(19)
(11)EP 3 342 797 A1

(12)EUROPEAN PATENT APPLICATION

(43)Date of publication:
04.07.2018 Bulletin 2018/27

(21)Application number: 18156449.3

(22)Date of filing:  15.01.2016
(51)International Patent Classification (IPC): 
C08G 77/58(2006.01)
C08L 83/16(2006.01)
B64C 3/00(2006.01)
C08G 77/04(2006.01)
B64C 1/00(2006.01)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(62)Application number of the earlier application in accordance with Art. 76 EPC:
16382017.8 / 3192824

(71)Applicant: The Boeing Company
Chicago, IL 60606-2016 (US)

(72)Inventors:
  • GONZALEZ GARCIA, Ana
    28042 MADRID (ES)
  • MARTIN ALONSO, Pedro Pablo
    28042 MADRID (ES)
  • LAPEÑA REY, Nieves
    28042 MADRID (ES)
  • GONZALEZ RODRIGUEZ, Tomas
    33011 OVIEDO (ES)
  • MARTINEZ ALONSO, Amelia
    33011 OVIEDO (ES)

(74)Representative: Carvajal y Urquijo, Isabel et al
Clarke, Modet & Co. Suero de Quiñones, 34-36
28002 Madrid
28002 Madrid (ES)

 
Remarks:
This application was filed on 13-02-2018 as a divisional application to the application mentioned under INID code 62.
 


(54)A METHOD FOR A CURING CYCLE OF AN INORGANIC THERMOSET RESIN


(57) An aspect of the present description is a method for a curing cycle of an inorganic thermoset resin, the method comprising:
(a) adding a hardener in a concentration of 20% by weight of the resin to said inorganic thermoset resin and
(b) curing the resin at a temperature of 80ºC during at least 60 minutes.
Another aspect of the present description is an inorganic thermoset resin comprising a hardener in a concentration of 20% by weight of the resin.
A further aspect of the present description is a vehicle interior panel comprising a composite comprising a composite matrix of a natural fibre set within the inorganic thermoset resin of an aspect of the present description.
The features, functions, and advantages that have been discussed can be achieved independently in various embodiments or may be combined in yet other embodiments further details of which can be seen with reference to the following description and drawings.




Description

FIELD



[0001] This description relates to methods for curing an inorganic thermoset resin using a short curing cycle. Particularly, this description relates to a method for curing an inorganic thermoset resin by adding a hardener to the resin and curing the resin at a selected temperature.

BACKGROUND



[0002] A geopolymer is an inorganic thermoset resin. This inorganic thermoset resin is essentially a mineral chemical compound consisting of repeating units, for example silico-oxide (-Si-O-Si-O-), silico-aluminate (-Si-O-AI-O-), ferro-silico-aluminate (-Fe-O-Si-O-Al-O-) or alumino-phosphate (-Al-O-P-O-), created through a process of geopolymerization.

[0003] Inorganic thermoset resins can be used for obtaining composite products. Different composite products can be obtained from inorganic thermoset resins. For example, vehicle interior panels can be obtained from geopolymeric resins. Aircraft, trains, automobiles, ships, and other vehicles may incorporate interior panels made from geopolymeric resins.

[0004] Inorganic thermoset resins have an outstanding fire performance.

[0005] Inorganic thermoset resins require hours (for example 2 hours) to cure at temperatures of about 80ºC.

[0006] It is possible to improve the curing process by reducing the curing time.

[0007] EP 2894136 A1 discloses a method of manufacturing an aircraft interior panel comprising a core sandwiched between first and second skins, wherein both skins are formed from a thermosetting resin composition comprising 15 wt.% of aluminium phosphate or copper phosphate as hardener, an anti-shrinkage additive and natural fibre.

DESCRIPTION



[0008] The present description provides a method for curing an inorganic thermoset resin, the method comprising:
  1. (a) adding a hardener in a concentration from 18 to 30% by weight of the resin to said inorganic thermoset resin and
  2. (b) curing the resin at a temperature from 110 to 120ºC.


[0009] The technical effect associated to the distinguishing features of the present description with respect to the state of the art is a reduction in curing time.

[0010] The problem in view of the state of the art can be defined as the provision of a method for curing an inorganic thermoset resin with a reduced curing time compared to the state of the art.

[0011] The examples show that if the resin contains hardener at 15% by weight of the resin, at 80ºC, more than 60 minutes are needed for curing the resin.

[0012] It the concentration of hardener is increased to 20% by weight of the resin, the curing cycle time at 80ºC is reduced to more than 30 minutes, which is very far from a curing cycle time of 8 minutes.

