WO2006128918A1 - Biodegradable plastic materials - Google Patents

Biodegradable plastic materials Download PDF

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Publication number
WO2006128918A1
WO2006128918A1 PCT/EP2006/062906 EP2006062906W WO2006128918A1 WO 2006128918 A1 WO2006128918 A1 WO 2006128918A1 EP 2006062906 W EP2006062906 W EP 2006062906W WO 2006128918 A1 WO2006128918 A1 WO 2006128918A1
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WO
WIPO (PCT)
Prior art keywords
compound
mixing
radical
poly
quantities
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Application number
PCT/EP2006/062906
Other languages
French (fr)
Inventor
Rosa Prati
Marco Angeli
Elisabetta Ranucci
Paolo Ferruti
Original Assignee
Tartarica Treviso S.R.L.
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Application filed by Tartarica Treviso S.R.L. filed Critical Tartarica Treviso S.R.L.
Publication of WO2006128918A1 publication Critical patent/WO2006128918A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/428—Lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers

Definitions

  • a method for obtaining co- poly (amide esters) comprising a first phase in which glycolic acid (OH-CH 2 -CO-OH) is made to react with lactic acid (OH-CH- (CH 3 ) -CO-OH) and succinic anhydride (C4H4O 3 ) to obtain a poly (lactic glycolic carboxy terminated) acid having a general formula [-OH-CO-C 2 H 4 -CO- [0-CH 2 -CO-O-CH 2 - (CH 3 ) -C0-0-] n -H] and a second phase in which the product that is obtained from the reaction of the first phase, is mixed with a first compound having a general formula Ri(COOH) 2 , and further mixed with a further compound having a general formula R 2 (NCO) 2 to bring about the polymerisation reaction, obtaining polyesters having a general formula [-NH-R 2 -NH-CO-R ⁇ -CO-NH-R 2 -NH-CO- C
  • the radical Ri may comprise two alcoholic functions (-0H) , and can be chosen between the aliphatic radicals or between the radicals containing double bonds, between the radicals having linear or branched, and/or cross-linked chain.
  • the first compound can be selected from the dihydroxy acids, in particular tartaric acid or a similar compound thereto can be used as a first compound.
  • Table 4 is the legend relating to the spectrum in Figure 7;
  • the product was precipitated by the reaction mixture through the addition of water, then the product was washed twice with water in order to eliminate the solvent and non-reacted tartaric acid, then filtered and subsequently washed with methanol to eliminate the non- reacted diisocyanate and any secondary products with a low molecular weight, then further washed with ethanol before being dried in a vacuum.
  • the test effected have also shown that too low quantities of solvent make the solubility of the reactants to decrease even in the first growing phase of the polymer to be obtained.
  • the solvent removed form the surface of the film can be easily recycled by condensation. Recycling the solvent become more important and convenient as the reaction is used industrially.
  • the film has also been washed in a suitable further solvent, for example a water-methanol mixing, or water, or also thinner films can be obtained.
  • a suitable further solvent for example a water-methanol mixing, or water, or also thinner films can be obtained.
  • the temperature of the system is kept at about 4O 0 C by using an ice bath during the reaction.
  • the reaction is identified by CO 2 developing, turbidity of the reaction system due to the formation of the oligomers and subsequently of the polymer, and the increasing of the viscosity of the reaction system.
  • the polymers spread on the support and dried in the oven has been extracted using a "Kumagawa extractor", that enables to remove the solvent of the reaction remained on the film of the polymer by using and extraction solvent in which the polymer is immersed.
  • the results of the sample obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate of 1:1.6 are shown; in the second row of the table, the results of the sample obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate of 1:1.4 are shown; in the third row of the table, the results of the sample obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate of 1:1.2 are shown; in the fourth row of the table, the results of the sample obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate of 1:1.1 are shown; in the fifth row of the table, the results of the sample obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate of 1:1.05 are shown.
  • Example 6 Synthesis of co-polyamides obtained from tartaric acid, suberic acid and HMDI .
  • Figure 5 shows the spectrum 1 H-NMR (d-DMSO)
  • Figure 6 shows the formula of the product obtained indicating the functional groups highlighted in the spectrum
  • Table 3 shows the legend relating to this spectrum
  • Figure 7 the spectrum 13 C-NMR (d-DMSO)
  • Figure 8 shows the formula of the product obtained indicating the functional group highlighted in the spectrum
  • Table 4 shows the legend relating to this spectrum.
  • the product was characterised through spectroscopy 1 H-NMR and 13 C-NMR, but not through chromatographic analysis GPC, the product being insoluble in the eluent that is compatible with the instruments provided.
  • the casting phase was conducted for the products obtained on supports of a different nature, in particular polyethylene supports, non-treated common glass and aluminium were used.
  • polymer films of PTPLGAHI were obtained that were able to adhere to the common glass, to the aluminium, inasmuch as they were perfectly resistant to the mechanical stress arising from the detachment thereof, and were able to interface with the aluminium.
  • Such polymers have great versatility that enables them to be used for surface coatings of the glass and for manufacture of packaging, coupling them with the aluminium, for example in food packaging, as such materials enable excellent protection from the humidity, from the air and from the light, that is anyway greater than that offered only by the polymer.
  • the system is stirred for about 30 min in nitrogen atmosphere, the temperature of the reaction system is kept at about 4O 0 C by using an ice bath.
  • CC>2 develops, the reaction system become more viscous and turbid for the progressive formation of the oligomers.
  • the polymer obtained is spread on a support, for example a LDPE sheet, and is left stand in N 2 atmosphere on the support till an optimum value of the viscosity it is achieved.
  • the colouring agent is absorbed and kept by the polymer, also by the dried polymeric film.
  • the colouring agent is kept into the polymers and has a good colouring efficacy even if used at very low concentration, for example concentrations of the order of 0.05%.
  • the colouring agent does not modify the features of the obtained polymer and do not favour and/or trigger degradative reactions .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

A method for obtaining polyamides having a general formula [-CO-R'1-CONH-R2-NH-] comprises mixing a first compound having a general formula R1(COOH)2 with a further compound having a general formula R2(NCO)2, to bring about a polymerisation reaction, wherein R1 is a radical provided with at least an alcoholic function; a biodegradable polyamide having a general formula [-CO-R'1-CONH-R2-NH-] is obtained from a first compound R1(COOH)2 and from a further compound R2(NCO)2, wherein R1 comprises a radical provided 10 with at least an alcoholic function.

Description

Biodegradable plastic materials
The invention relates to biodegradable plastic materials and methods for obtaining biodegradable plastic materials.
Known plastic materials are today cheap to make, they can be produced with properties that are also very different from one another and this means that they can be used for widely varying purposes and for producing objects with different purposes and different features.
Known plastic materials, however, have great drawbacks: they are mostly produced from non-renewable sources, such as petroleum, take a very long time to degrade, and are therefore materials that are highly pollutant for the environment .
A massive use of the various plastic materials furthermore makes such drawbacks even greater and means that the disposal of the known plastic materials is a major and very current drawback.
In order to overcome such drawbacks it was decided to recycle plastic products, but recycling can be applied in a limited manner because of qualitative restrictions and restrictions on the use of the final products obtained, and has drawbacks due to the possible production of polluting substances and the energy required for the process of treating material to be recycled. Also the incineration of the products in plastic material to obtain at least a partial recovery of energy may have the aforementioned drawbacks and is not therefore easy to implement .
In order to overcome the aforementioned drawbacks, to produce plastic materials, also renewable and/or biodegradable raw materials have been used, such as starch, PLA (polylactic acid) of natural origin that make produced plastic materials biodegradable .
Nevertheless, these raw materials have a high cost and very often require hard processing conditions, this making the final price of plastic materials produced with said raw materials very high.
Furthermore, plastic materials obtained from biodegradable raw materials have physical and mechanical features that greatly limit the use thereof.
For the aforementioned reasons, the use of biodegradable plastics is still very limited.
An object of the invention is to provide biodegradable plastic materials. A further object is to provide methods for obtaining biodegradable plastic materials.
A further object is to provide biodegradable plastic materials having a limited cost.
Still another object is to provide biodegradable plastic materials having good mechanical features and which can be easily processed.
Still another object is to provide plastic materials that have good physical and mechanical features and which can therefore be used like traditional plastics . In a first aspect a method is provided for obtaining polyamides having general formula [-CO-R/ 1-CONH-R2-NH-] comprising mixing a first compound having a general formula
Ri (COOH) 2 with a further compound having a general formula
R2 (NCO) 2, to bring about a polymerisation reaction, in which Ri is a radical provided with at least an alcoholic function.
In a second aspect, a method is provided for obtaining co- polyamides having a general formula [-CO-R3-CONH-R2-NHCO-R'!-
NH-R2-NH-] comprising mixing a first compound having a general formula Ri (COOH) 2 with a second compound having a general formula Rs(COOH)2 and further mixing with a further compound having a general formula R2(NCO)2 to bring about a polymerisation reaction, in which Ri is a radical provided with at least an alcoholic function.
In a third aspect, a method is provided for obtaining co- poly (amide esters) comprising a first phase in which glycolic acid (OH-CH2-CO-OH) is made to react with lactic acid (OH-CH- (CH3) -CO-OH) and succinic anhydride (C4H4O3) to obtain a poly (lactic glycolic carboxy terminated) acid having a general formula [-OH-CO-C2H4-CO- [0-CH2-CO-O-CH2- (CH3) -C0-0-] n-H] and a second phase in which the product that is obtained from the reaction of the first phase, is mixed with a first compound having a general formula Ri(COOH)2, and further mixed with a further compound having a general formula R2(NCO)2 to bring about the polymerisation reaction, obtaining polyesters having a general formula [-NH-R2-NH-CO-R^-CO-NH-R2-NH-CO- C2H4-CO-[O-CH2-CO-O-CH2- (CH3) -C0-0-] n-iCH2-CO-O-CH2- (CH3) -CO-] m, in which Ri is a radical provided with at least an alcoholic function.
In a fourth aspect, a method is provided for obtaining co- poly (amide urethanes) having a general formula [-NH-R2-NH-CO- Ri-CONH-R2-NH-CO- (0-CH2-CH2-) x- (O-CH (CH3) -CH2-) Y- (0-CH2-CH2-) z- 0-C0-] comprising mixing a first compound having a general formula Ri(COOH)2 with a fourth compound having a general formula H- (0-CH2-CH2-) x- (O-CH (CH3) -CH2-) Y- (0-CH2-CH2-) z-0H and further mixing with a further compound having a general formula R2(NCO)2 to bring about a polymerisation reaction, in which Ri is a radical provided with at least an alcoholic function.
In a fifth aspect, a method is provided for obtaining co- poly (amide urethanes) having a general formula [-NH-R2-NH-CO- Ri-CONH-R2-NH-CO- (0-CH2-CH2-) n-0-C0-] comprising mixing a first compound having a general formula Ri(COOH)2 with a fifth compound having a general formula H- (0-CH2-CH2-) n-0H and further mixing with a further compound having a general formula R2(NCO)2 to bring about a polymerisation reaction, in which Ri is a radical provided with at least an alcoholic function.
In a sixth aspect a method is provided for obtaining co- polyesters having a general formula [[ (-0- (CH2-) 5-CO) m-O-CH2- CH2-O-CH2-CH2-O- (-CO- (CH2-) 5-O) m]n-CO-Ri-CO-] comprising mixing a first compound having a general formula Ri(COOH)2 with a sixth compound having a general formula [ (-0- (CH2-) 5-CO) m-0- CH2-CH2-O-CH2-CH2-O- (-CO- (CH2-) 5-0) m]n to bring about a polymerisation reaction, in which Ri is a radical provided with at least an alcoholic function.
In a seventh aspect, a method is provided for obtaining co- poly (amide urethanes) having a general formula [-NH-R2-NH-CO-
R1-CONH-R2-NH-CO- (0-CH2-CH2-) n-0-CO-] comprising mixing a first compound having a general formula Ri(COOH)2 with a seventh compound having a general formula H-[O-CH-(CH3)-
CH2Jn-OH and further mixing with a further compound having a general formula R2(NCO)2 to bring about a polymerisation reaction, in which Ri is a radical provided with at least an alcoholic function.
In an eight aspect, a biodegradable polyamide is provided having a general formula [-CO-R' 1-CONH-R2-NH-] obtained from a first compound Ri(COOH)2 and from a further compound
R2(NCO)2, in which Ri comprises a radical provided with at least an alcoholic function.
The quantity of the first compound is comprised between 30% and 70%, preferably it is of the order of approximately 50%. The quantity of the further compound is comprised between 30% and 70%, preferably it is of the order of approximately 50%.
In a version, the first compound and the further compound are mixed in quantities that are stoichiometric to one another.
In further versions, the first compound and the further compound are mixed in quantities so that the reciprocal molar ratio is 1:1.05, and/or 1:1.1, and/or 1:1.2, and/or 1:1.4, and/or 1:1.6.
In a ninth aspect, a biodegradable polyamide is provided having a general formula [-CO-R3-CONH-R2-NHCO-R' 1-NH-R2-NH-] obtained from a first compound Ri(COOH)2 and from a further compound R2(NCO)2, and from a third compound R3(COOH)2, in which Ri comprises a radical provided with at least an alcoholic function.
