WO2013042019A1

WO2013042019A1 - Process for preparing manufactured products in conglomerate of granulate of stone material and resin with anhydrides from renewable sources

Info

Publication number: WO2013042019A1
Application number: PCT/IB2012/054789
Authority: WO
Inventors: Luca Toncelli
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-09-20
Filing date: 2012-09-14
Publication date: 2013-03-28
Anticipated expiration: 2014-03-20
Also published as: ITTV20110125A1

Abstract

The invention describes a process for manufacturing manufactured products made from concrete and, more specifically, a process for manufacturing manufactured products in slabs and blocks from a mix consisting of particles of stone or lithoid material and a setting resin, in which said resin is obtained by reaction between at least one triglyceride of epoxidised polyunsaturated fatty acids and at least one anhydride from a renewable source, preferably of terpenic origin, in the presence of a catalyst, of a polyalcohol and of a silane, preferably a trialkoxysilane.

Description

PROCESS FOR PREPARING MANUFACTURED PRODUCTS IN CONGLOMERATE OF GRANULATE OF STONE MATERIAL AND RESIN WITH ANHYDRIDES

FROM RENEWABLE SOURCES

Description

The present invention concerns the manufacture of manufactured products made from concrete and, more specifically, a process for manufacturing manufactured products in slabs and blocks from a mix consisting of particles of stone or lithoid material and a setting resin, in which said resin is obtained by reaction between at least one triglyceride of epoxidised polyunsaturated fatty acids and at least one anhydride from a renewable source, preferably of terpenic origin.

State of the art

For many years there has been a process for manufacturing manufactured products in blocks and slabs of the aforementioned type, also known by the generic name of Bretonstone™ technology, in which an initial mix is prepared consisting of a granulate of inorganic or organic stone material or lithoid material, having a selected granulometry, and a binder based on setting resin. This mix is deposited on a temporary support or in a mould, having the dimensions of the end manufactured product, and it is subjected to a vacuum compression step, with accompanying application of a vibration motion at predetermined frequency. The crude manufactured product is transferred to a setting step, at the end of which the manufactured product has the desired mechanical characteristics. The resulting slab, possibly obtained from a block by sawing, is then sent on for finishing machine processing (calibration, smoothing, polishing and the like).

For more information and details concerning Bretonstone™ technology please refer to patent applications EP786325 and WO2006/122892, both incorporated here by reference.

Patent application WO2007/138529, also incorporated here by reference, describes making manufactured products according to Bretonstone™ technology that not only keep the mechanical and aesthetic characteristics that can be obtained using the binding resins known previously but also resist yellowing due to exposure to UV rays. This purpose is accomplished with a process of the type indicated previously and that is characterised by the use of a polyester resin, without reactive solvent (like for example styrene), obtained by reaction between at least one epoxidised polyunsaturated fatty acid, preferably a triglyceride of epoxidised polyunsaturated fatty acids, and at least one aliphatic or aromatic anhydride.

WO99/43729 describes a setting composition containing: (a) a compound contained at least one epoxy group obtained by epoxidation of natural unsaturated oils; (b) an epoxy compound of synthetic origin; (c) a polycarboxylic acid anhydride; (d) a setting accelerant of the amine type; (e) a filler.

JP201 1094002 and KR100835671 respectively describe an organic compound coating based on epoxidised natural oils and an anti-slip composition containing epoxy resins.

Description of the invention

The purpose of the present invention is to provide a process for preparing manufactured products made from concrete and, more specifically, a process for preparing manufactured products in the form of slabs or blocks according to what is described in the aforementioned patent application WO2007/138529, which is based on the use of raw materials from renewable sources.

Such a purpose has been accomplished by using resins obtained by reaction between at least one triglyceride of epoxidised polyunsaturated fatty acids and at least one anhydride deriving from renewable sources.

Among the possible anhydrides deriving from renewable sources, anhydrides of terpenic origin have proven to be the most suitable ones.

