituted urea to suspend fibers in an organic phase.

## Background
This application is a §371 of International Application No. PCT/EP2014/061971 filed Jun. 10, 2014, and claims priority from European Patent Application No. 13178707.9 filed Jul. 31, 2013.
The present invention relates to a pumpable shelf-stable suspension of fibers in an organic phase and also to a method of using a disubstituted urea to suspend fibers in an organic phase.
The production of fiber-containing coatings, floorcoverings, tires, artificial leathers and the like generally requires the metered addition of fibers. Handling these fibers is often difficult. Especially when fibers are to be added to oily, hydrophobic liquids, unwelcome issues can arise because of insufficient suspendability on the part of the fibers, possibly also due to electrostatic effects, due to clumping of the fibers (known as “birdnesting”), etc. It is also the case that these kinds of fibers, in particular chopped fibers, are often difficult to convey. Batchwise addition, possibly by hand, to organic formulations in particular, by contrast, is associated with increased labor requirements and hence increased costs.
The problem addressed by the present invention was that of substantially resolving the aforementioned issues. The problem was more particularly that of providing a fiber preparation which is readily handleable, ideally conveyable mechanically and does not throw a sediment even in the course of prolonged storage. The problem addressed was more particularly that of providing the pumpable shelf-stable suspension of the present invention.
The problem is solved by the features of the independent claims. The dependent claims relate to preferred embodiments of the present invention.
It was found that, surprisingly, disubstituted ureas are able to stabilize a multiplicity of fibers permanently and in the form of a pumpable suspension.
The present invention accordingly provides in a first aspect a pumpable shelf-stable suspension of fibers in an organic phase, comprising 1.0-60 wt % of fibers, and 0.01-10 wt % of a disubstituted urea (the organic phase comprises the remainder). The suspension can additionally comprise further ingredients, in which case all percentages have to sum to 100 wt %, as will be appreciated.
Preferably, the suspension of the present invention comprises 10-60 wt %, especially 25-50 wt % of fibers.
It is further preferable for the suspension of the present invention to comprise 0.05-10 wt %, especially 0.1-5 wt % of the disubstituted urea.
For the purposes of the present invention, an “organic phase” is generally any liquid organic compound that is not miscible with water. Not miscible with water is to be understood in this context as meaning that two phases form in the organic compound/water system. More particularly, said organic compound shall have a solubility in water at 20° C. of less than 10 wt %, preferably less than 2 wt % and especially less than 1 wt %.
“Organic phase” is preferably to be understood as meaning, by contrast, a mineral oil, crude oil, paraffin oil, benzine, petroleum, naphthenic oil, aromatic oil, an aliphatic or aromatic hydrocarbon such as, for example, benzene, toluene and xylene, a fatty oil (triglyceride), a fatty acid ester such as, for example, biodiesel, a silicone oil, but also customary plasticizers such as, for example, various phthalate esters and hydrogenated phthalate esters. The “organic phase” can further also be a reactive component for polymer formation, for example an acrylate or an isocyanate. Mixtures of two or more of these compounds can also be used, however. Aliphatic and aromatic hydrocarbons are very particularly preferred.
“Fibers” are flexible structures which are thin compared with their length in that they have a length/diameter ratio of preferably not less than 10:1 and more preferably of not less than 100:1. Fibers suitable for the purposes of the present invention can consist of a multiplicity of different materials, for example of polyolefins comprising polyethylene and polypropylene; polyvinyl alcohol; polyacrylonitrile; polyesters comprising polyglycol adipate, polyethylene terephthalate, polylactic acid (PLA); polyamides comprising polycaprolactam, nylon 66, nylon 6T; inorganic materials comprising glass, carbon, basalt and metals; or renewable materials comprising cellulose and lignin; and mixtures thereof.
The fibers conveniently have diameters of 2 μm to 2 mm, preferably 10 μm to 100 μm, and lengths of conveniently 0.1 mm to 25 cm, preferably of 1 mm to 10 cm, subject to the proviso of an aspect ratio (length/diameter ratio) of not less than 10, preferably not less than 100. Particularly preferred chopped fibers are not more than 2.5 cm in length.
The “disubstituted urea” is obtainable from a monoisocyanate or polyisocyanate and an organic amine. The monoisocyanate conforms to the formula R1—NCO, where R1 is preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethyl-n-hexyl, n-lauryl, cyclohexyl, phenyl and benzyl. The polyisocyanate is preferably an aliphatic isocyanate, an aromatic isocyanate or a combined aliphatic-aromatic isocyanate having an NCO functionality (number of NCO groups in the molecule) from 2 to 5, preferably from 2 to 3. Suitable polyisocyanates comprise tetramethylene 1,4-diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), 2,2,4- and 2,4,4-trimethylhexamethylene 1,6-diisocyanate (TMDI), dodecamethylene 1,12-diisocyanate, lysine diisocyanate, lysine ester diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate—IPDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 2,2′-, 2,4′- and 4,4′-dicyclohexylmethane diisocyanate (H12MDI), cyclohexane 1,3-diisocyanate and cyclohexane 1,4-diisocyanate (CHDI), 1,3- and 1,4-bis(isocyanatomethyl)-cyclohexane, 4,4′-diisocyanatodicyclohexyl-2,2-propane, m- and p-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl (TOBI), 2,4- and 2,6-tolylene diisocyanate (TDI), 2,2′-, 2,4′- and 4,4′-diphenylmethane diisocyanate (MDI), naphthalene 1,2-diisocyanate and naphthalene 1,5-diisocyanate (NDI), m- and p-xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and also any desired mixtures thereof. For the purposes of the present invention, the polyisocyanates of the present invention shall also comprise dimers (uretdiones) and trimers (isocyanurates). The HDI trimer is particularly important here. Oligomers shall further also be comprehended, an example being “polymeric MDI” where n=1 to 8:




The “organic amine” is preferably an unsubstituted unbranched, branched or cyclic, saturated or olefinically mono- or polyunsaturated primary amine, preferably a primary aliphatic amine and especially a fatty amine.
The present invention has been found to work particularly well with C6-22alkylamines, especially oleylamine and this especially in combination with MDI.
The disubstituted urea obtainable by reacting the isocyanate with the organic amine is either prepared directly in the organic phase or prepared in a solvent and obtained as redissolvable powder by drying.
The present invention further provides the method of using said disubstituted urea to suspend fibers in said organic phase.
The examples which follow illustrate the invention.


EXAMPLES
Example 1: Reaction of Oleylamine with MDI
100 g of oleylamine were dissolved in 300 g of toluene. Under vigorous agitation, 46.77 g of MDI (Lupranat® MI from BASF SE—isomer mixture) were dissolved in 300 g of toluene in another vessel and gradually (the temperature rises) added to the oleylamine solution. Agitation was continued for a further 30 min before the solvent was evaporated to obtain the product as a whitish waxy powder.
Example 2: Reaction of Oleylamine with MDI
34.07 g of oleylamine were mixed with 600 g of paraffin oil (C11-25 fraction) under vigorous agitation. Under vigorous agitation, 15.93 g (Lupranat® MI from BASF SE—isomer mixture) were dissolved in 300 g of toluene in another vessel and gradually added to the oleylamine solution (slight rise in temperature). Agitation was continued for a further 30 min to obtain the product as a colorless, slightly opaque, viscous, thixotropic but nonetheless pressure-pumpable solution.
Example 3: Properties of Fiber Suspension According to the Present Invention
A suspension was prepared from 50 ml of paraffin oil (C11-25 fraction), 3.0 g of product from Example 1 and 40 g of polylactic acid fibers (about 6 mm in length, <20 μm in thickness) and stored in a screw lid jar for 3 hours or 1 week. There was no observable sedimentation of fibers. Suspension pumpability was tested using a pressure-driven cartridge press. Using a pumping pressure of 1 bar, a hole diameter of 20 mm and a cartridge diameter of 4.6 cm, an 80.1 g quantity of the suspension could be pumped within 3 seconds (26.7 g/s). No observable separation occurred during pumping.
Example 4: Various Test Series
Example 3 was repeated with different fibers, solvents and dispersants. The results are shown in table 1 (storage tests) and table 2 (pumping tests). Hand pumping was used in contrast to Example 3. It is apparent that only the disubstituted ureas of the present invention solve the problem defined at the beginning, and that oleylamine combined with MDI works best.

















TABLE 1









Amount








Test

Amount of

of
Fiber
Fiber
Stab.
Stab.
Stab.


No.
Dispersant
dispersant
Solvent
solvent
type
quantity
1 h
24 h
14 d
Comments

























1
none

paraffin oil
 50 ml
PLA, PP
10 g
no
no
no
unbrushable, separates


2
none

aromatics
 50 ml
PLA, PP
10 g
no
no
no
unbrushable, separates


3
Lutensol ® GD 70
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


4
Triton ® CG 110
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


5
Triton ® H 66
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


6
sodium dodecylsulfate
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


7
Sovermol ® 1111
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


8
Sovermol ® 920
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


9
methyl laurate
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


10
butyl acetate
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


11
BYK ® 306
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


12
Disperbyk ® 180
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


13
BYK ® W 980
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


14
DBE-IB
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


15
castor oil
1 g
aromatics
100 ml
PLA, PP
 3 g
no
no
no
unbrushable, separates


16
oleylamine-Lupranat ® MI
1 g
aromatics
100 ml
PLA
 3 g
yes
yes
yes
thickening effect, brushable