[0013] If the resin contains hardener in the range of 18-30% by weight of the resin in combination to a curing cycle at a temperature in the range of 110 to 120ºC, then, surprisingly, the curing cycle time is drastically reduced to 8 minutes.
The examples show that, surprisingly, if the resin and the temperature are in these ranges, the polycondensation reaction is carried out, which accounts for the improved kinetics obtained with the features of the curing cycle of the present description.

[0014] The reduced curing time enables producing goods made of this resin at a production rate for 1 good/less than 10 minutes.

[0015] The curing cycle in less than 10 minutes allows the production of sustainable sidewall panels at industrial scale. The method of the present description enables production rates of 1 panel/less than 10 minutes. The method is feasible for aerospace industry.

[0016] An aspect of the present description is a method for a curing cycle of an inorganic thermoset resin, the method comprising:
  1. (a) adding a hardener in a concentration from 18 to 30% by weight of the resin to said inorganic thermoset resin and
  2. (b) curing the resin at a temperature from 110 to 120ºC.


[0017] In the present description, the term "inorganic thermoset resin" include, but are not limited to silico-oxide (-Si-O-Si-O-) resins, silico-aluminate (-Si-O-Al-O-) resins, ferro-silico-aluminate (-Fe-O-Si-O-Al-O-) resins or alumino-phosphate (-Al-O-P-O-) resins.

[0018] In this aspect of the present description, the inorganic thermoset resin is preferably a silico-aluminate resin. Said silico-aluminate resin is of the type -Si-O-Al-O-.

[0019] In this aspect of the present description, curing time is from 5 to 20 minutes. Preferably, said curing time is from 5 to 10 minutes. More preferably, said curing time is from 7 to 8 minutes.

[0020] In the first aspect of the present description, the concentration of said hardener in step (a) is preferably from 18 to 25% by weight of the resin. More preferably, the concentration of said hardener in step (a) is from 19 to 24% by weight of the resin or from 20 to 23% by weight of the resin.

[0021] In the first aspect of the present description, the temperature in step (b) is preferably from 112 to 118 ºC. More preferably, the temperature in step (b) is from 114 to 116ºC.

[0022] In a further aspect of the present description, the hardener, compatible with inorganic thermoset resins is selected from the group consisting of aluminium phosphate, copper phosphate, and mixtures thereof.

[0023] In a further aspect of the present description, an anti-shrinkage additive is added in step (a) to said inorganic thermoset resin. In an example of this aspect of the present description, said anti-shrinkage additive is aluminium silicate or metakaolin.

[0024] In a further aspect of the present description, the inorganic thermoset resin comprises halloysite nanotubes (Al2Si2O5(OH)4). Halloysite nanotubes may be added in replacement of an anti-shrinkage additive. Inorganic thermoset resins comprising halloysite nanotubes don't shrink during the resin curing.

[0025] In a further aspect of the present description, a natural fibre is added in step (a) to said inorganic thermoset resin. In an example of this aspect of the present description, said natural fibre is selected from the group consisting of flax, jute, hemp and sisal. In another example of this aspect of the present description, said natural fibre comprises a flame retardant. Said flame retardant is selected from the group consisting of disodium octaborate tetrahydrate (Na2B8O13·4H2O), phosphate nano-particles and nanographene. Preferably, the flame retardants are compatible with flax fibers.

[0026] In a further aspect of the present description, a flame retardant is added in step (a) to said aluminium silicate inorganic thermoset resin. In an example of this aspect of the present description, said flame retardant is selected from the group consisting of disodium octaborate tetrahydrate (Na2B8O13·4H2O), phosphate nano-particles and nanographene.

[0027] Another aspect of the present description is an inorganic thermoset resin comprising a hardener in a concentration from 18 to 30% by weight of the resin.

[0028] A further aspect of the present description, wherein the hardener is selected from the group consisting of aluminium phosphate, copper phosphate, and mixtures thereof. The hardener forms a chemical bond between the inorganic thermoset resin (polymerization) during the curing process.

[0029] In a further aspect, the inorganic thermoset resin of the present description comprises an anti-shrinkage additive. Preferably, said anti-shrinkage additive is aluminium silicate or metakaolin.

[0030] Another aspect of the present description is a vehicle interior panel comprising a composite comprising a composite matrix of a natural fibre set within the inorganic thermoset resin of the second aspect of the present description.

[0031] A further aspect of the present description, wherein said natural fibre is selected from the group consisting of flax, jute, hemp and sisal.