The object of the present invention is therefore represented by a process for preparing manufactured products made from concrete, preferably in the form of slabs or blocks, by setting a mix consisting of particles of stone material or of lithoid material and a setting resin, characterised in that said resin is obtained by reaction between at least one triglyceride of epoxidised polyunsaturated fatty acids and at least one anhydride from a renewable source, preferably of terpenic origin, in the presence of a catalyst, of a polyalcohol and of a silane, preferably a trialkoxysilane.

In this way, a concrete is obtained in the form of slabs or blocks with comparable characteristics to those obtained with the process described in WO2007/138529 both from the chemical and physical point of view, using both anhydrides and epoxy compounds deriving from renewable sources; in other words without using epoxy compounds of synthetic origin, like for example the compounds (b) described in W099/43729 and/or the synthetic anhydrides described in the same WO2007/138529.

For the purposes of the present invention, by the term "anhydrides from a renewable source" we mean anhydrides able to be obtained by Diels-Alder reaction between a monounsaturated anhydride, i.e. having a double carbon- carbon bond, and a conjugated diene or triene coming from a renewable source, for example belonging to the class of terpenes or sorbates; in particular, by the term "anhydrides of terpenic origin", we mean the aforementioned anhydrides in which the conjugated diene or triene is of the terpene type.

The monounsaturated anhydrides able to be used for the purposes of the present invention are, preferably, C₄-C₈ anhydrides, even more preferably C₄ or C₅, such as maleic anhydride and itaconic anhydride, with maleic anhydride being particularly preferred.

For the purposes of the present invention, by the term "conjugated diene or triene" we mean a conjugated diene or triene able to be obtained by thermal decomposition of, for example, a terpene having at least one double bond or a terpene containing at least two conjugated double bonds. In both cases, they are conjugated C5-C15 dienes, even more preferably C10 dienes; preferably a conjugated terpene-based diene or triene.

The thermal decomposition of terpenes is known in the literature and is described, for example, in US2325422, incorporated here by reference; it occurs at temperatures generally comprised between 160 and 400 °C, preferably between 180 and 280 °C, even more preferably between 225 and 250 °C.

Among the conjugated dienes able to be obtained by thermal decomposition of a terpene, the preferred one is allo-ocimene, i.e. the conjugated triene able to be obtained by thermal decomposition of α-pinene or of β-pinene; among the terpenes containing two conjugated double bonds, the preferred ones are a- terpinene and β-mircene. The most preferred conjugated terpene-based diene for the purposes of the present invention is allo-ocimene.

Diels-Alder reactions are equally well-known in the literature and are described, for example, in Jerry March, Advanced Organic Chemistry, Third Edition, John Wiley & Sons, 1985, pag. 745-758, incorporated here by reference. In particular, Diels-Alder reactions between a monounsaturated anhydride and a conjugated diene able to be obtained by thermal decomposition of a terpene are described in US3078235 and US4332733, also incorporated here by reference. The preferred anhydride of terpenic origin for the purposes of the present invention is the anhydride of 3,4-dimethyl-6-(2-methyl-1 -propenyl)-4- cyclohexene-1 ,2-dicarboxylic acid, i.e. the anhydride that is obtained by Diels- Alder reaction between allo-ocimene and maleic anhydride.

Among the sorbates from a renewable source there are the CrC₄ sorbates, like for example methyl sorbate, isopropyl sorbate.

According to an aspect of the present invention, anhydrides from a renewable source, preferably of terpenic origin, can be used in a mixture with one or more anhydrides not from a renewable source, preferably not of terpenic origin and, in particular, with one or more of the anhydrides described in WO2007/138529. For the purposes of the present invention, said at least one triglyceride of epoxidised polyunsaturated fatty acids is, preferably, a mixture of triglycerides of epoxidised polyunsaturated fatty acids having a long chain, i.e. having from 14 to 24 carbon atoms. According to a preferred aspect of the invention, said mixture of triglycerides is an oil of natural origin, like for example: linseed oil, soybean oil, colza oil, cornseed oil, sunflower oil, palm oil, tallow, fish oil; linseed oil is the preferred natural oil.