The molar quantity of the first compound is comprised between 10% and 80%, preferably between 35% and 45%, still preferably it is of the order of approximately 25%. The molar quantity of the further compound is comprised between 10% and 80%, preferably between 40% and 60%, still preferably it is of the order of approximately 50%. The molar quantity of the third compound is comprised between 10% and 80%, preferably between 35% and 45%, still preferably it is of the order of approximately 25%.
In a version, the first compound and third compound are mixed in quantities that are equimolar to one another. In a tenth aspect, a biodegradable co-poly (amide ester) is provided having a general formula [-NH-R2-NH-CO-R' 1-CO-NH-R2- NH-CO-C2H4-CO- [0-CH2-CO-O-CH2- (CH3) -CO-O-] n-iCH2-CO-O-CH2- (CH3) - C0-]m, obtained from a first compound having a general formula Ri(COOH)2, a compound of the type of a poly (lactic glycol carboxy terminated) acid having a general formula OH- CO-C2H4-CO- [0-CH2-CO-O-CH2- (CH3) -CO-O-Jn-, and a further compound having a general formula R2(NCO)2, in which Ri is a radical provided with at least an alcoholic function. The poly (lactic glycol carboxy terminated) acid can be obtained from glycolic acid, lactic acid and succinic anhydride .
The molar quantity of the first compound is comprised between 10% and 80%, preferably between 35% and 45%, still preferably it is of the order of approximately 25%. The molar quantity of the further compound is comprised between 10% and 80%, preferably between 40% and 60%, still preferably it is of the order of approximately 50%. The molar quantity of the poly (lactic glycol carboxy terminated) acid is comprised between 10% and 80%, preferably between 35% and 45%, still preferably it is of the order of approximately 25%.
In a version, the first compound and poly (lactic glycol carboxy terminated) acid are mixed in quantities that are equimolar to one another. In some versions, the polyamides, the co-polyamides and the co-poly (amide esters) obtained have an almost linear structure and R' i is a radical having the same formula as Ri. In other versions, the polyamides, Ie co-polyamides and the co-poly (amide esters) obtained have a branched and/or a cross-linked structure and R' i is a radical comprising in the formula thereof the radical R2 and having a general formula [-CH (OH) -CH-O (-CONH-R2-NH-) -CO-] .
In a eleventh aspect a biodegradable co-poly (amide urethane) is provided having a general formula [-NH-R2-NH-CO-RI-CONH-R2- NH-CO- (0-CH2-CH2-) x- (O-CH (CH3) -CH2-) Y- (0-CH2-CH2-) z-0-C0-] that is obtained from a first compound having a general formula Ri(COOH)2, a fourth compound having a general formula H-(O- CH2-CH2-) x- (O-CH (CH3) -CH2-) Y- (0-CH2-CH2-) z-OH, and a further compound having a general formula R2(NCO)2, in which Ri is a radical provided with at least an alcoholic function. The fourth compound is chosen from the block co-polymers with poly (ethylene glycol) -poly (propylene glycol) -poly (ethylene glycols) (PEG-PPG-PEG) , copolymers can be used having molecular weights that differ from one another, in particular the poloxamer 1100 can be used as a fourth compound. In a version, the fourth compound comprises poloxamer having molecular weight comprised between 200 and 2000, preferably poloxamer having molecular weight of about 1100. The weight quantities of the first compound and of the fourth compound can be appropriately varied so that the ratio between the reciprocal weight quantities is between 4 and 0.5, in particular, the aforementioned quantities can be chosen in such a way that the ratio thereof is appropriately equal to 1.
The molar quantity of the further compound is comprised between 10% and 80% of the stoichiometric ratio, preferably between 40% and 60%, still preferably it is of the order of approximately 50%.
In an twelfth aspect, a biodegradable co-poly (amide urethane) is provided, having a general formula [-NH-R2-NH-CO-RI-CONH-R2- NH-CO- (0-CH2-CH2-) n-0-C0-] obtained from a first compound having a general formula Ri(COOH)2, a fifth compound having a general formula H- (0-CH2-CH2-) n-0H, and a further compound having a general formula R2 (NCO) 2, in which Ri is a radical provided with at least an alcoholic function.
The fifth compound is chosen between the oligomers of poly (ethylene glycol). The fifth compound may be also chosen between the oligomers of the poly (propylene glycol).
The fifth compound may be chosen between the block copolymers comprising PEG blocks and/or PPG blocks. The molecular weight of the fifth compound may be comprised between 500 and 5000, in particular between 1000 and 4000.
The molar quantities of the first compound and of the fifth compound can be appropriately varied in such a way that the ratio between the reciprocal molar quantities is comprised between 4 and 0.5, in particular, the aforementioned quantities can be selected in such a way that the ratio thereof is equal to 1.
The molar quantity of the further compound is comprised between 10% and 80% of the stoichiometric ratio, preferably between 40% and 60%, still preferably it is of the order of approximately 50%.
In a thirteenth aspect, a biodegradable co-polyester is provided having a general formula [[ (-0- (CH2-) 5-CO) m-O-CH2- CH2-O-CH2-CH2-O- (-CO- (CH2-) 5-O) m]n-CO-Ri-CO-] obtained from a first compound having a general formula Ri(COOH)2, and from a sixth compound having a general formula [ (-0- (CH2-) 5-CO) m-0- CH2-CH2-O-CH2-CH2-O- (-CO- (CH2-) 5-O) m]n, in which Ri is a radical provided with at least an alcoholic function.
The sixth compound chosen from the polymers of the caprolactone, polymers can be chosen having molecular weights that are different from one another.
The molar quantities of the first compound and of the sixth compound can be varied in such a way that the ratio between the aforementioned quantities is comprised been approximately 4 and approximately 0.2, in particular, said compounds can be mixed in quantities that are stoichiometric in relation to one another. Owing to this aspect of the invention, it is possible to obtain plasticising substances, i.e. substances that can be added to other polymeric substances, for example PVC, decreasing the vitreous transition temperature thereof, in order to thus increase the workability, flexibility and extendibility thereof.
The plasticisers added to the polymers are not bonded permanently to the structure of the polymers and can therefore be released by the latter. This constitutes a drawback because the plasticising substances, such as for example phthalates, are usually cancerogenous and/or toxic, and may have negative effects on the respiratory, endocrinal, circulatory and reproductive systems and create great limits to the use of plasticised polymers .
The polymers obtained on the basis of this aspect of the invention, as they can be obtained by co-monomers of natural origin, are not toxic and, on the other hand, form with the PVC very durable bonds, so that the release thereof is very limited.
This enables PVC polymer blends with improved characteristics to be obtained that do not have restricted use due to the release of possible toxic or harmful substances. In a fourteenth aspect of the invention, a biodegradable co- poly (amide urethane) is provided, having a general formula [- NH-R2-NH-CO-RI-CONH-R2-NH-CO- (0-CH2-CH2-) X- (0-CH- (CH3) -CH2] Y- (0- CH2-CH2-) z-O-CO] obtained from a first compound having a general formula Ri(COOH)2, a seventh compound having a general formula H- [O-CH- (CH3) -CH2] n-0H, and a further compound having a general formula R2(NCO)2, in which Ri is a radical provided with at least an alcoholic function.
Preferably the seventh compound is chosen between the polymers of the poly (propylene glycol), PPG. Still preferably the seventh compound comprises poly (propylene glycol) having a molecular weight of about 400. In a fifteenth aspect, a composite material is provided comprising at least a layer made with at least one of the plastic materials according to any one of the aspects eighth to fourteenth, and a further layer made in a further material .
In a version said further layer comprises ordinary glass, silanised glass, silicone rubber, Teflon-butyl rubber, nylon sheets, PVC sheets, LDPE sheets, aluminium sheets. In a sixteenth aspect of the invention, a polymer blend is obtained by mixing at least one of the plastic materials according to any one of the aspects eighth to fourteenth, with a further plastic material.
In a seventeenth aspect of the invention, is provided the use of at least one of the plastic materials according to any one of the aspects eighth to fourteenth to make biodegradable objects .
In a eighteenth aspect of the invention, is provided the use of at least one of the plastic materials according to any one of the aspects eighth to fourteenth to make biocompatible objects.
The radical Ri may comprise two alcoholic functions (-0H) , and can be chosen between the aliphatic radicals or between the radicals containing double bonds, between the radicals having linear or branched, and/or cross-linked chain. The first compound can be selected from the dihydroxy acids, in particular tartaric acid or a similar compound thereto can be used as a first compound.
The radical R2 comprises an aliphatic radical, or a radical provided with double bonds, or having linear or branched, and/or cross-linked or cyclical chain, or also aromatic chain .
The further compound preferably comprises terminal diisocyanate that can be chosen from the aliphatic chain diioscyanates, or from diioscyanates provided with double bonds, or having linear, or branched, and/or cross-linked, or cyclical chain. In particular, the diisocyanate can be chosen from
Hexamethylene Diisocyanate (HMDI), 1,8 diisocyanatooctane
(OMDI), 1,12 diisocyanatododecane (DMDI).
In a version, using an organometal compound, in particular dibutyl tin laurate (DBLT), as a catalyst is provided for.
In a version, amalgamating the first compound to anhydrous
DMF (N, N-dimethylformamide) is provided for.
Owing to the aspects of the invention, it is possible to obtain biodegradable plastic materials. It is furthermore possible to obtain plastic materials having features that are very different from one another and which can be used for different purposes and to replace a vast range of traditional plastic materials.
By varying the quantities of reactants introduced it is possible to obtain polymers with branched, or cross-linked, or linear chain.
In particular, when the first product is mixed with the further product in quantities that are greater than the stoichiometric quantities and/or in quantities that are approximately the same as the stoichiometric quantities, it is possible to obtain linear chain polymers.
If, on the other hand, the further product is mixed with the first product in quantities that are greater than the stoichiometric quantities, it is possible to obtain branched and/or cross-linked chain polymers.
In a nineteenth aspect of the invention, a composite material is provided comprising at least a layer made with at least one of the plastic materials according to the invention, and a further layer made of a further material. The further material may comprise, for example aluminium, polyethylene, glass, ceramics.
Owing to this aspect of the invention, it is possible to obtain composite materials comprising a layer in biodegradable plastic material. With these materials various objects can thus be made, such as for example containers, for examples containers of food substances or of medical preparations, in which the layer of biodegradable plastic material is intended to enter into contact with a given product the chemical-physical and/or the sterility of which it is necessary to maintain, and in all the cases in which it is necessary to avoid the release of possibly harmful or toxic substances from the materials that come into contact with this product.
Plastic materials according to the invention can be obtained by starting from tartaric acid and biodegradable polymeric compounds, such as for example PEG, PCL, PLGA, and in certain cases also from polymeric biocompatible compounds, such as for example PEG, PCL and PLGA that are commonly used for biomedical uses, so also the respective plastic materials obtained can be considered to be not only biodegradable but also biocompatible and, therefore, usable in a biomedical context, for example to create structural materials such as screws, or prostheses, or also to make soft synthetic tissues that partially replace human tissues, or also to make pharmaceutical compositions. Plastic materials obtained according to the invention, have been analysed to be able to be characterised when the latter has been revealed to be possible, in fact the obtained polymers having a branched or cross-linked structure were revealed to be insoluble in many solvents such as for example: DMF anhydrous (N,N-dimethylformamide) , CHCI3
(methylene chloride) , DMSO (d-dimethyl sulfoxide) , acetone, ethyl ether, CH3COOH, water, ethyl acetate, CH3OH, CH2Cl2, for which reason it is not possible to characterise them either with NMR (Nuclear Magnetic Resonance) , or with GPC (Gel Permeation Chromatography) , or with viscometric measurements. The linear structure polymers were revealed to be insoluble in methylene chloride, so it was not possible to characterise them with GPC, on the other hand they were subjected, when possible, to NMR using a "Bruker UltraShield Advance" 400-MHz spectrometer using d-DMSO (d-dimethyl sulfoxide) as a solvent, with IR spectroscopy with a "Perkin Elmer 1725X" spectrophotometer, and with viscometric tests conducted with a glass viscometer for solutions of the Ubbelholde-type with N, N dimethylformamide as a solvent operating at a temperature of approximately 250C owing to a thermostatic bath. The viscometric measurements enabled the variation in the molecular weight of the polymers to be followed in the course of the respective polymerisation reactions.
From the results obtained, for all the types of polymers, a low molecular weight value it is noted for all the classes of polymers obtained, the average molecular weight of the co- poly (amide esters) being slightly greater than those of the other classes of polymers.
The average molecular weight of the polymers increases if the polymers were subjected to extraction, for example an extraction with a "Kumagawa extractor", this enabling the residual reaction solvent and the oligomers to be removed from the polymers .
Samples of the polymers obtained according to any one of the aspect of the invention, have been subjected furthermore to rotational rheometry tests, in order to investigate the stress behaviour of the samples.