17
oleylamine-Lupranat ® MI
1 g
aromatics
100 ml
PLA
20 g
yes
yes
yes
thickening effect, brushable


18
oleylamine-Lupranat ® MI
2 g
aromatics
100 ml
PLA
10 g
yes
yes
yes
thickening effect, brushable


19
oleylamine-Lupranat ® MI
2 g
aromatics
100 ml
PLA
30 g
yes
yes
yes
thickening effect, brushable


20
oleylamine-Lupranat ® MI
4 g
aromatics
100 ml
PLA
 3 g
yes
yes
yes
thickening effect, brushable


21
oleylamine-Lupranat ® MI
4 g
aromatics
100 ml
PLA
10 g
yes
yes
yes
thickening effect, brushable


22
oleylamine-Lupranat ® MI
1 g
paraffin oil
 50 ml
PLA
20 g
yes
yes
yes
thickening effect, brushable


23
oleylamine-Lupranat ® MI
1 g
paraffin oil
 50 ml
PLA
30 g
yes
yes
yes
thickening effect, brushable


24
oleylamine-Lupranat ® MI
2 g
paraffin oil
 50 ml
PLA
20 g
yes
yes
yes
thickening effect, brushable


25
oleylamine-Lupranat ® MI
2 g
paraffin oil
 50 ml
PLA
30 g
yes
yes
yes
thickening effect, brushable


26
oleylamine-Lupranat ® MI
3 g
paraffin oil
 50 ml
PLA
40 g
yes
yes
yes
thickening effect, brushable


27
oleylamine-Lupranat ® MI
2 g
paraffin oil
 50 ml
PP
10 g
yes
yes
yes
thickening effect, brushable


28
oleylamine-Lupranat ® MI
2 g
paraffin oil
 50 ml
PVA
10 g
yes
yes
yes
thickening effect, brushable


29
oleylamine-Lupranat ® MI
2 g
paraffin oil
 50 ml
cellulose
10 g
yes
yes
yes
thickening effect, brushable


30
octadecylamine-Lupranat ® MI
5 g
paraffin oil
 50 ml
PLA, PP
20 g
yes
yes
yes
minimal sedimentation


31
ethylhexylamine-Lupranat ® MI
5 g
paraffin oil
 50 ml
PLA, PP
20 g
yes
yes
yes
minimal sedimentation


32
oleylamine-Desmodur ® N3600
3 g
paraffin oil
 50 ml
PLA, PP
10 g
yes
no
no
stable for some hours


33
tallowamine-Lupranat ® MI
3 g
paraffin oil
 50 ml
PLA, PP
10 g
yes
yes
yes
moderately thickening effect





Legend


paraffin oil: C11-25 fraction


PLA: polylactic acid fibers, about 6 mm in length, <20 μm in thickness


PLA, PP: the two fiber types were tested separately


cellulose: cellulose fibers, approximately identical dimensions


Triton ® CG 110: Dow Chemicals ® alkylpolyglucoside surfactant


Sovermol ® 1111: BASF SE-branched polyether polyol


BYK ® 306: silicone surfactant from Byk


DBE-IB: high-boiling oxygenated solvent-containing diisobutyl adipate, glutarate


and succinate mixture from Invista


Lupranat ® MI: BASF SE-MDI isomer mixture


tallowamine: aminated animal tallow (fatty amine)


aromatics: mixture of C9 aromatics


PP: polypropylene fibers, approximately identical dimensions


PVA: polyvinyl alcohol fibers, approximately ca. identical dimensions


Lutensol ® GD 70: BASF SE-alkylpolyglucoside surfactant


Triton ® H 66: Dow Chemicals-anionic phosphate polyether surfactant


Sovermol ® 920: BASF SE-branched polyether polyol


Disperbyk ® 180: dispersing additive for organic systems, from Byk


BYK ® W 980: dispersing additive for organic resins, from Byk


Desmodur ® N 3600: Bayer AG, HDI trimer























TABLE 2









Amount


Pumped





Test

Amount of

of

Fiber
quantity
Pumping
Ejection


No.
Dispersant
dispersant
Solvent
solvent
Fiber type
quantity
[%]
time
hole
Comments

























1
oleylamine-Lupranat ® MI
2 g
aromatics
100 ml 
PLA
30 g
70%
10 s
Ø 1 cm
hole clogs up