For use in the present invention the triglycerides, i.e. the oils, are subjected to an epoxidising reaction of the double bonds present (a per se well-known reaction), before being used for preparing the resin.

Like in the case of the process described in WO2007/138529, also in the process according to the present invention it is necessary for there to be a catalyst; which, according to its type and amount, acts to reduce both the reaction times and the process temperatures.

Among the possible initiators, there can be the following: alkaline metals halides, organometallic compounds of aluminium, zinc and tin, quaternary ammonium halides, aliphatic and aromatic amines, boron and titanium-based complexes. For the purposes of the present invention, C₃-C₆ aromatic amines and, in particular, C₃-C₆ aromatic diamines, proved to be particularly suitable; among these, 1 -methyl-imidazole is particularly preferred.

For a better end result in terms of physical properties of the concrete, the cross linking of the resin by reaction between at least one triglyceride of epoxidised polyunsaturated fatty acids and at least one anhydride from a renewable source, preferably of terpenic origin, is carried out in the presence of a polyalcohol and a silane.

The polyalcohol is preferably a C₂-C₂o polyalcohol, even more preferably C₂-C₆; according to a preferred aspect of the invention, it is selected among glycerine, 1 ,3-butanediol, 2,4-butanediol, 1 ,4-butanediol, ethylene glycol and propylene glycol, even more preferably glycerine.

The silane is different from the stone or lithoid material present in the mix. Advantageously, the silane is a trialkoxysilane.

According to an aspect of the invention, said trialkoxysilane has an epoxy end group and, preferably, it has from 7 to 14 carbon atoms, even more preferably from 9 to 12; according to an aspect of the invention, said trialkoxysilane having an epoxy end group is preferably selected among (3-glycidoxypropyl)- trimethoxysilane, (3-glycidoxypropyl)-triethoxysilane, (3-glycidoxymethyl)- trimethoxysilane, (3-glycidoxyethyl)-trimethoxysilane, (3-glycidoxybutyl)- trimethoxysilane, (3-glycidoxymethyl)-triethoxysilane, (3-glycidoxyethyl)- triethoxysilane, (3-glycidoxybutyl)-triethoxysilane, with (3-glycidoxypropyl)- trimethoxysilane being particularly preferred. According to a further aspect of the invention, said trialkoxysilane is vinyltrimethoxysilane.

According to a further aspect of the invention, the particles of said stone or lithoid material have an average granulometry of between 0.001 mm and 10 mm, preferably between 0.010 mm and 5 mm; more specifically said particles of stone material or of lithoid material consist of quartz filler (also known as air- classified powder) having average granulometry comprised between 0.001 mm and 0.05 mm, preferably between 0.005 and 0.015 mm and granulate of stone or lithoid material preferably selected between 0.05 mm and 10 mm, even more preferably between 0.1 and 4.8 mm.

For a better end result, said resin consists of 30 to 70 parts by weight of said triglyceride of epoxidised polyunsaturated fatty acids, preferably from 40 to 60; from 40 to 80 parts by weight of said anhydride of terpenic origin, preferably from 50 to 70; from 1 .5 to 2.5 parts by weight of said catalysis initiator, preferably from 1 .75 to 2.25; from 0.5 to 1 .5 parts by weight of said polyalcohol, preferably from 0.75 to 1 .25; from 0.5 to 1 .5 parts by weight of said silane, preferably from 0.75 to 1 .25.

Moreover from 3 to 20 parts by weight of said particles of stone material or of lithoid material, preferably from 5 to 15, are used for one part by weight of said resin based on triglyceride of epoxidised polyunsaturated fatty acids and anhydride from terpene sources.

According to a further aspect, the setting reaction of the resin occurs at a temperature of between 80 and 180 °C, preferably between 1 10 and 150 °C. According to a preferred aspect of the invention, the mix is deposited on a temporary support or in a mould, having the dimensions of the end manufactured product, and it is subjected to a vacuum compression step, with accompanying application of a vibration motion at predetermined frequency; the resulting crude manufactured product is then left to set until the end product is obtained. The following example illustrates the process of the present invention, not for limiting purposes.