Such tests, enabled some polymers having typical thermoplastic characteristics and some others polymers having typical thermosetting characteristics to be identified. The capacity of adhesion of the polymers obtained to various supports chosen between the most commonly used materials was further investigated, in order to evaluate the possible couplability of the polymers obtained on such materials. These tests were conducted according to the casting procedure, explained with greater detail in the following examples, and have enabled good couplability of the polymers to certain supports to be shown, for example aluminium and polyethylene, in particular LDPE, some polymers shows furthermore a good adhesion to the ordinary glass, the silanized glass, rubber. Accordingly, the polymers obtained can be used for producing composite materials, for example materials to be used to produce containers such as those used to contain certain types of foods . The obtained polymer materials had good workability with all the known techniques for processing plastic materials, they gave good responses both to extrusion processing, injection moulding processing, thermoforming processing, and furthermore have excellent filming processability filming, in fact polymer films are obtained that are provided with excellent features of regularity and with a thickness that is also very limited.
The obtained samples furthermore have features that are very different from one another, for example certain samples have great deformability and elasticity, others were revealed to be soft, still others had certain stiffness.
With the reactions done, it was possible to obtain different kinds of polymers, furthermore, by varying the relative concentration of the reactants, as will be in detail explained with reference to example 4, it was possible to obtain plastic material of the same kind but with mechanical properties different from one another, i.e. for example thermoplastic and thermosettable polyamides . It was also possible to modulate in an almost continuous manner the properties of the different plastic materials of the same kind, thus obtaining polymers of the same kind that can be very well used for many uses very different from one another. As said, with the invention it is possible to obtain biodegradable polymer materials, the biodegradability of which can furthermore be varied by acting on structural parameters such as the percentage of reticulation, crystallinity and also the degree of swelling in water, to obtain each time, the requested specific features. In particular, it is normally found that high percentages of swelling in water foster biodegradation. In the case of co (polyamides-urethanes) with inserted PEG chains, a highly hydrophile material, a certain degree of swelling it is observed that is variable according to the total percentage of PEG in the co-polymer and also to the molecular weight of the used PEG.
For weight percentages of PEG that are variable from 20 to 40%, percentage increases in water of 5-20% are observed. Thus, by modifying the percentages of the single monomers, and/or the degree of reticulation of the plastic materials obtained, it is possible to vary the biodegradability of the plastic materials and, therefore the possible intended uses of such plastic materials and/or of products obtained from such plastic materials. To test the biodegradability of the plastic materials according to the invention, the samples of obtained materials were all subjected to degradation tests that were carried out in plastic cups, filling them Η full with the appropriate terrain and arranging at the centre thereof the polymer sample in a horizontal manner. The tests were conducted in 3 terrains that were different from one another: soil, universal loam, and activated soil that differs from the simple soil inasmuch as at the interior thereof the nutrients for the microorganism present are increased. The weight loss to which the samples are subjected is determined at 6 different analysis times, at 1, 2, 3, 4, 6 and 8 weeks from the start of the process, each single sample, after being removed from the terrain to be analysed is not then reintroduced into the terrain. Each test was then conducted in triplicate so as to ensure certain representativity in the data obtained.
During the biodegrading process each sample is wet 3 times a week (Monday - Wednesday - Friday) with lOcc of tap water, so as to maintain the humidity of the terrain constant for as long as possible. For the tests in activated soil, the microorganisms need to be provided with the necessary nutrients: the first 3 times that the samples are wet, lOcc of a 43,86 rtiM saccharose solution is used. After the first week, also these samples are wet with lOcc of tap water.
These tests have been conducted by laying 1.5 g of film of the polymeric materials in a 1 g suspension of terrain in 100 ml of a solution of mineral salts and adding a saccharose solution that has been supplied to the terrain in a progressive manner during the first week, separating the saccharose solution equally into 3 different corresponding supplies rather than inserting the saccharose solution completely at the initial time. Before adding the saccharose solution, an attempt is made for generating a sort of preferential channel in the terrain that fosters the diffusion of the nutrient as far as the sample. The saccharose solution was produced by dissolving 7.5 g of saccharose in 500 ml of tap water, and providing each sample with 10 ml of the obtained solution after it has been suitably homogenised.
In the totality of the three additions, 450 mg are added to each sample subjected to the study. At the end of the appropriate degradation period, the samples have to be gently removed from the terrain and efficiently cleaned of the terrain dirtying the surface thereof. Distilled water is used to facilitate the cleaning operation, water that has to be removed from the sample first with the assistance of a little filter paper, then with a drying period in an oven for 24 hours at 35 0C.
After that can be detected the losses for each sample in weight percentages that are indicative of the biodegradation efficiency to which each sample was subjected. A certain degradation of the plastic materials subjected to these tests has always been witnessed, that has confirmed the fact that biodegradable plastic materials have really been produced.
The results obtained enable it to be concluded that produced plastic materials have good degradability, as expected, and that this degradability can be varied by varying the structure of the various plastic materials, for example by varying the molecular ratio between the various original monomers used to obtain the plastic materials, and the degree of reticulation of such plastic materials. This enables various uses of the obtained plastic materials to be expected, and to be able to obtain each time, through simple modifications to the productive process, plastic materials having the effective desired features, for example degradation times that are suitable for a desired product obtained with these plastic materials.
This enables various objects to be produced with such plastic materials having a degradability that is such as to be able to be disposed of without any problem, for example together with organic rubbish, but such as not to entail too early degradation of such objects before the use thereof has been terminated.
Obtained plastic materials were further subjected to toxicological tests to determine whether during the degradation process such plastic materials can release toxic substances .
For the test, 3 polymer samples of the synthesised plastic materials and 6 spathyphyllum plants each positioned in a pot were used. The polymeric films are vertically buried in 3 pots, taking great care not to break the roots of plants during the operation, whilst the remaining 3 plants simply have the role of a blank.
The analysis is continued for 30 days, during which the 6 pots are periodically wet in as even homogeneously as possible. At the end of the set period, the films extracted from the terrain are washed with distilled water and are then dried in an oven for 24 hours at 35 0C. Therefore the samples are analysed. The analysis show that all the samples are biodegraded, and that the biodegradative process has almost a regular course over time, i.e. the biodegradation degree of the samples is almost proportional to the degradation time, this correlation being independent from the particular terrain used. Nevertheless the samples buried in universal loam show a higher degradation degree in relation to the degradation degree of the sample buried into the soil and into the activated soil, independently from the polymeric material of the sample. In fact the universal loam is naturally very rich in nutrient, and therefore the microorganisms can develop better and more quickly.
Furthermore, amongst the polymers according to the invention, samples of PTPLGAHI polyamide polyester polymers appear more degraded than the samples of the other polymers . Obtained plastic materials were further subjected to swelling tests that enable for almost all the obtained plastic materials, a low tendency to swelling in water, i.e. low softening, to be highlighted. In other words, the obtained polymers show a certain tendency to swell in water, this promoting the degradation of such polymers, but swelling it is not so fast, so that degradation process is not so fast, and therefore such polymers may be used for obtaining biodegradable objects without the risk that such objects begin to degrade too fast as desired. This behaviour, together with the degradability of such plastic materials, enables different use to be provided for these plastic materials also because on the one hand these plastic materials are sufficiently resistant as not to deteriorate too soon, for example during the use of an object produced with such plastic materials, for example bags for organic rubbish, and on the other hand the degradability thereof enables the disposal thereof with the organic substances .
Between the obtained plastic materials, the co (polyamides- urethanes) with inserted PEG chains has a swelling degree that is greater than that of the other plastic materials and is variable in function of the total percentage of PEG present in the co-polymer, and also of the molecular weight of the PEG used. Such plastic materials show a biodegradability that varies in a fairly consistent manner, varying the molecular weight of the PEC and the percentage thereof.
For example, by varying the PEG weight percentages from 20 to 40% a water percentage increases of 5-20% were observed. This enables that the plastic materials provided with the PEG as a starting co-polymer to be used for all those uses in which a certain swelling and very short degradation times are requested, it being established that these two features, degradation and swelling time, can be appropriately varied, as seen, by varying the PEG percentage and the molecular weight thereof.
For example, the above plastic materials can be used in the production of pharmaceutical compositions for which a certain swelling is required, or in the production of soft textiles. Plastic materials obtained according to the invention, can, furthermore, be mixed with polymer substances of different types, in particular low-cost polyesters, such as polyadipates, polysuccinates, polycaprolactone or, alternatively, natural polysaccharides such as hemicellulose starches or cellulose to obtain polymer blends, having the most widely varying physical, mechanical properties, such properties being if possible also very different from those of the original polymers and furthermore enabling polymer blends to be obtained having a lower cost than plastic materials according to the invention. The technology of the polymer blends is a rapid and economic approach for obtaining materials that are different from those of the individual constituents .
The quality of a polymer mixture depends on the compatibility between the components of the system and three general cases may arise:
• mixable blends, obtained from polymers that are completely mixable together that form a single homogenous phase, with good inter-segmental interaction; • non-mixable blends, obtained from polymers that are completely unmixable together and in which two or three distinct phases are present;
• partially mixable blends, obtained from polymers that are mixable together, but in which zones of dishomogeneity can be noted with contours that are not well defined.
The compatibility of the components of a blend can be defined on the basis of the property-composition curves, where property is defined as the macroscopic features of the material, such as the mechanical, rheological properties, etc..
In most cases, the properties of the blends are intermediate between those of the components, although they are often different from the expected ones and do not follow ideal laws of additivity. In reality, few pairs of polymers are mixable together in a thermodynamic sense, thus giving origin to a blend of the first type.
In most cases the polymer blends are compatible, i.e. they are not mixable in a thermodynamic sense but are mixed and are dispersed very homogenously with a phase with a temporal stability that is made possible by factors of kinematic type. In order to improve adhesion, i.e. the compatibility of the polymer mixtures, it is necessary to decrease the interfacial tension between the two phases, by exploiting for example the formation of physical or chemical bonds between the phases owing to the addition of small quantities of a further component, such component being said coupling agent. The coupling agents are normally block co-polymers in which a block consists of repeating units that are the same of (or at least mixable in) the other phase.
Plastic materials according to the invention were suitable for obtaining polymer blends, of all three types and, using appropriate coupling agents, it was possible to improve the features of the obtained blends . Obtained plastic materials have mechanical and processability features that are also very different from one another, for example plastic materials have been obtained that have pronounced elastic performance, and others have been obtained that have low deformability . This enables widely differing uses to be provided for these plastic materials, and to suppose being able to replace many- known plastic materials that have the aforementioned drawbacks with plastic materials according to the invention. Furthermore, as already said, repeating the reaction explained above, and varying the stoichiometric ratio between the reactants, it is possible to obtain plastic materials of the same kind, but with different features between each others . In particular, tests have been effected for obtaining different plastic materials of the same kind, the tests have been conducted in similar manner for all the different plastic materials, but will be explained in detail the tests made for polyamides materials (PTHI) . The different tests for the different plastic materials according to the invention, show similar results for all the plastic materials, i.e. the tests show that by varying the relative percentage of the different reactants plastic materials of the same kind but with different features can be obtained. Therefore, plastic materials of the same kind but suitable for being used for many different uses can be obtained, such different uses requiring plastic materials having, for example, different behaviour at high/low temperature, different mechanical features, etc..
The disclosed reactions, of which is herein below shown the diagram, that have been repeated with different quantities of the reactants, enabled in any case good plastic materials to be obtained, having a good polymerisation degree and suitable to be subjected to different various subsequent processing operations . In any case polymers that can be easily worked and processed, event with different technique from which regular, homogeneous and thin film can be obtained, are produced. Both the thermoplastic and the thermosetting polymers obtained have shown a good processability and filmability, therefore for both the two different kinds of polymers many different uses can be supposed.
For example thermoplastic polymers can be used for obtaining sheet materials, film materials, even very thin, plastic bags, into the packaging field, for encapsulating tablets, medicines, plant protection products, for obtaining blisters, or also as intermediate products for obtaining polyester resins .
Furthermore, since all the polymers according to the invention are biodegradable and non-toxic materials, can be used for obtaining biodegradable products, for example the bags for collecting the organic fractions of the waste, or also the pot to be planted directly with the plant so as no to break the roots of the plant and that after a preset period of time degrade. The possible sector of use of the polymers according to the invention are various, preferably those uses in which the biodegradability, and the biocompatibility thereof is exploited. Cross-linked or branched polymers cannot be worked in melted conditions; therefore such polymers are preferably processed by injection. All the polymers obtained can be used for obtaining materials in which two different materials are coupled one another, for example for soaking paper, or generally, for soaking all known cellulosic materials instead of using present plasticizing materials, so as to obtain biodegradable paper products .
The polymers obtained can be spread on the materials, i.e. the paper, or can also mixed to other materials, for example to fibrous materials. The polymer can also be used in biomedical field, for example for producing cannulas, surgical yarn, prosthesis or implantations that have to be absorbed after a certain period of time, etc ..
