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WO2013042019A1 - Procédé pour la préparation de produits manufacturés sous forme de conglomérat de granulat de matériau en pierre et de résine avec des anhydrides provenant de source renouvelable, de préférence d'origine terpénique - Google Patents

Procédé pour la préparation de produits manufacturés sous forme de conglomérat de granulat de matériau en pierre et de résine avec des anhydrides provenant de source renouvelable, de préférence d'origine terpénique Download PDF

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Publication number
WO2013042019A1
WO2013042019A1 PCT/IB2012/054789 IB2012054789W WO2013042019A1 WO 2013042019 A1 WO2013042019 A1 WO 2013042019A1 IB 2012054789 W IB2012054789 W IB 2012054789W WO 2013042019 A1 WO2013042019 A1 WO 2013042019A1
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WIPO (PCT)
Prior art keywords
process according
anhydride
oil
epoxidised
triene
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Ceased
Application number
PCT/IB2012/054789
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English (en)
Inventor
Luca Toncelli
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/14—Polyepoxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/18—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1006—Absence of well-defined organic compounds
    • C04B2111/1012—Organic solvents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/54—Substitutes for natural stone, artistic materials or the like

Definitions

  • 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.
  • Patent application WO2007/138529 also incorporated here by reference, describes making manufactured products according to BretonstoneTM 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.
  • a polyester resin without reactive solvent (like for example styrene)
  • 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.
  • 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.
  • 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.
  • 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.
  • 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, C 4 -C 8 anhydrides, even more preferably C 4 or C 5 , such as maleic anhydride and itaconic anhydride, with maleic anhydride being particularly preferred.
  • 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.
  • 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.
  • the preferred one is allo-ocimene, i.e. the conjugated triene able to be obtained by thermal decomposition of ⁇ -pinene or of ⁇ -pinene; among the terpenes containing two conjugated double bonds, the preferred ones are a- terpinene and ⁇ -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.
  • 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.
  • sorbates from a renewable source there are the CrC 4 sorbates, like for example methyl sorbate, isopropyl sorbate.
  • anhydrides from a renewable source 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.
  • 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.
  • 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.
  • the triglycerides i.e. the oils
  • the triglycerides are subjected to an epoxidising reaction of the double bonds present (a per se well-known reaction), before being used for preparing the resin.
  • alkaline metals halides organometallic compounds of aluminium, zinc and tin, quaternary ammonium halides, aliphatic and aromatic amines, boron and titanium-based complexes.
  • C 3 -C 6 aromatic amines and, in particular, C 3 -C 6 aromatic diamines proved to be particularly suitable; among these, 1 -methyl-imidazole is particularly preferred.
  • 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 C 2 -C 2 o polyalcohol, even more preferably C 2 -C 6 ; 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.
  • the silane is a trialkoxysilane.
  • 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 trialkoxypropyl)-
  • 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.
  • quartz filler also known as air- classified powder
  • 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.
  • the setting reaction of the resin occurs at a temperature of between 80 and 180 °C, preferably between 1 10 and 150 °C.
  • 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.
  • epoxidised linseed oil 184 g 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 BretonstoneTM 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention porte sur un procédé pour la fabrication de produits manufacturés fabriqués à partir de béton et, plus précisément, sur un procédé pour la fabrication de produits manufacturés sous forme de dalles et de blocs à partir d'un mélange constitué de particules de pierre ou de matériau lithoïde et d'une résine de durcissement, ladite résine étant obtenue par la réaction entre au moins un triglycéride d'acides gras polyinsaturés époxydés et au moins un anhydride provenant d'une source renouvelable, de préférence d'origine terpénique, en présence d'un catalyseur, d'un polyol et d'un silane, de préférence d'un trialcoxysilane.
PCT/IB2012/054789 2011-09-20 2012-09-14 Procédé pour la préparation de produits manufacturés sous forme de conglomérat de granulat de matériau en pierre et de résine avec des anhydrides provenant de source renouvelable, de préférence d'origine terpénique Ceased WO2013042019A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000125A ITTV20110125A1 (it) 2011-09-20 2011-09-20 Processo per la preparazione di manufatti in conglomerato di granulato di materiale lapideo e resina con anidridi di origine terpenica
ITTV2011A000125 2011-09-20

Publications (1)

Publication Number Publication Date
WO2013042019A1 true WO2013042019A1 (fr) 2013-03-28

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IT (1) ITTV20110125A1 (fr)
WO (1) WO2013042019A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2848596A3 (fr) * 2013-09-11 2015-07-29 Sorge, Günther Bloc de construction à vide pouvant être fabriqué en différentes matières
IT201700102110A1 (it) * 2017-09-12 2019-03-12 Rosa Riccardo Salvatore La Composto, lapideorinforzato a basso peso, ottenuto da scarti di fanghi e polveri delle lavorazioni lapidee, processo di recupero dalle lavorazioni e metodo per l'utilizzo di detti materiali di risulta all'interno dello stabilimento di produzione o presso strutture esterne
US10513566B2 (en) 2017-06-22 2019-12-24 ACS Technical Products, Inc. Epoxidized oil and resin compositions
IT201900010329A1 (it) * 2019-06-27 2020-12-27 Luca Toncelli Manufatto in materiale conglomerato, assieme composito comprendente il manufatto e metodo di produzione del manufatto in materiale conglomerato
US10913829B2 (en) 2017-06-22 2021-02-09 ACS Technical Products, Inc. Epoxidized oil binder compositions and process for preparation of thermoset hardened products