[0032] A further aspect i of the present description, wherein said natural fibre comprises a flame retardant. Preferably, said flame retardant is selected from the group consisting of disodium octaborate tetrahydrate (Na2B8O13·4H2O), phosphate nano-particles and nanographene. These examples have flame retardance-mechanisms compatible with natural fibers.

[0033] A further aspect of the present description, wherein said vehicle is selected from the group consisting of aircraft, train, automobile, and ship.

BRIEF DESCRIPTION OF THE FIGURES



[0034] 

Figure 1. DSC analysis of the geopolymeric resin. Weight results.

Figure 2. DSC analysis of the geopolymeric resin. Heat flow results.

Figure 3. DSC analysis of the geopolymeric resin. Derivative heat flow results.


EXAMPLES


Example 1. Differential Scanning Calorimetry (DSC) analysis of the geopolymeric resin



[0035] A Differential Scanning Calorimetry (DSC) analysis of the geopolymeric resin (an inorganic thermoset resin, a silico-aluminate inorganic thermoset resin of the -Si-O-Al-O- type comprising 20% wt. of hardener (aluminium phosphate 20% by weight of the resin). The results (with the same resin sample) are provided in Figures 1, 2 and 3. The DSC results showed that the polymerization reaction between the hardener and the resin occurred in the 112-116ºC range.

[0036] The main processes and the type of reactions that occur during the DSC analysis are summarized in Table 1 (below).
Table 1. Summary of the DSC analysis of the geopolymeric resin.
Type of processTemperature range (ºC)Type of reaction
Endothermic 55 Water evaporation
Exothermic 68 Gel formation
Exothermic 112-116 Polycondensation reaction


[0037] The DSC analysis allows concluding that the polymerization of the geopolymeric resin comprises three processes taking place at different temperatures.
  • At about 55 ºC, non-chemically bonded water is released.
  • At about 68 ºC, gels in the geopolymeric resin are reorganized (gel formation step).
  • In the 112 ºC-116ºC range, the resin and the hardener polycondensates (polycondensation reaction between the hardener and the resin)


[0038] At 116ºC the overall mass loss is about 10 % by weight of the resin.

Example 2. Preparation of a geopolymeric resin



[0039] The geopolymeric resin is obtained by mixing a silico-aluminate inorganic thermoset resin of the -Si-O-Al-O- type with a hardener (aluminium phosphate 20% by weight of the resin). An anti-shrinkage additive (metakaolin, 5% by weight with respect of the resin) is added to the resin.

[0040] A single step curing cycle of 115ºC during 8 min was carried out.

Example 3. Tests



[0041] The result of the curing cycle of Example 2, which is according to the description, is shown in the last row of Table 2.

[0042] Several comparative test were carried out, not according to the description, in order to show the surprising effect achieved by the present description.

[0043] These tests are summarized in Table 2.

[0044] If the resin contains hardener at 15% by weight of the resin, at 80ºC and 60 minutes curing cycle, the resin is not cured. More than 60 minutes are needed for curing the resin.

[0045] If the resin contains hardener at 15% by weight of the resin, and a cycle of 80ºC 15 minutes + 110ºC 15 minutes is used, the resin is cured.

[0046] If the resin contains hardener at 20% by weight of the resin, at 80ºC and 30 minutes curing cycle, the resin is not cured. More than 30 minutes are needed for curing the resin.

[0047] Surprisingly, if the resin contains hardener at 20% by weight of the resin, and the temperature is 115ºC, the curing cycle is drastically reduced to 8 minutes.
Table 2. Comparative tests
Curing cycle timeHardener (% in wt.)Temperature (ºC)Curing state
120 minutes 10% 80ºC Uncured
15% Cured
20% Cured
25% Cured
90 minutes 10% 80ºC Uncured
  15%   Cured
  20%   Cured
  25%   Cured
60 minutes 10% 80ºC Uncured
  15%   Uncured
  20%   Cured
  25%   Cured
30 minutes 10%   Uncured
  15%   Uncured
  20%   Uncured
  25%   Uncured
15 minutes + 15 minutes 15% 80ºC 15 minutes + 110ºC 15 minutes Cured
8 minutes 20% 115 ºC Cured

Example 4. Boilling Water Tests (BWTs) on the geopolymeric resin



[0048] The Boiling water test (BWT) is a test procedure known by the skilled person that determines whether a thermoset inorganic resin has undergone a correct polymerization and, therefore, if it has properly cured. The appropriate polymerization of the resin is crucial for the applicability of the resin so it could also be considered as a screening test before fine tuning any process development for inorganic thermoset resins.