The invention may be better understood and implemented with reference to the attached examples that show some embodiments thereof by way of example and with reference to the attached
Figures in which:
Figure 1 shows the spectrum 1H-NMR (d-DMSO) of a polyamide obtained according to the first example; Figure 2 shows the general formula of the polyamide obtained according to the first example showing the functional groups of the spectrum NMR in Figure 1;
Table 1 shows the legend relating to the spectrum in Figure l; Figure 3 shows the spectrum 13C-NMR (d-DMSO) of a polyamide obtained according to the first example;
Figure 4 shows the general formula of the polyamide obtained according to the first example showing the functional groups of the spectrum NMR in Figure 3; Table 2 shows the legend relating to the spectrum in Figure
3;
Figure 5 shows the spectrum 1H-NMR (d-DMSO) of a polyamide obtained according to the fifth example;
Figure 6 is the general formula of the polyamide obtained according to the sixth example showing the functional groups of the spectrum NMR in Figure 5; Table 3 is the legend relating to the spectrum in Figure 5;
Figure 7 is the spectrum 13C-NMR (d-DMSO) of a polyamide obtained according to the sixth example;
Figure 8 is the general formula of the polyamide obtained according to the sixth example showing the functional groups of the spectrum NMR in Figure 7;
Table 4 is the legend relating to the spectrum in Figure 7;
Figure 9 is the spectrum 1H-NMR (d-TFA) of an oligomer PLGA-
COOH obtained according to the ninth example; Figure 10 is the general formula of the oligomer PLGA-COOH obtained according to the ninth example showing the functional groups of the spectrum NMR in Figure 9;
Table 5 is the legend relating to the spectrum in Figure 9;
Figure 11 is the spectrum 13C-NMR (d-TFA) of an oligomer PLGA-COOH obtained according to the ninth example;
Figure 12 is the general formula of the oligomer PLGA-COOH obtained according to the ninth example showing the functional groups of the spectrum NMR in Figure 11;
Table 6 is the legend relating to the spectrum in Figure 11; Figure 13 shows the spectrum IR (CH2CI2) of the oligomer
PLGA-COOH obtained according to the ninth example;
Table 7 is the legend relating to the spectrum in Figure 13;
Figure 14 is the spectrum 1H-NMR (d-TFA) of a polyamide
(PTPLGAHI) obtained according to the ninth example; Figure 15 is the general formula of the polyamide obtained according to the ninth example showing the functional groups of the spectrum NMR in Figure 14;
Table 8 is the legend relating to the spectrum in Figure 14;
Figure 16 is the spectrum 13C-NMR (d-TFA) of a polyamide (PTPLGAHI) obtained according to the ninth example;
Figure 17 is the general formula of the polyamide obtained according to the ninth example showing the functional groups of the spectrum NMR in Figure 16;
Table 9 is the legend relating to the spectrum in Figure 16; Figure 18 is the spectrum 1H-NMR (CDCl3) of a polyester PTPCL obtained according to the fourteenth example; Figure 19 is the general formula of the polyester obtained according to the fourteenth example showing the functional groups of the spectrum in Figure 18;
Table 10 shows the legend relating to the spectrum in Figure 18;
Figure 20 is the spectrum 13C-NMR (CDCl3) of a polyester PTPCL obtained according to the fourteenth example;
Figure 21 shows the formula of a polyester PTPCL obtained according to the fourteenth example showing the functional groups of the spectrum in Figure 20;
Table 11 is the legend relating to the spectrum in Figure 20.
Figure 22 shows the spectrum IR (from solution CH2CI2) of a polyester PTPCL obtained according to the fourteenth example;
Table 12 shows the legend of the spectrum in Figure 21. Figure 23 shows the mean values of the glass transition temperature for the polymers obtained according to the example 4, and measured both on the polymers before the extraction with "Kumagawa extractor" and on the polymers after the extraction with "Kumagawa extractor"; Figure 24 shows the viscosity [Pa*s] measured for the samples obtained according to the example 4 vs. the shear rate [1/s] .
Example 1 Synthesis of polyamides obtained from tartaric acid and HMDI (Hexamethylene Diisocyanate) .
This is achieved by mixing stoichiometric quantities of the reactants .
In an inert atmosphere, at room temperature, and through stirring, tartaric acid and HMDI (Hexamethylene Diisocyanate) were made to react in quantities that were stoichiometric to one another, in an anhydrous DMF (N,N-dimethylformamide) solution (at 40% reactants weight) , in the presence of DBLT dibutyl tin laurate) as catalyst that is 2% in weight.
Following a polycondensation reaction, linear structure polymers have been obtained.
In a previously dehumidified three-necked flask that is provided with a mechanical stirrer and with a cannula for nitrogen bubbling, under an inert atmosphere in this order tartaric acid (1.9389 g; 12.9174 mmoles), DBLT (83 μl) and anhydrous DMF (6.6 ml) are loaded, and after this mixture has become homogenous HMDI (2.0 ml; 12.8763 mmoles) is added. The reaction system is then heated to 5O0C, maintaining these conditions for approximately three hours .
Temperature was kept constant using a silicon oil bath and a thermostat .
After approximately three hours, the product was precipitated by the reaction mixture through the addition of water, then the product was washed twice with water in order to eliminate the solvent and non-reacted tartaric acid, then filtered and subsequently washed with methanol to eliminate the non- reacted diisocyanate and any secondary products with a low molecular weight, then further washed with ethanol before being dried in a vacuum.
Subsequently, the product was further washed with water at 7O0C for three hours (about 20 ml/g of dried product) so as to completely eliminate all the DMF. The quantity of subproducts with a low molecular weight collected after precipitation by ethyl ether of the mother liquors obtained by washing with methanol is always negligible .
The reaction was conducted in anhydrous conditions for avoiding the reaction between isocyanate and water, which can lead to the formation of the corresponding carbamic acid, which then evolves to the amine losing CO2.
Furthermore, operations were conducted under a flow of nitrogen to enable removal of the secondary product of the polycondensation, namely CO2, and to prevent possible oxidising phenomena.
The product of the reaction was characterised by 1H-NMR and 13C-NMR and viscometric measurements; for a product obtained with the aforementioned reaction, Figure 1 shows the spectrum 1H-NMR (d-DMSO) , Figure 2 the general formula of the polyamide showing the functional groups of the spectrum NMR, and Table 1 shows the legend relating to this spectrum, Figure 3 shows the spectrum 13C-NMR (d-DMSO) , Figure 4 shows the general formula of the polyamide highlighting the functional groups of the spectrum NMR, and Table 2 shows the legend relating to this spectrum. The above reaction was repeated with various concentrations of tartaric acid, in particular increasing the concentrations progressively up to an excess of tartaric acid of 10% on a molar base with respect to the stoichiometric quantities thereof. The diagram of the reaction is set out below.
Figure imgf000027_0001
These tests have enabled polyamides with various physical and mechanical features to be obtained.
Example 2 Synthesis of polyamides obtained from tartaric acid and diioscyanates . Stoichiometric quantities of the reactants were mixed.
The reaction shown in example 1 was repeated using diisocyanates having a chain of different length, both a linear, branched, and/or cross-linked and cyclical chain, thus obtaining polyamides with mechanical features that vary in function of the chain of the diisocyanate and having a structure in which the length of the radical coming from the diisocyanate consequently varies according to the particular diisocyanate used. In particular, by subjecting the various polyamides obtained to tests to assess the response thereof to stress, it is noted that increasing the length of the chain of diisocyanate used, polyamides are obtained with less flexibility and which were therefore provided with a greater degree of crystalunity . On the other hand, by contrast decreasing in the length of the chain of diisocyanate used, polyamides are obtained having greater flexibility and therefore greater resistance to tension stress.
Example 3 Synthesis of polyamides with a branched and/or cross-linked structure obtained from tartaric acid and HMDI (Hexamethylene Diisocyanate) .
The reaction indicated with reference to example 1 was also used for the synthesis of polyamides with a branched and/or cross-linked structure from tartaric acid and HMDI, but using an excess of the 5% moles of HMDI with respect to the stoichiometry, as indicated by the following reaction.
In an inert atmosphere, at room temperature, and through stirring, tartaric acid and HMDI are made to react by loading 5% excess HMDI in moles with respect to the stoichiometric, in anhydrous DMF (N,N-dimethylformamide) solution (40% in reactant weight) in the presence of DBLT (dibutyl tin laurate) 2% in weight as a catalyst.
At room temperature and in an inert atmosphere, in two-necked flask that has been previously dehumidified through nitrogen vacuum cycles, tartaric acid (1.2887 g; 8.5856 mmoles) , DBLT (56 μl) and anhydrous DMF (4.5 ml) were introduced, and only- after this mixture had become homogenous was HMDI added (1.4 ml; 9,0134 mmoles) .
The reaction system was then heated to 5O0C, maintaining these conditions for about three hours . The temperature was kept constant by using a silicon oil bath and a thermostat.
At this point, once the visible evolution of CO2 had terminated, the mixture obtained was poured into polyethylene container with a flat bottom, that had previously been conditioned in an oven at 1000C, then bringing about the reaction per casting in an oven at 7O0C for approximately 36 hours, at the end of which a homogenous straw-coloured polymer film was collected that was dried under a vacuum to a constant weight. At the end of the turbulent production phase of the carbon dioxide, the reaction mixture was deposited on the bottom of a container with a flat bottom, bringing about the polymerisation reaction thanks to the action of the heat, at
7O0C temperature.
The technique mentioned above, known as casting technique, has enabled polymeric films to be obtained that are homogenous and provided with fairly good mechanical properties .
Such polymeric films were subjected to vacuum drying to a constant weight to eliminate the solvent contained inside and, subsequently, to further washing in water for some hours followed by drying to a constant weight.
The casting tests mentioned above were repeated using diisocyanates that are different from one another and varying the nature of the chosen support. The stated quantities refer to a product obtained with the reaction disclosed above, and the test was repeated by also working with supports of common non-treated glass, and aluminium.
Owing to the insolubility in the solvents, a peculiar feature of such polymers with a branched and/or cross-linked structure, it was not possible to characterise the products by NMR spectroscopy or through chromatographic analysis GPC.
The operating conditions used in excess of 5% in moles with respect to the stoichiometric HMDI, also enabled the hydroxyl groups that were present to react, giving rise to polyamides with a branched and/or cross-linked structure as shown in the following reaction:
Figure imgf000029_0001
The above-described reaction has been repeated so as to evaluate the reproducibility thereof, also varying some of the parameters of the reaction, and seeking for preferred values of the experimental parameters . The quantity of solvent (DMF) has been varied, and it has been noticed that the solvent has to preferably be present in quantity comprised between about 10% in weight and 55% on the weight of the reactants, more preferably comprised between about 30% in weight and 50% in weight on the weight of the reactants. Further preferably the concentration of DMF is about 40% in weight considered over the weight of the reactants .
The test effected have also shown that too low quantities of solvent make the solubility of the reactants to decrease even in the first growing phase of the polymer to be obtained.
In other words low quantities of solvent, for example 30% in weight, allow the reaction mixing to be solubilized at the beginning, but as the first reaction products, the first oligomers of the polyamide, form, the oligomers precipitate into the mixing reaction thus separating from the reactants . Therefore the polymerisation reaction cannot go on. The effected tests have also proved that the aforementioned effect shows when the solvent is present in quantities less than about 40% in weight calculated over the total weight of the mixing reaction.
The afore mentioned reaction has been also repeated by varying the temperature if the reaction, and it has been noticed that the best results have been achieved when the temperature of the reaction system is kept around about the room temperature.
Therefore many different methods have been used for avoiding undesired increases of the temperature of the reaction system.
It is important to find a good method for avoiding the increases of the temperature most of all when the reaction is conducted with industrial quantities if reactants, i.e. when a scale-up of the system is made.
For decreasing the temperature of the system and avoiding overheating, an ice bath is used, enveloping the flask in which the reaction occurs and absorbing the heat produced by the reaction.
Tests made have shown an optimal reaction time of about 30 min. After this time the production of CO2 finishes and the mixing roils, this being an optical effect due to the formation of the first oligomers, and the viscosity of the reaction system increases, this being also due to the formation of the first oligomers .
Following the reaction phase, the obtained polymers have been subjected to a casting procedure, by laying the polymer down, as already seen, forming a film in the bottom of a container with a flat bottom.
In some tests the containers has been substituted by a LDPE film on which a film of the obtained polymer has been spread.
The film has been then positioned in an oven under N2 stream for about 36 h for aiding the removal of the solvent used
(DMF) form the surface of the film and for terminating the polymerisation process.
The solvent removed form the surface of the film can be easily recycled by condensation. Recycling the solvent become more important and convenient as the reaction is used industrially.
In the oven, furthermore, the film has been maintained at a temperature comprised between about 4O0C and about 6O0C, so as to aid the drying of the film, in particular the temperature has been increased of about 1O0C every about 45 min .
The afore mentioned treatments can last a time range comprised between about 24 h and 96 h (4 days) ; after such treatments, for example after 36 h, film having about constant weight have been obtained. By increasing the drying period of time, the quantity of solvent removed from the surface of the polymeric film increases .
In other words, at the end of the drying treatment, an analogous treatment different form that just discussed can also be used, a polymeric product that can be considered a finished product, with an almost constant weight is obtained. Since the polymer obtained is stable over time, can be deduced that the polymerisation reaction is finished and that such reaction has good yield.
For further improving the removal of DMF form the polymeric films, the film has also been washed in a suitable further solvent, for example a water-methanol mixing, or water, or also thinner films can be obtained. The afore mentioned methods are both efficacious even if used together with the afore explained drying in oven under N2 stream.
Nevertheless for industrially applicability of the reaction, thinner films are suggested. At the end of the above mentioned operations, a polymer having a good viscosity in melt conditions, that can be easily processed in subsequent operations, that is stable over time, and that can be easily spread over a suitable support forming a film continuous, even very thin, and free of fracture points, and of air bubbles.