Example 1

184 g of epoxidised linseed oil were mixed with 220 g of anhydride of terpenic origin of 3,4-dimethyl-6-(2-methyl-1 -propenyl)-4-cyclohexene-1 ,2-dicarboxylic acid. This was added to with 3.7 g of glycerine, 7.6 g of 1 -methyl-imidazole, 4.2 g of (3-glycidoxypropyl) trimethoxysilane. The mixture was mixed at room temperature for at least 15 minutes. The resin thus obtained was poured into a mixture of 3255 g of quartz granulate having a size of between 0.1 and 1 .2 mm and 1 .330 g of air-classified powders having average granulometry comprised between 0.005 and 0.025 mm. The mixture is mixed, poured into a mould and finally vibro-compacted, set and polished according to the standard Bretonstone™ method.

The manufactured product thus obtained was subjected to bending, water absorption and deep abrasion resistance tests. It was thus found that: it has a bending resistance equal to about 60 MPa; if subjected to water absorption for at least 24 hours it has an increase in weight equal to 0.03 %; the deep abrasion test generates an impression with a chord length of 30 mm.

Example 2

178 g of epoxidised linseed oil were mixed with 254 g of anhydride deriving from the Diels-Alder reaction between isopropyl sorbate and maleic anhydride. The mixture was added to with 6.3 g of glycerine, 7.3 g of 1 -methyl-imidazole, 4.5 g of (3-glycidoxypropyl) trimethoxysilane. Such a mixture was mixed at room temperature for at least 15 minutes and it was then poured into 3255 g of quartz granulate having a size of between 0.1 and 1 .2 mm and 1 .331 g of air-classified powders having average granulometry comprised between 0.005 and 0.025 mm. The mixture is mixed, poured into a mould and finally vibro-compacted, set and polished according to the standard Bretonstone™ method.

Claims

1 . Process for preparing manufactured products made from concrete, preferably in the form of slabs or blocks, by setting a mix consisting of particles of stone material or of lithoid material and a setting resin, characterised in that said resin is obtained by reaction between at least one triglyceride of epoxidised polyunsaturated fatty acids and at least one anhydride from a renewable source, preferably of terpenic origin, in the presence of a catalyst, of a polyalcohol and of a silane.

2. Process according to claim 1 , characterised in that said mix is deposited on a temporary support or in a mould, having the dimensions of the end manufactured product, and is subjected to a vacuum compression step, with accompanying application of a vibration motion at predetermined frequency, after which there is the setting step of the binding resin.

3. Process according to claim 1 , characterised in that said anhydride from a renewable source, preferably of terpenic origin, is obtained by Diels-Alder reaction between a monounsaturated anhydride and a conjugated diene or triene from a renewable source.

4. Process according to claim 3, characterised in that said conjugated diene or triene is obtained by thermal decomposition of a terpene.

5. Process according to claim 3, characterised in that said monounsaturated anhydride is a C -C₈ anhydride, preferably C₄-C₅.

6. Process according to claim 5, characterised in that said C₄-C₅ monounsaturated anhydride is maleic anhydride or itaconic anhydride, preferably maleic anhydride.

7. Process according to claim 3, characterised in that said conjugated diene or triene is a conjugated C₅-Ci₅ diene or triene, preferably a C₁₀ diene or triene.

8. Process according to claim 7, characterised in that said conjugated C₅-Ci₅ diene or triene is selected among the decomposition products of a-pinene or of β-pinene.

9. Process according to claim 8, characterised in that said decomposition products of α-pinene or of β-pinene are selected among allo-ocimene, a- terpinene and β-mircene, preferably it is allo-ocimene.

10. Process according to claim 3, characterised in that said anhydride of terpenic origin is the anhydride of 3,4-dimethyl-6-(2-methyl-1 -propenyl)-4- cyclohexene-1 ,2-dicarboxylic acid.

1 1 . Process according to claim 3, characterised in that said conjugated diene or triene is a sorbate, preferably a C-i-C₄ sorbate.