[0049] The test consists of introducing small pieces of the cured resin in boiled water during 20 minutes. There are two possible scenarios:
  • The samples of the cured resin do not suffer deformation or degradation after the boiling water tests, indicating the correct polymerization of the resin. In this case, the resin passes the Boiling water test, showing that the resin has properly cured.
  • The samples of cured resin suffer deformation or disintegration after (or before) the 20 min boiling water test, indicating that the resin has not polymerized. In this case the resin fails the BWT, showing that the resin has not properly cured.


[0050] To provide an accurate estimation of whether the samples suffer deformation and/or disintegration during such test, the diameter of the small pieces of cured resin samples subjected to the test are measured before and after the BWTs. This allows measuring any possible variation that the diameter of the cured samples could suffer at a millimeter scale.

Boiling water test results:



[0051] Samples of the of the geopolymeric resin as disclosed in Example 2 were subjected to the BWTs in order to assess if the resin had properly polymerized. The resin successfully passed the BWTs since the cured resin samples show diameter resilience and no shape deformation after being inmersed in boiling water. These results showed that the resin has polymerized correctly.

Example 5. Rheological study of the geopolymeric resin



[0052] A rheological study of the resin as disclosed in Example 2 was performed. The results are compared to the results obtained with a resin with a hardener (aluminium phosphate) concentration of 15% (not according to the description, but for comparison).

[0053] The results, shown in Table 3, show that the viscosity obtained for the resin comprising 20% by weight of the hardener is similar to the viscosity obtained for the resin comprising 15% by weight of hardener.
Table 3: Rheological studies (at 150 rpm and 8 rpm) of geopolymeric resin.
Amount of hardenerViscosity at 150 rpm (21ºC)Viscosity at 8 rpm (21ºC)
15% wt. resin 0.34 Pa*s 1.04 Pa*s
20% wt. resin 0.25 Pa*s 0.44 Pa*s

Example 6. Preparation of a product comprising a geopolymeric resin and a natural fibre treated with a flame retardant



[0054] The product comprises an inorganic thermoset resin (a silico-aluminate inorganic thermoset resin of the -Si-O-Al-O- type) and a natural fibre treated with a flame retardant.

[0055] The resin comprises a hardener (aluminium phosphate 20% by weight of the resin) and an anti-shrinkage additive (metakaolin, 5% by weight with respect of the resin).

[0056] The natural fibre in this example is flax treated with the flame retardant disodium octaborate tetrahydrate (Na2B8O13·4H2O).

[0057] After mixing all the components of the product a single step curing cycle of 115ºC during 8 min was carried out.


Claims

1. A method for a curing cycle of an inorganic thermoset resin, the method comprising:

(a) adding a hardener in a concentration of 20% by weight of the resin to said inorganic thermoset resin; and

(b) curing the resin at a temperature of 80ºC during at least 60 minutes.


 
2. The method according to claim 1, wherein the hardener is selected from the group consisting of aluminium phosphate, copper phosphate, and mixtures thereof.
 
3. The method according to claim 1 or 2, wherein an anti-shrinkage additive is added in step (a) to said inorganic thermoset resin.
 
4. The method according to claim 3, wherein said anti-shrinkage additive is aluminium silicate or metakaolin.
 
5. The method according to any of claims 1 to 4, wherein a natural fibre is added in step (a) to said inorganic thermoset resin.
 
6. The method according to any claim 5, wherein said natural fibre is selected from the group consisting of flax, jute, hemp, and sisal.
 
7. The method according to claim 5 or 6, wherein said natural fibre comprises a flame retardant.
 
8. The method according to any one of claims 1 to 7, wherein a flame retardant is added in step (a) to said inorganic thermoset resin.
 
9. The method according to claim 7 or claim 8, wherein said flame retardant is selected from the group consisting of disodium octaborate tetrahydrate (Na2B8O13·4H2O), phosphate nano-particles, and nanographene.
 
10. An inorganic thermoset resin, comprising a hardener in a concentration of 20% by weight of the resin.
 
11. The inorganic thermoset resin according to claim 10, wherein the hardener is selected from the group consisting of aluminium phosphate, copper phosphate and mixtures thereof.
 
12. The inorganic thermoset resin according to claim 10 or 11, comprising an anti-shrinkage additive.
 
13. A vehicle interior panel, comprising a composite comprising a composite matrix of a natural fibre set within an inorganic thermoset resin according to any one of claims 10 to 12.
 
14. The vehicle interior panel according to claim 13, wherein said natural fibre comprises a flame retardant.
 
15. The vehicle interior panel according to claim 13 or 14, wherein said vehicle is selected from the group consisting of aircraft, train, automobile, and ship.
 




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Search report




Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description