The obtained polymer may be also used just as obtained, without subsequent processing operation as film. In particular, tests have been conducted by spreading the polymer on different supports as in ordinary glass, silanised glass, silicone rubber, Teflon-butyl rubber, nylon sheets, PVC sheets, LDPE sheets, aluminium sheets.
Spreading the polymer on the supports in ordinary glass, a good adhesion, difficult detaching has been observed; on the supports in silanised glass good adhesion, detaching slightly easier than with the ordinary glass has been observed; on the supports in silicone rubber good adhesion, difficult detaching has been observed; on the supports in Teflon-butyl rubber not good adhesion has been observed; on the nylon sheets optimum adhesion, no detaching has been observed; PVC it is not compatible with DMF, therefore the PVC sheet tends to dissolve; on the LDPE sheets good adhesion, good detaching has been observed; on the aluminium sheets optimum adhesion no detaching has been observed.
In all the tests done a regular and thin film, free of air bubble, and of fracture points, has been spread in the chosen support, especially if the polymer is spread as a suitable viscosity suitable for spreading has been reached.
The tests have also shown a good detaching of the polymeric film from the supports, mainly in cold conditions, and mainly from LDPE sheets. This allows the polymeric materials obtained to be used for producing composite materials of different kind and thus suitable to be used for many different uses.
The effected tests have also shown that the LDPE sheets are the most preferred support for spreading the polymeric materials according top the invention, since such sheets have the proper adhesion features and also the film spread on such supports are the most homogeneous and regular, thinnest and free of air bubbles and of fracture points .
After the casting procedure, for further removing the solvent form the film, the polymeric film can also be otherwise dried in vacuum at a pression of about 1 torr and at a temperature comprised between about 4O0C and about 6O0C.
In case the polymer film can also be chopped before drying.
After such treatment the polymer can be also melted and then subjected to desired processing operation.
Example 4 Synthesis of polyamides with a branched and/or cross-linked structure obtained from tartaric acid and HMDI
(Hexamethylene Diisocyanate) , by varying the reacted quantity of HMDI. The reaction indicated with reference to the example 1, has been repeated also for producing polyamides with a branched and/or cross-linked structure obtained from tartaric acid and variable quantities of HMDI .
By varying the quantity of HMDI in relation to the other reactants used, polymers having a different branching and/or cross-linking degree from one another have obtained.
The reaction process used is the same as shown with reference to the example 3, and in particular as the variation described with reference with this example. A 5% excess of diisocyanate in relation to tartaric acid, allows, as already seen in respect to example 3, branched and/or cross-linked polymer to be obtained.
Such excess has been progressively increased thus conducting reaction with a value of the ratio Tartaric AcidrHexamethylene Diisocyanate respectively of 1:1.05; 1:1.1; 1:1.2; 1:1.4; 1:1.6.
The operating conditions used and the excess of HMDI with respect to the stoichiometric quantity in respect to the other reactants of the reaction, also enabled the hydroxyl groups that were present to react, giving rise to polyamides with a branched and/or cross-linked structure as shown in the following reaction:
Figure imgf000034_0001
At room temperature and in a N2 inert atmosphere, in a 100 ml flask that has been previously dehumidified through 5 nitrogen vacuum cycles, tartaric acid (1.64 g) , DBLT (65 μl) and anhydrous DMF (6.1 ml) were introduced, and the system is stirred till a homogeneous and clear solution is obtained. The sequence for adding DBLT and DMF can also be reversed. Subsequently, HMDI is added the quantity of which depends in the excess of HMDI desired, for example if the reaction having a ratio Tartaric Acid: Hexamethylene Diisocyanate respectively of 1:1.2; is desired, 2 ml of HMDI are added, therefore the reaction system is stirred for about 30 min a N2 environment. Similar reaction system have been created varying the quantity of HMDI, and varying also the quantity of the other reactants and of the solvent DMF so as the reactants Tartaric Acid and Hexamethylene Diisocyanate make up together about weight 40% of the mixing reaction and DMF make up about 60%, i.e. (Tartaric Acid + Hexamethylene Diisocyanate) : 4=DMF: 6.
The temperature of the system, is kept at about 4O0C by using an ice bath during the reaction. The reaction is identified by CO2 developing, turbidity of the reaction system due to the formation of the oligomers and subsequently of the polymer, and the increasing of the viscosity of the reaction system.
The reticulation degree of the polymers affects the features of the polymers, for example the behaviour at high temperatures . With the different values of the ratio Tartaric Acid: Hexamethylene Diisocyanate polymers with different reticulation degree and thus with different features have been obtained, and also, as will be explained in greater detail below, thermosetting and thermoplastic polymers have been obtained.
In any case polymers that can be easily worked and processed, event with different technique from which regular, homogeneous and thin film can be obtained, are produced. Both the thermoplastic and the thermosetting polymers obtained have shown a good processability and filmability, therefore for both the two different kinds of polymers many different uses can be supposed.
The reaction used for obtaining branched and/or cross-linked polyamides has been repeated varying the percentage of HMDI in the reaction system. The reaction mixing has been analysed in the different reactions in the first stages of the reaction, i.e. when the formation of the first oligomers begins .
It has been noticed that the viscosity of the reaction system decreases by increasing the excess of HMDI in relation to the quantity of Tartaric Acid.
All the polymers obtained, after being spread on a support and positioned into a oven, as already seen for removing the solvent, show a low tendency to form air bubbles, i.e. continuous and thin film can obtained.
Nevertheless increasing the excess of HMDI, the polymeric film shows a greater tendency to fold.
This means that such films can be spread in a more difficult way, in the sense that such polymers reach more slowly the viscosity suitable for being spread, and that such films tend to remain as adherent as possible to the support on which are spread. After such polymers are spread on a support, tend to adhere very well to the support, and since such polymers tend to fold when drying, drag the support so bending it. In fact, in a branched and/or cross-linked polymer, the branches of the different chain of the polymer tend to form bound between each other, so that the different chain of the polymer cannot be any more distinguished. Therefore such polymers could be used for obtaining coating that completely and uniformly cover the support and that can be sprayed on the support.
Mainly if the support has not a plane surface the afore mentioned feature of the polymers can be very useful for coating such supports . In fact when a substance is sprayed in a support, the problem arises of a complete covering of the surface of the support. On the other side, when a substance is sprayed that tends spontaneously to cover the entire surface of the support, a continuous and homogeneous coating is obtained. This allows material to be saved. Increasing the quantity of HMDI in relation to the quantity of tartaric acid, a polymer even more rigid and fragile it is obtained.
The polymer obtained with the afore described reaction and with the values of the ratio Tartaric AcidrHexamethylene Diisocyanate respectively of 1:1.05; 1:1.1; 1:1.2; 1:1.4; 1:1.6 have been spread on a support, dried in a oven, as already described for removing the solvent and terminating the polymerisation reaction, in case washed for further removing residuals of solvent, and then analysed.
The polymers spread on the support and dried in the oven, has been extracted using a "Kumagawa extractor", that enables to remove the solvent of the reaction remained on the film of the polymer by using and extraction solvent in which the polymer is immersed.
The extraction solvent is poured in a tank positioned at the base of the extractor and is drawn to the polymeric film absorbing the solvent of the reaction remained and the low molecular weight product, the oligomers. As extraction solvent methanol can be used.
The extraction process can be last for example for about 8 hours .
The extraction solvent is recycled during the extraction process, and the concentration of DMF, the solvent of the reaction, and of the oligomers progressively increase.
The extraction process has been repeated for each one of the different polymers obtained, and at each cycle the extraction solvent is renewed. At the end of the extraction process a polymeric film insoluble into the extraction solvent is obtained, the quantity of the polymeric insoluble film changes with the percentage of HMDI .
In the case of a reaction conducted with a value of the ratio Tartaric Acid:Hexamethylene Diisocyanate of 1:1.6, about 92% polymeric insoluble film is obtained, whereas with a value of the ratio Tartaric AcidrHexamethylene Diisocyanate of 1:1.05, about 60% polymeric insoluble film is obtained. The remaining part, comprising mainly DMF and oligomers, is dragged away by the extraction solvent. The above value show that increasing the excess HMDI in relation to Tartaric Acid, polymers with a higher polymerisation degree are obtained, in which the percentage of oligomers decrease. The eluate obtained by the extraction process, i.e. a mixing containing the extraction solvent, DMF, and oligomeri, is limpid and colourless in the extraction of the polymer obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate respectively of 1:1.6, whereas the eluate turns progressively yellow as the excess of HMDI is decreased.
The yellow coloration is due to the presence of the oligomers into the eluate, and as already seen the concentration of the oligomers increase as the excess of HMDI decreases. The eluate from the polymer obtained with a molar excess of HMDI respectively of 60%, (AT : HMDI=I : 1.6) , and 40% (AT :HMDI=1 : 1.4) , is limpid and colourless, whereas the eluate from the polymer obtained with a molar excess of HMDI respectively of 20%, (AT :HMDI=1 : 1.2) , 10%, (AT : HMDI=I : 1.1) and 5% (AT : HMDI=I : 1.05) turns progressively to yellow. The eluate has been analysed with gas chromatography that has revealed that the concentration of DMF in the eluate of the polymers obtained with a molar excess of HMDI of 60%, is about 4%, whereas the concentration of DMF in the eluate of the polymers obtained with a molar excess of HMDI of 5%, is about 15%.
The polymer obtained with the above mentioned reactions have been further subjected to Relative Humidity analysis in a controlled environment, for measuring the tendency to absorb water by measuring the weight variations of the samples of the different polymers starting from dry samples. For drying the samples, the polymeric film have been positioned in an oven at a temperature of about 6O0C under N2 stream for about 24 hours for removing the water, till the samples show a weight constant over time.
Therefore the sample have been introduced in a closed container into which a NaCl saturated solution for 24 hours was present for 24 hour, so to crate an environment with a relative humidity of about 75% at 250C.
The weight increases of the different samples of the different polymers have been measured after different period of time.
The maximum weight, and therefore the maximum water absorption occurs after 48 hours.
The weight increases have similar trends for all the samples.
The tests have shown that the samples of all the polymers obtained absorb water reaching a maximum hydration after about 48 hours in an environment at 250C and a relative humidity of 75%.
The results are summarized in the following table:
Figure imgf000039_0001
Table 13
In the first row of the table, the results of the sample obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate of 1:1.6 are shown; in the second row of the table, the results of the sample obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate of 1:1.4 are shown; in the third row of the table, the results of the sample obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate of 1:1.2 are shown; in the fourth row of the table, the results of the sample obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate of 1:1.1 are shown; in the fifth row of the table, the results of the sample obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate of 1:1.05 are shown. As can be seen from the table, a certain swelling has been observed for each sample, therefore all the polymers obtained have a good hydrophilicity and thus a good degradability, since the softening of the polymers into the water favour their degradation. Therefore since the polymers absorb water, it is easier for bacteria degrading the material to grow up, and then the degradative process can be favoured and speed up. The samples of the different polymers have been, furthermore, subjected to TGA analysis (Thermogravimetric Analysis) for measuring the change in the weight as function of the temperature and/or over time.
This technique being also suitable for measuring the degradation temperature of the polymers the quantity of residual solvent, and for measuring the maximum value of the temperature at which the polymer may be subjected without loosing their features.
The TGA analysis allows evaluating the temperature at which the polymers are not more stable and begins to liberate volatile compounds such as CO2, NOx. For the analysis a thermo-balance "Mettler-Toledo TGA/SDTA851e", has been used, and the TGA analysis has been conducted in nitrogen environment with a speed scanning of about 10°C/min, in temperature range comprised between about 250C and HOO0C. TGA analysis has been conducted on the samples after the samples had been dried in the oven and both on the samples before extraction with "Kumagawa extractor" and also after extraction. The results obtained by the TGA analysis show that all the samples of the polymers obtained have a similar behaviour one with another and have a weight loss that begins at about 2000C and continues till about 5000C.
Furthermore, the samples analysed before the extraction with "Kumagawa extractor" show a greater weight loss due to the residual solvent, such weight loss decreases in the samples analysed after the extraction with "Kumagawa extractor" using methanol as extraction solvent. In fact the weight losses at low temperature, about 2000C, are due to the evaporation of the solvent, DMF. All the samples analysed have a residual that do not degrade even at a temperature of about HOO0C and that represents about 5-10% weight percentage of the original sample. The samples have been further subjected to DSC (Differential Scanning Calorimetry) , for examining the thermal transition of the polymer, i.e. for determining the glass transition temperature of the polymers .
DSC analysis has been conducted using a "Mettler-Toledo DSC 821e" and an analysing cycle comprising two heating phases and two cooling phases, and working at a temperature comprised between about -4O0C and 15O0C.
In particular the thermal cycle comprises a first heating phase having a heating speed of about 20°C/min, followed by a first cooling phase having a cooling speed of about 10°C/min, therefore the samples have been re-heated with a heating speed of about 10°C/min and re-cooled with a cooling speed of about a 20°C/min.