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2325422A (en) 1940-12-23 1943-07-27 Newport Ind Inc Process of making allo-ocimene
US3078235A (en) 1958-10-24 1963-02-19 Minnesota Mining & Mfg Liquid anhydride hardener compositions for epoxy resins
US4332733A (en) 1979-02-28 1982-06-01 Mitsubishi Petrochemical Co., Ltd. Process for liquefying acid anhydride
DE19627165A1 (de) * 1995-07-05 1997-01-09 Preform Gmbh Polymerwerkstoff, Verfahren zu seiner Herstellung und dessen Verwendung
EP0786325A1 (fr) 1996-01-29 1997-07-30 TONCELLI, Marcello Méthode et dispositif pour la fabrication de carreaux à partir d'aggrégats minéraux et/ou de sable et de résine durcissable
WO1999043729A1 (fr) 1998-02-27 1999-09-02 Vantico Ag Composition durcissable comprenant des huiles naturelles epoxydees
WO2006122892A1 (fr) 2005-05-19 2006-11-23 Luca Toncelli Procede et usine destines a la fabrication de blocs de roche ou de ceramique agglomeree
WO2007138529A2 (fr) 2006-05-31 2007-12-06 Luca Toncelli Procédé de fabrication de dalles ou de blocs d'aggloméré de pierre et de résine polyester
KR100835671B1 (ko) 2007-12-20 2008-06-05 주식회사 포이닉스 노면 미끄럼 방지용 포장재 조성물 및 공법
JP2011094002A (ja) 2009-10-29 2011-05-12 Nippon Paint Co Ltd 天然油脂を原料とする有機無機複合コーティング組成物

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2325422A (en) 1940-12-23 1943-07-27 Newport Ind Inc Process of making allo-ocimene
US3078235A (en) 1958-10-24 1963-02-19 Minnesota Mining & Mfg Liquid anhydride hardener compositions for epoxy resins
US4332733A (en) 1979-02-28 1982-06-01 Mitsubishi Petrochemical Co., Ltd. Process for liquefying acid anhydride
DE19627165A1 (de) * 1995-07-05 1997-01-09 Preform Gmbh Polymerwerkstoff, Verfahren zu seiner Herstellung und dessen Verwendung
EP0786325A1 (fr) 1996-01-29 1997-07-30 TONCELLI, Marcello Méthode et dispositif pour la fabrication de carreaux à partir d'aggrégats minéraux et/ou de sable et de résine durcissable
WO1999043729A1 (fr) 1998-02-27 1999-09-02 Vantico Ag Composition durcissable comprenant des huiles naturelles epoxydees
WO2006122892A1 (fr) 2005-05-19 2006-11-23 Luca Toncelli Procede et usine destines a la fabrication de blocs de roche ou de ceramique agglomeree
WO2007138529A2 (fr) 2006-05-31 2007-12-06 Luca Toncelli Procédé de fabrication de dalles ou de blocs d'aggloméré de pierre et de résine polyester
KR100835671B1 (ko) 2007-12-20 2008-06-05 주식회사 포이닉스 노면 미끄럼 방지용 포장재 조성물 및 공법
JP2011094002A (ja) 2009-10-29 2011-05-12 Nippon Paint Co Ltd 天然油脂を原料とする有機無機複合コーティング組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JERRY MARCH: "Advanced Organic Chemistry, Third Edition,", 1985, JOHN WILEY & SONS, pages: 745 - 758

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2848596A3 (fr) * 2013-09-11 2015-07-29 Sorge, Günther Bloc de construction à vide pouvant être fabriqué en différentes matières
US10513566B2 (en) 2017-06-22 2019-12-24 ACS Technical Products, Inc. Epoxidized oil and resin compositions
US10913829B2 (en) 2017-06-22 2021-02-09 ACS Technical Products, Inc. Epoxidized oil binder compositions and process for preparation of thermoset hardened products
IT201700102110A1 (it) * 2017-09-12 2019-03-12 Rosa Riccardo Salvatore La Composto, lapideorinforzato a basso peso, ottenuto da scarti di fanghi e polveri delle lavorazioni lapidee, processo di recupero dalle lavorazioni e metodo per l'utilizzo di detti materiali di risulta all'interno dello stabilimento di produzione o presso strutture esterne
IT201900010329A1 (it) * 2019-06-27 2020-12-27 Luca Toncelli Manufatto in materiale conglomerato, assieme composito comprendente il manufatto e metodo di produzione del manufatto in materiale conglomerato
WO2020261109A1 (fr) * 2019-06-27 2020-12-30 Luca Toncelli Article constitué de matériau aggloméré, ensemble composite comprenant un tel article et procédé de fabrication de l'article constitué de matériau aggloméré
US20220227920A1 (en) * 2019-06-27 2022-07-21 Luca Toncelli Article made of conglomerate material, composite assembly comprising such article and method for manufacturing the article made of conglomerate material

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