12. Process according to claim 1 1 , characterised in that said C C₄ sorbate is methyl sorbate or isopropyl sorbate.

13. Process according to claim 1 , characterised in that said at least one triglyceride of epoxidised polyunsaturated fatty acids is a mixture of triglycerides of epoxidised Ci₄-C₂4 polyunsaturated fatty acids.

14. Process according to claim 13, characterised in that said mixture of triglycerides of epoxidised Ci₄-C₂₄ polyunsaturated fatty acids is a natural epoxidised oil.

15. Process according to claim 14, characterised in that said natural oil is selected among linseed oil, soybean oil, colza oil, comseed oil, sunflower oil, palm oil, fish oil, preferably linseed oil.

16. Process according to claim 1 , characterised in that said catalyst is selected among alkaline metals halides, organometallic compounds of aluminium, zinc and tin, quaternary ammonium halides, aliphatic and aromatic amines, boron and titanium-based complexes.

17. Process according to claim 16, characterised in that said aromatic amine is a C₃-C₆ aromatic amine, preferably a C₃-C₆ diaromatic amine, even more preferably 1 -methyl-imidazole.

18. Process according to claim 1 , characterised in that said polyalcohol is a C₂-C₂o polyalcohol, preferably C₂-C₆.

19. Process according to claim 1 , characterised in that said C₂-C₆ polyalcohol is selected among glycerine, 1 ,3-butanediol, 2,4-butanediol, 1 ,4-butanediol, ethylene glycol and propylene glycol, preferably glycerine.

20. Process according to claim , characterised in that said silane is different from the lithoid material or lithoid present in the mix.

21 . Process according to claim 1 , characterised in that said silane is a trialkoxysilane.

22. Process according to claim 21 , characterised in that said trialkoxysilane has from 7 to 14 carbon atoms, preferably from 9 to 12, and an epoxy end group.

23. Process according to claim 22, characterised in that said trialkoxysilane having an epoxy end group is selected among (3-glycidoxypropyl)- trimethoxysilane, (3-glycidoxypropyl)-triethoxysilane, (3-glycidoxymethyl)- trimethoxysilane, (3-glycidoxyethyl)-trimethoxysilane, (3-glycidoxybutyl)- trimethoxysilane, (3-glycidoxymethyl)-triethoxysilane, (3-glycidoxyethyl)- triethoxysilane, (3-glycidoxybutyl)-triethoxysilane, preferably (3- glycidoxypropyl)-trimethoxysilane.

24. Process according to claim 21 , characterised in that said trialkoxysilane is vinyltrimethoxysilane.

25. Process according to claim 1 , characterised in that said setting reaction occurs at a temperature of between 80 and 180 °C, preferably between 1 10 and 150 °C.

26. Process according to claim 1 , characterised in that the particles of said lithoid material or of lithoid material have an average granulometry of between 0.001 mm and 10 mm, preferably between 0.01 mm and 5 mm.

27. Process according to claim 1 , characterised in that it uses from 30 to 70 parts by weight of said triglyceride of epoxidised polyunsaturated fatty acids, preferably from 40 to 60; from 40 to 80 parts by weight of said anhydride from a renewable source, preferably from 50 to 70; from 1 .5 to 2.5 parts by weight of said catalysis initiator, preferably from 1 .75 to 2.25; from 0.5 to 1 .5 parts by weight of said polyalcohol, preferably from 0.75 to 1 .25; from 0.5 to 1 .5 parts by weight of said silane, preferably from 0.75 to 1 .25.

28. Process according to claim 1 , characterised in that it uses from 3 to 20 parts by weight of said particles of stone material or of lithoid material, preferably from 5 to 15, for one part by weight of said resin based on triglyceride of epoxidised polyunsaturated fatty acids and anhydride from renewable sources.

29. Process according to claim 1 , characterised in that it is carried out in the absence of solvents, preferably in the absence of styrene.

30. Manufactured product made from concrete, preferably in the form of slabs or blocks, obtainable through the process according to any one of the previous claims.