The DSC spectra obtained for the different samples are very similar one with the other: the samples are all amorphous and have a glass transition temperature. The glass transition temperature changes for the same sample if measured both in the samples extracted with "Kumagawa extractor" and in the samples not subjected to extraction with "Kumagawa extractor" . In the following table 14, in column 2 have been indicated the mean values of the glass transition temperature, approximated to the unity value, calculated in the samples not subjected to the extraction, whereas in the column 3 the values calculated in the samples subjected to the extraction. In the first row of the table 14 the values of the samples of the polymer obtained with a value of the ratio Tartaric Acid: Hexamethylene Diisocyanate of 1:1.6; in the second row the values for a value of the ratio of 1:1.4; in the third row the values for a value of the ratio of 1:1.2; in the fourth row the values for a value of the ratio of 1:1.1; in the fifth row the values for a value of the ratio of 1:1.05. The same value has been represented also in the graph of Figure 23.
Figure imgf000042_0001
Table 14
As can be seen from the table 14 the values of the glass transition temperature decrease as the percentage of HMDI decrease, both for the values measured in the sample not extracted and in the samples extracted.
Therefore the extraction with "Kumagawa extractor" produces and increase of the glass transition temperature of about
25°-60°C.
The samples have furthermore subjected to rotational rheometry for evaluating the viscosity of the melted materials .
After the extraction with the "Kumagawa extractor", the samples have been dried under vacuum for about 24 hours and then subjected to a rheometric analysis.
Similar analysis may also be conducted on the samples that have not been extracted.
The tests have been conducted using a rheometric rotational analyser "ARES" of the "Rheometric Scientific". The melted samples have been introduced between a pair of plates about 25mm thick at a temperature of about HO0C, and subjected to a rotation into opposite directions. Rheometric test allows identifying two different kinds of polymers obtained by varying the value of the ratio Tartaric AcidrHexamethylene Diisocyanate : thermoplastic and thermosetting polymers .
In particular polymers obtained with values of the ratio Tartaric AcidrHexamethylene Diisocyanate of 1:1.4 and 1:1.6 do not strain under stress, but keep the shape of a sheet, and the pieces prepared are not homogeneous but formed up by different initial little pieces. This demonstrates that such samples have a good reticulation degree and are thermosettable polymers . The samples of this group of polymers have been heat-pressed so as to obtain rectangular pieces using a pression of about 5 ton and a temperature of about HO0C. Such pieces have been again subjected to reometrico at higher temperature so as to try to melt the pieces, but they do not melt, and during the time single parts of polymers that were be heat pressed for forming up the pieces would separate each other. On the other side, the samples obtained with values of the ratio Tartaric Acid:Hexamethylene Diisocyanate of 1:1.05, 1:1.1, and 1:1.2 show a certain fluidity measured at HO0C, are thermoplastic polymers .
If the measurements are repeated on the samples of the above- mentioned polymers, a good strain is always noticed, therefore such polymer can be repeatedly melted and processed. This also show that during the measurements no degradation reactions occur, and then that the polymers are stable over time .
On the sample of the last group, a viscosity measure has been further conducted to measure the viscosity over the speed strain: this measurement could be done since the polymers of this group melt. As can be seen form the graph of Figure 24, the samples of each one of the polymers of such group, show a viscosity decreasing increasing the speed strain, nevertheless no one of the samples reach the Newtonian plateau, i.e. no one of the sample reach the stress value over which the viscosity remains constant increasing the stress.
The maximum value of the viscosity measured amongst the thermoplastic polymers, has been measured in the sample obtained with a value of the ratio Tartaric AcidrHexamethylene Diisocyanate of 1:1.2, such viscosity having a value of the order of about 105 Pa*s, comparable with the viscosity values of known mouldable polymers. It has been noticed also that the viscosity increases with the increase of the HMDI excess. The tests made on the samples obtained with a value of the ratio Tartaric AcidrHexamethylene Diisocyanate of 1:1.6 and 1:1.4, show that it is not possible to measure the viscosity of such samples, since such samples do not melt, this behaviour being typical for the thermosettable polymers . The viscosity measurements allow confirming the hypothesis that two different group of polymers, thermoplastic and thermosettable polymers, can be obtained by simply varying the value of the ratio Tartaric Acid:Hexamethylene Diisocyanate in the mixing reaction. A first group comprises the polymers obtained with a value of the ratio Tartaric Acid:Hexamethylene Diisocyanate respectively of 1:1.4 and 1:1.6, that are thermosettable and branched and/or cross-linked polymers; whereas the second group comprises the polymers obtained with a value of the ratio Tartaric Acid:Hexamethylene Diisocyanate respectively of 1:1.05, 1:1.1 and 1:1.2, that are thermoplastic and not cross-linked polymers.
The samples of the polymer GC34-MA39, this abbreviation identifies the polymers obtained with a value of the ratio Tartaric Acid:Hexamethylene Diisocyanate equal to 1:1.6, have been positioned into the rheometer at a temperature of about HO0C, and subjected to the rotational rheometric analysis, but it was not possible to melt the samples, since the polymers is a cross-linked polymers; for confirming such hypothesis the samples have been brought to a temperature of about 15O0C, at which the samples have not melted, but gels have begun to form.
The samples of the polymer GC34-MA40, this abbreviation identifies the polymers obtained with a value of the ratio Tartaric AcidrHexamethylene Diisocyanate equal to 1:1.4, have been positioned into the rheometer at a temperature of about HO0C, and subjected to the rotational rheometric analysis, but it was not possible to melt the samples, since the polymers is a cross-linked polymers; for confirming such hypothesis the samples have been brought to a temperature of about 15O0C, at which the samples have not melted, but gels and bubbles, probably for the evaporation of the solvent, have begun to form.
From the samples of the polymers GC34-MA39 and GC34-MA40, sheets have been obtained, therefore such polymers are extrudable and mouldable.
The samples of the polymer GC34-MA41, this abbreviation identifies the polymers obtained with a value of the ratio Tartaric AcidrHexamethylene Diisocyanate equal to 1:1.2, have been positioned into the rheometer at a temperature of about HO0C, and subjected to the rotational rheometric analysis, and have reached a considerable fluidity, therefore the viscosity vs. strain speed has measured. The results of such measurement have been reported in the graph of Figure 24. The samples of the polymer GC34-MA42, this abbreviation identifies the polymers obtained with a value of the ratio Tartaric AcidrHexamethylene Diisocyanate equal to 1:1.1, have been positioned into the rheometer at a temperature of about HO0C, and subjected to the rotational rheometric analysis, and have reached a good fluidity, therefore the viscosity vs. strain speed has measured. The results of such measurement have been reported in the graph of Figure 24. The samples of the polymer GC34-MA43, this abbreviation identifies the polymers obtained with a value of the ratio Tartaric AcidrHexamethylene Diisocyanate equal to 1:1.05, have been positioned into the rheometer at a temperature of about HO0C, and subjected to the rotational rheometric analysis, and have reached a remarkable fluidity, therefore the viscosity vs. strain speed has measured. The results of such measurement have been reported in the graph of Figure 24. The rheologic tests allowed also to demonstrate that it is possible to continuously modulate the mechanical properties of the polymeric materials according to the invention by simply varying the reciprocal percentage of the reactants, and obtaining thermoplastic and thermosettable polymers . Furthermore it also possible, in order to modulate the mechanical properties of the polymeric materials, to choose the treatment to which subjecting the polymers after the reaction, and/or the degree of such treatments and the duration thereof. Furthermore, similar results can also be obtained for the other polymer according to the invention, by varying the reciprocal percentage of the reactants, and obtaining polymers of the same kind, polyamide, poly (amides urethane) , etc, but with different mechanical properties one from another.
The film of the thermoplastic polymers, obtained with a value of the ratio Tartaric AcidrHexamethylene Diisocyanate respectively of 1:1.05, 1:1.1 and 1:1.2, show also a wide range of molecular weights, i.e. oligomers at low molecular weight are present.
The oligomers at low molecular weight modulate the features of the fractions of the polymers having high molecular weight and act as plasticizers, this being undoubtedly a good feature since the processability of the polymers is improved. It has been noticed that the glass transition temperature of the polymers is usually low, lower that the room temperature, but the extraction make the glass transition temperature to increase because the methanol, or in case the extraction solvent absorb the oligomers .
This explains also the weight losses of the polymers during the extraction, since the residual reaction solvent and the oligomers are removed from the polymer.
The tests conducted have also shown that the polymer obtained with a value of the ratio Tartaric AcidrHexamethylene Diisocyanate of 1:1.2 is the most interesting product, mainly form some particular use thereof.
Such reaction produce a polymer that is near to reticulation limit, and therefore has very high viscosity, very high mechanical resistance, but that is at the same time a thermoplastic polymer. Example 5 Synthesis of polyamides with a branched and/or cross-linked structure obtained from tartaric acid and chain diisocyanates of varying length.
Stoichiometric quantities of the reactants were mixed. The reaction of the example 3 was repeated by making the tartaric acid react with diisocyanates with chain of a different length with respect to that of the HMDI, whether linear, reticulate or cyclical chain diisocyanates, obtaining polyamides with a branched and/or cross-linked structure and with mechanical properties varying according to the length of the chain of the diisocyanate.
In general, a certain increase in the flexibility of the prepared polymeric films was noted starting with a diisocyanate with a shorter chain, probably due to the lesser degree of crystallinity resulting from the structure of the resulting polymers .
In particular, DMDI (1,12 diisocyanatododecane) was used as an isocyanate that enabled polyamides to be obtained having good mechanical features . Furthermore, the nature of the support for the casting procedure has been changed, and materials were used like polyethylene, common non-treated glass and aluminium, with the aim of assessing the degree of adhesion of the polymeric film to the support.
Also in this case, by subjecting the various polyamides obtained to tests in order to assess the reaction thereof to the tension stress, it is noted that with the increase of the length of the chain of the diisocyanate used, polyamides with less flexibility are obtained and which are therefore provided with a greater degree of crystallinity .
On the other hand, with the decrease in the length of the chain of diisocyanate polyamides are obtained having greater flexibility and therefore greater resistance to tension stress .
Tests have been also been conducted for modulating the properties of the polyamides obtained by varying the value of the ratio of Tartaric Acid: Diisocyanate, obtaining results comparable with those discussed with reference to example 4.
Varying the reciprocal ratio of the reactants and the particular isocyanate used and the features thereof, linear, branched and/or cross-linked, or cyclical chain, it is possible to continuously modulate the properties of the polymer obtained. It is thus possible to obtain a polymer fitted to a particular desired use.
Therefore, it is possible to suppose to obtain polymers suitable for replacing all the various known plastic materials.
In particular using OTDI (octometildiisocyanate) or DMDI
(1,12 diisocyanatododecane) polymers similar to those obtained with reference to example 4 were obtained.
Furthermore by varying the reaction condition as already discussed with reference to example 4 it is possible to modulate the features of the polymers obtained.
Example 6 Synthesis of co-polyamides obtained from tartaric acid, suberic acid and HMDI .
The reaction used for these syntheses closely follows the one seen with reference to the example 1, both in terms of the percentages of compounds loaded into the reaction system and in terms of the reaction conditions and the dynamics of the reaction, with the variation that suberic acid is also added to the reaction system in quantities that are equimolar with respect to the tartaric acid (X moles of suberic acid and X moles of tartaric acid) before the addition of HMDI (2X moles of HMDI) , as indicated by the reaction reported below:
Figure imgf000049_0001
in which R in the reaction product indicates radical comprising for example (CH2) 6 and/or CH(OH)CH(OH).
Into a previously dehumidified three-necked flask, equipped with a mechanical stirrer and cannula for bubbling nitrogen in an inert atmosphere, in the following order tartaric acid
(1.0067 g; 6.7068 mmoles) , suberic acid (1.1845 g; 6.6636 mmoles) , DBLT (87 μl) and anhydrous DMF (6.9 ml) were introduced, and only after the thus composed mixture had become homogenous was HMDI (2.0 ml; 12.8763 mmoles) added.
The reaction conditions used were similar to those of example
1.
The reaction product was subsequently characterised by spectroscopy 1H-NMR and 13C-NMR and viscosimetric measurements .
For a product obtained with the reaction disclosed, Figure 5 shows the spectrum 1H-NMR (d-DMSO) , and Figure 6 shows the formula of the product obtained indicating the functional groups highlighted in the spectrum, and Table 3 shows the legend relating to this spectrum, in Figure 7 the spectrum 13C-NMR (d-DMSO) , Figure 8 shows the formula of the product obtained indicating the functional group highlighted in the spectrum, and Table 4 shows the legend relating to this spectrum. The reaction shown above was repeated by varying the percentage of the individual reactants with respect to the stoichiometric quantities and using diisocyanates having a chain of various length that are different from one another. The results obtained are similar to those discussed with reference to the previous example.
Example 7 Synthesis of co-polyamides obtained from tartaric acid, suberic acid and diisocyanates with chain of various length.
Stoichiometric quantities of the reactants were mixed. In a similar manner to what has been seen in example 2, the reaction of the example 5 was repeated using chain diisocyanates of various length, linear chain, branched and/or cross-linked chain, cyclical chain, aromatic chain diisocyanates obtaining variable-chain co-polyamides with slightly different mechanical properties from one another. Also in this case, by subjecting the various co-polyamides obtained to tests to assess the reaction thereof to stress, it was noted that at the increase of the length of the chain of the diisocyanate used, polyamides with less flexibility were obtained and which were thus provided with a greater degree of crystallinity . On the other hand, as the length of the chain of the diisocyanate decreases, polyamides are obtained having greater flexibility and therefore greater resistance to the tension force. Example 8 Synthesis of co-polyamides with a branched, and/or cross-linked structure obtained from tartaric acid, suberic acid and HMDI .