2
oleylamine-Lupranat ® MI
4 g
aromatics
100 ml 
PLA
10 g
70%
10 s
Ø 1 cm
ejection almost












complete before












clogging


3
oleylamine-Lupranat ® MI
1 g
paraffin oil
50 ml
PLA
10 g
96%
10 s
Ø 2 cm
works very well,












homogeneous extrudate


4
oleylamine-Lupranat ® MI
1 g
paraffin oil
50 ml
PLA
20 g
96%
10 s
Ø 2 cm
works very well,












homogeneous extrudate


5
oleylamine-Lupranat ® MI
2 g
paraffin oil
50 ml
PLA
20 g
96%
10 s
Ø 2 cm
works very well,












homogeneous extrudate


6
oleylamine-Lupranat ® MI
2 g
paraffin oil
50 ml
PLA
25 g
96%
10 s
Ø 2 cm
works very well,












homogeneous extrudate


7
oleylamine-Lupranat ® MI
1 g
paraffin oil
50 ml
PLA
30 g
96%
10 s
Ø 2 cm
works poorly, clogs up,












too little dispersant


8
oleylamine-Lupranat ® MI
2 g
paraffin oil
50 ml
PP
10 g
96%
10 s
Ø 2 cm
works very well,












homogeneous extrudate


9
oleylamine-Lupranat ® MI
2 g
paraffin oil
50 ml
PVA
10 g
96%
10 s
Ø 2 cm
works very well,












homogeneous extrudate


10
oleylamine-Lupranat ® MI
2 g
paraffin oil
50 ml
cellulose
10 g
96%
10 s
Ø 2 cm
works very well,












homogeneous extrudate


11
oleylamine-Lupranat ® MI
2 g
paraffin oil
50 ml
PLA
30 g
96%
10 s
Ø 2 cm
works very well,












homogeneous extrudate


12
oleylamine-Lupranat ® MI
3 g
paraffin oil
50 ml
PLA
40 g
96%
10 s
Ø 2 cm
works very well,












homogeneous extrudate


13
oleylamine-Lupranat ® MI
2.5 g  
paraffin oil
50 ml
PLA
50 g
90%
10 s
Ø 2 cm
still works fairly well,












homogeneous extrudate





Legend as for Table 1

## Claims

1. A pumpable shelf-stable suspension of fibers in an organic phase, comprising:
1.0-60 wt % of fibers; and
0.01-10 wt % of a disubstituted urea.

2. The pumpable shelf-stable suspension according to claim 1, wherein the fibers are present in an amount of from 10-60 wt %.

3. The pumpable shelf-stable suspension according to claim 1, wherein the fibers are present in an amount of from 25-50 wt %.

4. The pumpable shelf-stable suspension according to claim 1, wherein the disubstituted urea is present in an amount of from 0.05-10 wt %.

5. The pumpable shelf-stable suspension according to claim 1, wherein the disubstituted urea is present in an amount of from 0.1-5 wt %.

6. The pumpable shelf-stable suspension according to claim 1, wherein the organic phase comprises at least one member selected from the group consisting of mineral oil, crude oil, paraffin oil, benzene, petroleum, a naphthenic oil, an aromatic oil, an aliphatic hydrocarbon, an aromatic hydrocarbon, a fatty oil, a fatty acid ester, a silicone oil and a phthalate ester.

7. The pumpable shelf-stable suspension according to claim 1, wherein the fibers comprise a material selected from the group consisting of a polyolefin, a polyester, a polyvinyl alcohol, a polyacetonitrile, a polyamide, polyethylene terephthalate, a polylactic acid, nylon 66 and nylon 6T.

8. The pumpable shelf-stable suspension according to claim 1, wherein the fibers comprise at least one material selected from the group consisting of polyethylene, polypropylene, polyglycol adipate and polycaprolactam.

9. The pumpable shelf-stable suspension according to claim 1, wherein the fibers comprise an inorganic material.

10. The pumpable shelf-stable suspension according to claim 9, wherein the inorganic material comprises at least one member selected from the group consisting of glass, carbon, basalt and a metal.

11. The pumpable shelf-stable suspension according to claim 1, wherein the fibers comprise a member selected from the group consisting of a renewable material, wherein said renewable material comprises a member selected from the group consisting of cellulose and lignin.

12. The pumpable shelf-stable suspension according to claim 1, wherein the fibers have a diameter of from 2 μm to 2 mm subject to the proviso of an aspect ratio of not less than 10.

13. The pumpable shelf-stable suspension according to claim 1, wherein the disubstituted urea is obtained from a monoisocyanate or polyisocyanate and a fatty amine.

14. The pumpable shelf-stable suspension according to claim 1, wherein the disubstituted urea is obtained from oleylamine and diphenylmethane diisocyanate (MDI).

15. A method of preparing the pumpable shelf-stable suspension according to claim 1 comprising adding to a mixture of the fibers in the organic phase the disubstituted urea.