The reaction already indicated with reference to the example 3, was also used for synthesis of co-polyamides with a branched, and/or cross-linked structure from tartaric acid, suberic acid and HMDI.
The reaction system differs from that specified in example 6 because HDMI is added in excess of the 5% in moles with respect to the stoichiometric ratio, also enabling the hydroxyl groups present to react. At room temperature and in an inert atmosphere, into a two- necked flask, dehumidified by means of nitrogen vacuum cycles, tartaric acid (0.6419 g; 4.2765 mmoles) , suberic acid (0.7561 g; 4.2536 mmoles), DBLT (58 μl) and anhydrous DMF (4.6 ml), were introduced and only after this mixture had become homogenous was HMDI (1.4ml; 9.0134 mmoles) added.
At this point, the operating procedure is identical to the one followed for synthesising polyamides with a branched, and/or cross-linked structure of the example 3, also in this case the casting procedure was repeated by varying the nature of the support used.
The reaction was furthermore repeated by varying the diisocyanate used.
The reaction was furthermore repeated by varying the value of the ratio between the diisocyanate and the other reactants, tartaric acid and suberic acid.
Results similar to those previously discussed with reference to the previous example have been obtained.
The diagram of the reaction used and the structure of the co- polyamides obtained are shown below:
Figure imgf000051_0001
Example 9 Synthesis of polyamide polyesters from tartaric acid, PGLA-COOH (poly (lactic glycol) carboxy terminated) acid,
HMDI.
Stoichiometric quantities of the reactants were mixed.
These polyester polyamides were synthesised in two successive moments : first of all the oligomer precursor PLGA-COOH was prepared by a polycondensation reaction of lactic acid, glycolic acid and succinic anhydride, subsequently the compound obtained was made to react with tartaric acid and HMDI.
The preliminary synthesis of oligomers of functionalised PLGA so as to have at the two ends of the chain of the PLGA carboxy groups, is obtained through thermal polycondensation of lactic acid, glycolic acid and succinic anhydride and polycondensation between the product of the previous reaction and tartaric acid and HMDI . Synthesis of PLGA-COOH In previously dehumidified two-necked flask, on which an overlapped item is superimposed and which is provided with a tap for the nitrogen or the vacuum, lactic acid (12.1047g; 0.1344 moles), glycolic acid (10.3466 g; 0.1346 moles) and succinic anhydride (2.7769 g; 0.0269 moles) were loaded. The lactic acid and glycolic acid were introduced in equimolar quantities (X moles for each) , and in great excess with respect to the succinct anhydride, which is present in quantities equal to 0.2*X moles. At this point, the reaction system has been heated to 12O0C in an inert atmosphere for two hours, after the end of which time, after the system has returned to room temperature, the overlapping item was replaced by a Claisen and the reaction system was heated to 16O0C first for 22 hours under nitrogen stream and then, after taking the system to a reduced pressure, for another 24 hours.
The oligomer PLGA-COOH thus obtained was then titrated with a standard solution of tetrabutylammonium hydroxide 0.1 M in the presence of phenolphthalein as an indicator, dissolving approximately 200 mg of phenolphthalein in 25 ml of anhydrous benzyl alcohol, for the purpose of determining the average numeral molecular weight of the oligomer PLGA-COOH. The tests were conducted by obtaining a product the spectrum 1H-NMR (d-TFA, d-trifluoroacetic acid) of which is shown in Figure 9, and the formula of the product obtained from the above mentioned reaction is shown in Figure 10 with the functional groups indicated in the spectrum being highlighted, and Table 5 shows the legend relating to this spectrum.
Figure 11 shows the spectrum 13C-NMR (d-TFA) of the product obtained from the above mentioned reaction, Figure 12 shows the formula of the product obtained indicating the functional groups highlighted in the spectrum, and Table 6 shows the legend relating to this spectrum.
The oligomer - comonomer obtained from the above reaction was also characterised by means of IR spectrophotometry in a solution in CH2CI2 solution. The graph obtained is shown in Figure 13, and in Table 7 the legend of the graph is shown. Synthesis of PTPLGAHI
The PLGA-COOH oligomer previously prepared (8.3150 g; 9,6617 mmoles; Mn = 860.6), tartaric acid (1.4552 g; 9,6949 moles), the DBLT catalyst (257 μl, equivalent of 2% in weight) and the anhydrous DMF (20.6 ml; 40% solution in weight of the reactants) were introduced in an inert atmosphere into a previously dehumidified three-necked flask, equipped with a mechanical stirrer and cannula for bubbling the nitrogen, and once the mixture had become homogenous HMDI was added (3.0 ml; 19.3234 mmoles) .
The reaction was conducted using the same method as that adopted for synthesis of the other linear structure polymers mentioned so far, i.e. that of the example 1. The same test was repeated using the oligomer PLGA-COOH derived from the above test as a co-monomer for the synthesis of PTPLGAHI.
The product was characterised through spectroscopy 1H-NMR and 13C-NMR, but not through chromatographic analysis GPC, the product being insoluble in the eluent that is compatible with the instruments provided.
Figure 14 shows the spectrum 1H-NMR (d-TFA) , Figure 15 shows the formula of the product obtained with the functional groups shown in the spectrum indicated, and Table 8 shows the legend relating to this spectrum, Figure 16 shows the spectrum 13C-NMR (d-TFA) , Figure 17 shows the formula of the product obtained with the functional groups shown in the spectrum indicated, and Table 9 shows the legend relating to this spectrum. The reactions used are shown in the following diagram.
Figure imgf000054_0001
PTPLGAHI
Also for this type of polymer casting tests were conducted, varying the nature of the support used, for example polyethylene, common glass and aluminium, using the same procedure seen with reference to example 3. Example 10 Synthesis of polyester polyamides PTPLGAHI with branched and/or cross-linked structure from tartaric acid, PGLA-COOH, HMDI.
The preparation of the PTPLGAHI with branched and/or cross- linked structure was conducted in a similar manner to what is indicated with reference to the example 3 with relation to PTHI with branched and/or cross-linked structure, and, also in this case, with respect to the reaction conditions, the same remarks apply as were made about example 3. In fact, the same reactions were used as specified for example 9, with the sole difference that HMDI in excess of 5% in moles with respect to the stoichiometric amount was added. The more drastic reaction conditions compared with those of example 9, i.e. similar to those of example 3, and the excess of 5% in moles with respect to the stoichiometric amount enabled also the hydroxyl groups present to react with tartaric acid and PLGA-COOH, similar to what was seen previously for the other polymers with a branched and/or cross-linked structure.
The above reactions were repeated, obtaining different products, for example varying the excess of HMDI, and/or the particular diisocyanate used.
The casting phase was conducted for the products obtained on supports of a different nature, in particular polyethylene supports, non-treated common glass and aluminium were used. Following the above reactions, polymer films of PTPLGAHI were obtained that were able to adhere to the common glass, to the aluminium, inasmuch as they were perfectly resistant to the mechanical stress arising from the detachment thereof, and were able to interface with the aluminium. Such polymers have great versatility that enables them to be used for surface coatings of the glass and for manufacture of packaging, coupling them with the aluminium, for example in food packaging, as such materials enable excellent protection from the humidity, from the air and from the light, that is anyway greater than that offered only by the polymer.
Example 11 Synthesis of co-poly (amide urethanes) PTPOLHI from tartaric acid, poloxamer 1100, HMDI.
Stoichiometric quantities of the reactants were mixed.
The procedure of the reaction in question is identical to that seen with reference to the example 1, with the sole variation that before adding the diisocyanate, also poloxamer 1100, block co-polymer poly (ethylene glycols) — poly (propylene glycols) — poly (ethylene glycols) was added in the weighted ratio 1:1 with respect to the tartaric acid. Into a previously dehumidified three-necked flask, equipped with a mechanical stirrer and cannula for bubbling the nitrogen, in an inert atmosphere in this order tartaric acid
(1.6970 g; 11.3058 mmoles) , POLOXAMER (1.7018 g; 1.5471 mmoles; Mn = 1100), DBLT (110 μl equivalent of 2% in weight) and anhydrous DMF (8.8 ml; 40% solution in weight of the reactants) were loaded, and only after the mixture became homogenous was HMDI added (2.0 ml; 12.8763 mmoles) . The reaction procedure followed was in this case identical to what has already been disclosed with reference to example 1. The products obtained by the polymerisation in question were shown to be insoluble in the solvents, and it was therefore not possible to conduct any characterisation.
The reactions were repeated with the same reaction system, but operating with less than 10% HMDI moles, also in this case polymer solutions were obtained that were insoluble in the solvents and which it was not therefore possible to characterise .
The insolubility of the products obtained suggests that polymers were obtained with a branched and/or cross-linked structure, this is probably due to a preferential reactivity of HMDI to POLOXAMER with respect to tartaric acid. The synthesis of PTPOLHI was conducted in the same way as for the previous classes of co-polymers, as far as the obtaining of both linear-chain and branched and/or cross-linked- structure polyurethane polyamides is concerned, by working with a weight ratio of 1:1 between POLOXAMER (Mw = 1100) and tartaric acid in the supply.
The synthesis reaction was repeated using diisocyanates that differed from one another and by varying the relative quantities of the different reactants with respect to the stoichiometric quantities, in particular decreasing the quantity of diisocyanate with respect to the stoichiometric ratio . Also decreasing the concentration of diisocyanate with respect to the stoichiometric ratio, to a defect of 10% with respect to the stoichiometric ratio, branched and/or cross- linked structure polymeric compounds were obtained for which, therefore, it was not possible to carry out a spectroscopic characterisation . The diagram of the reaction used is shown:
Figure imgf000057_0001
The afore described reactions have been repeated varying the values of the different experimental parameters so as to obtain polymers that were not insoluble, and therefore analysable, in particular in order to obtain polymer that could be processed, for example by casting procedure, and analysed.
The reaction has been repeated using about weight 20% of
Poloxamer 1100 calculated on the total weight of the reactants, namely weight of (Tartaric Acid+HMDI) *20/100= weight of Poloxamer 1100.
Into a flask, previously dehumidified by means of 5 nitrogen/vacuum cycles, and having a 100 ml capacity, equipped with a mechanical stirrer and cannula for bubbling the nitrogen, in an inert atmosphere and at room temperature,
2.34 g of Poloxamer 1100, 195 μl of DBLT, and 6.0 ml of HMDI were loaded.
The reaction system has been stirred for about 30 min, at room temperature and in nitrogen atmosphere. Therefore 27.0 ml of anhydrous DMF were added, the system is then stirred for about 5 min at room temperature and in nitrogen atmosphere, and subsequently 4.93 g of tartaric acid were added.
Subsequently the system is stirred for about 30 min in nitrogen atmosphere, the temperature of the reaction system is kept at about 4O0C by using an ice bath. CC>2 develops, the reaction system become more viscous and turbid for the progressive formation of the oligomers. The polymer obtained is spread on a support, for example a LDPE sheet, and is left stand in N2 atmosphere on the support till an optimum value of the viscosity it is achieved.
Afterwards the polymer film is subjected to drying in an oven using the same methods as those seen with reference with the previous example 4, at a temperature comprised between about 4O0C and about 6O0C for about 45 min and increasing the temperature of about 1O0C every 45 min till a temperature of about 6O0C is reached. The polymer films were then left in the oven for about 36 hours, or also for a period of time so that the polymer films remain into the oven for a total period of time of about 36 hours. Using the same reaction above seen, the reaction system has been changed by varying the concentration of DMF, so as to decrease the concentration of residual solvent, DMF, in the polymer obtained. Tests conducted have shown that the minimum value of the concentration of DMF so that the reaction system remains homogeneous during the reaction and the precipitation of the oligomers do not occur, is about 65% by weight considered on the total weight of the mixing reaction, namely weight of (Tartaric acid+HMDI+poloxamer 1100) *65/35=weight of DMF. The afore described reaction has been also repeated by varying the concentration of poloxamer, and using a concentration of Poloxamer of about 40% by weight, namely weight of (Tartaric acid+HMDI) *40/100=weight of poloxamer 1100. Into a flask, previously dehumidified by means of 5 nitrogen/vacuum cycles, and having a 100 ml capacity, equipped with a mechanical stirrer and cannula for bubbling the nitrogen, in an inert atmosphere and at room temperature, 4.58 g of Poloxamer 1100, 195 μl of DBLT, and 6.0 ml of HMDI were loaded. The reaction system has been stirred for about 30 min, at room temperature and in nitrogen atmosphere.
Therefore 34.0 ml of anhydrous DMF were added, the system is then stirred for about 5 min at room temperature and in nitrogen atmosphere, and subsequently 4.93 g of tartaric acid were added.
Subsequently the system is stirred for about 30 min in nitrogen atmosphere, the temperature of the reaction system is kept at about 4O0C by using an ice bath. CO2 develops, the reaction system become more viscous and turbid for the progressive formation of the oligomers. The polymer obtained is spread on a support, for example a LDPE sheet, and is left stand in N2 atmosphere on the support till an optimum value of the viscosity it is achieved. Afterwards the polymer film is subjected to drying in an oven using the same methods as those seen with reference with the previous example 4, at a temperature comprised between about 4O0C and about 6O0C for about 45 min and increasing the temperature of about 1O0C every 45 min till a temperature of about 6O0C is reached. The polymer films were then left in the oven for about 36 hours, or also for a period of time so that the polymer films remain into the oven for a total period of time of about 36 hours. Also in this reaction system, it has been provided for varying the concentration of DMF, so as to decrease the concentration of residual solvent, DMF, in the polymer obtained.
Tests conducted have shown that the minimum value of the concentration of DMF so that the reaction system remains homogeneous during the reaction and the precipitation of the oligomers do not occur, is about 67% by weight considered on the total weight of the mixing reaction, namely weight of (Tartaric acid+HMDI+poloxamer 1100) *67/33=weight of DMF. The polymers obtained using a concentration of poloxamer 1100 in the reactants comprised between about 20% and 40% have been shown to have a viscosity suitable for casting. Such polymers are also suitable to be processed with many different techniques.
Example 12 Synthesis of co-poly (amide urethanes) PTPOLHI from tartaric acid, Poloxamer 1100, diisocyanate . The same reaction seen with reference to the example 11 was repeated using the casting procedure of the polymeric products obtained on various supports .
In particular, casting on polyethylene, non-treated common glass and aluminium was used, following the same operating method seen with reference to the examples 5 and 10, to which reference is made.
Furthermore the reaction was repeated using diisocyanate having chain with different length in respect to HMDI, and diisocyanate with linear, and/Or branched, and or cyclical and/or aromatic chain were used.
Results obtained were similar to those previously discussed with reference to the other polymers .
Example 13 Synthesis of co-poly (amide urethanes) PTPEGHI from tartaric acid, poly (ethylene glycols), HMDI. The reaction used for the synthesis of these polyurethane polyamides is shown in the diagram below; the general stoichiometric coefficients n and z appear therein because both the molecular weight of the oligomer PEG used as a comonomer and the molar and weighted ratios between the comonomers in the macromolecule resulting from the synthesis have been varied.
Figure imgf000060_0001
Figure imgf000060_0002
The reaction procedure followed as the same as that seen with reference to example 1, so it is not repeated. These polymers were obtained through casting on a polyethylene support following a similar method to that seen with reference to the examples 5 and 10.
In particular, various tests were conducted, starting from PEG with various molecular weight and varying the molar ratio between tartaric acid, PEG and HMDI in the reaction mixture and the fraction in weight of PEG in the desired product. In each test a product was obtained with satisfactory- features and products were obtained having features different from on another as regards, for example mechanical processability and degradation.
Therefore, also for this kind of polymers, al already discussed with reference to polyamides, it is possible to continuously modulate the features of the polymers obtained by varying the mixing reaction, for example the molecular weight of the PEG, and/or the value of reciprocal ratio between the reactants, thus obtaining both thermoplastic and thermosettable polymers . The sample of a product obtained with the reaction disclosed above was then subjected to simulated degradation, in static conditions, in pH 7.4 physiological solution for a 0.025 M phosphate buffer.
From the polymer film several portions of an exactly known weight were cut, and each one of the latter was immersed in a volume of physiological solution for a certain number of days, after which the weight loss thereof was measured. The time required for total or at least very advanced degradation is not long, as in less than thirty days of exposure to the degrading environment the residual quantity of each sample is less than 20% of the initial quantity; furthermore, the degradation phenomenon, after a first phase in which it was found to be particular sudden, slowed. With regard to these PTPEGHI polymers, for use in systems with controlled release of pharmaceuticals or of pesticides can be postulated, varying the degradation time and, therefore the release time by suitably varying the features of the original reactants, for example the molecular weight of the PEG, and the reaction ratios between the individual reactants .
Example 14 Synthesis of PTPCL co-polyesters from tartaric acid, PCL (polycaprolactone dihydroxy terminated) .
Into a three-necked flask, provided with mechanical stirring, with a tap for the nitrogen or the vacuum, and a U fitting with collecting pipe for collecting the water that has formed during the reaction, PCL diol (28.0727 g; 22.4581 moles; Mw = 1250;), tartaric acid (3.3763 g; 22.4936 mmoles) and DBTO catalyst (dibutyl tin oxide) (0.3177 g; 1% in weight) were loaded.
The temperature of the reaction was controlled through the use of a silicon oil bath. The reaction mixture was heated up to the temperature of about 13O0C under a nitrogen stream, by starting stirring when the solid mass has started to melt, maintaining these conditions for two hours, after which the system was taken to up to a reduced pressure, still at 13O0C under vigorous stirring.
These conditions were maintained for 24 hours, after which the degree of polymerisation achieved by titrating the samples of the reaction mixture with a standard solution of tetrabutylammonium hydroxide 0.1 M in benzyl alcohol as a solvent, using phenolphthalein as an indicator was evaluated. At this point, the raw material was purified through precipitation by CH2CI2 in ethyl ether and vacuum drying. The reaction product was characterised through 1H-NMR (CDCI3, d-chloroform) and 13C-NMR (CDCl3) spectroscopy and IR spectrophotometry .
Figure 18 shows the spectrum 1H-NMR (CDCl3) , Figure 19 the formula of the product obtained with the functional groups shown in the spectrum highlighted, and Table 10 shows the legend relating to this spectrum, Figure 20 the spectrum 13C- NMR (CDCl3) , in Figure 21 Ia formula of the product obtained with the functional groups shown in the spectrum highlighted, and Table 11 shows the legend relating to this spectrum. Figure 22 shows the spectrum IR (from solution CH2CI2) and Table 12 shows the legend of this spectrum.
The disclosed reactions, of it us herein below represented the diagram, were repeated with various quantities of the reactants .
Figure imgf000063_0001
PCL
Figure imgf000063_0002
In particular: into a high-vacuum reactor, provided with mechanical stirring, with a tap for nitrogen or vacuum, and with a U fitting with collecting tube for the water that has formed during the reaction, PCL diol (112.29 g; 89,86 mmoles;
Mw = 1250;), tartaric acid (13.49 g; 89.86 mmoles) and DBTO catalyst (1.26 g; 1% in weight) were loaded.
The reaction was conducted according to the same methods already indicated in example 14.
Example 15 Synthesis of co-poly (amide urethane) PTPPGHI from tartaric acid, PPG (poly (propylene glycol)), HMDI.
Poly (propylene glycol) is a non toxic substance, widely used for pharmaceutical preparations, and may be used for preparing a pre-polymer, a polyurethane making the PPG to react with diisocyanate, to which subsequently tartaric acid is added for obtaining a poly (amide urethane) identified by the acronym PTPPGHI .
Into a flask, previously dehumidified through 5 cycles vacuum/N2 and having 100 ml capacity, at room temperature
1.15 g PPG-400, 97 μl DBLT, and 3.0 ml of HMDI were loaded.
The reaction system is the stirred for about 30 min at room temperature and under N2 atmosphere. Therefore 9.0 ml of anhydrous DMF are added, subsequently the reaction system is stirred for about 5 min at room temperature and under N2 atmosphere, and subsequently 2.46 g of tartaric acid were added. Therefore reaction system is stirred for about 30 min under N2 atmosphere, and the temperature of the reaction system is maintained at about 4O0C using an ice bath.
As the reaction proceed, CO2 development and turbidity and viscosity increasing of the reaction system due to the formation of the first oligomers, may be observed.
After the reaction terminate, the obtained polymers is then spread by casting procedure in a support, for example a LDPE sheet, and is left stand in N2 atmosphere on the support till an optimum value of the viscosity it is achieved. Afterwards the polymer film is subjected to drying in an oven using the same methods as those seen with reference with the previous example 4, at a temperature comprised between about 4O0C and about 6O0C for about 45 min and increasing the temperature of about 1O0C every 45 min till a temperature of about 6O0C is reached. The polymer films were then left in the oven for about 36 hours, or also for a period of time so that the polymer films remain into the oven for a total period of time of about 36 hours. It is herein below represented the diagram of the above disclosed reactions.
Figure imgf000064_0001
Figure imgf000064_0002
Also in this reaction system, it has been provided for varying the reciprocal concentration of the reactants, for example the concentration of PPG.
Tests conducted have shown that the optimum value of the concentration of PPG is about 20% by weight considered on the total weight of all the reactants, namely weight of (Tartaric acid+HMDI) *20/100=weight of PPG.
Also in this reaction system, it has been provided for varying the value of the concentration of DMF, so as to decrease the concentration of residual solvent, DMF, in the polymer obtained.
Tests conducted have shown that the minimum value of the concentration of DMF so that the reaction system remains homogeneous during the reaction and the precipitation of the oligomers do not occur, is about 45% by weight considered on the total weight of the mixing reaction, namely weight of
(Tartaric acid+HMDI+PPG) *55/45=weight of DMF. In other words, the optimum value of the concentration of DMF is so that the weight of DMF is equal to 1.5 times the weight of (AT+HMDI) . Furthermore the above reaction has been repeated varying the molecular weight of the PPG and varying the stoichiometric percentage of PPG in relation to the other reactants .
Therefore different co-polymers have been obtained, that have been analysed. The analysis have shown that using a PPG having a means molecular weight of about 400, and using about 20% by weight of PPG, (as already seen PPG/ (AT+HMDI) =20/100, the preferred polymers are obtained.
The polymers obtained with the above condition id a colourless polymer tending to yellow over time, shaped as a sheet .
Such polymer sheet has been subjected to casting on a suitable support, and to a drying procedure.
Tests have also been made for testing if the polymer could absorb a colouring agent. The colouring agent named as
"dispersed red", that is a polar colouring agent, has been added to the reaction mixture from the beginning of the reaction.
Analysing the obtained polymer, it has been noticed that the colouring agent is absorbed and kept by the polymer, also by the dried polymeric film. In other words, the colouring agent is kept into the polymers and has a good colouring efficacy even if used at very low concentration, for example concentrations of the order of 0.05%. Furthermore, the colouring agent does not modify the features of the obtained polymer and do not favour and/or trigger degradative reactions .
The obtained polymers have been spread on supports of various kind for testing the adhesiveness of the polymers, for example paper, common glass, polyethylene, aluminium have been used.
Effected test have shown a good adhesiveness of the obtained polymers to all the supports .
Therefore this kind of polymers may be used for producing composite materials. The above seen reaction has been varied so as to obtain a mixing reaction free of a precipitate inside it and having the viscosity suitable for casting.
Also in this reaction system, it has been provided for varying the value of the concentration of DMF, so as to decrease the concentration of residual solvent, DMF, in the polymer obtained, so exploiting the solvent properties of the PPG.
Tests conducted have shown that the DMF is necessary inside the reaction system for conducting the polymerisation reaction and that the minimum value of the concentration of DMF so that the reaction system remains homogeneous during the reaction and the precipitation of the oligomers do not occur, is about 60% by weight, namely weight of DMF/weight of (Tartaric acid+HMDI) =60/40. The samples obtained have been subjected to thermal analysis, for example TGA and DSC analysis. Such tests have shown that the PTPPGHI obtained polymer is an amorphous material, having a glass transition temperature of comprised between about -30C and about 50C.
Samples have been furthermore subjected to TGA analysis, but it was not possible to measure the quantity of possible residual solvent, since a certain degradation of the polymer occurs .
The samples have been furthermore subjected to dynamic- mechanic rheometric capillary analysis, that has shown that the obtained polymers have until a temperature of about 7O0C values of the elasticity and viscosity coefficient comprised between about 108 and about 1010 Pa, at temperature values higher than 7O0C the polymers have are probably subjected to glass transition and this make the mechanical properties of the polymers to be changed.
At temperature values higher than 13O0C a visible degradation of the polymer occurs .
The afore described rheometric capillary analysis has also shown that certain quantities of the solvent are remained into the polymer, the polymer may be removed by subjecting the polymer to the treatment already discussed in connection to the other polymers according to the invention.

Claims

1. Method for obtaining polyamides having a general formula [-CO-R/ 1-CONH-R2-NH-] comprising mixing a first compound having a general formula Ri(COOH)2 with a further compound having a general formula R2(NCO)2, to bring about a polymerisation reaction, wherein Ri is a radical provided with at least an alcoholic function.
2. Method according to claim 1, wherein adding said first compound in quantities comprised between 30% and 70% is provided for.
3. Method according to claim 1, wherein adding said first compound in quantities of the order of approximately 50% is provided for.
4. Method according to any one of claims 1 to 3, wherein adding said further compound in quantities comprised between 30% and 70% is provided for.
5. Method according to any one of claims 1 to 3, wherein adding said further compound in quantities of the order of approximately 50% is provided for.
6. Method according to claim 1, wherein said mixing comprises mixing said first compound and said further compound in quantities that are stoichiometric to one another.
7. Method according to any one of claims 1 to 6, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost linear structure .
8. Method according to any one of claims 1 to 7, wherein said mixing said first compound comprises adding a compound comprising a radical Ri having the same formula as R'i.
9. Method according to any one of claims 1 to 6, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost branched and/or cross-linked structure.
10. Method according to any one of claims 1 to 9, wherein the radical R' i of said polyamide is a radical comprising in the formula thereof the radical R2 of said further compound.
11. Method according to any one of claims 1 to 10, wherein the radical R' 1 of said polyamide is a radical having a general formula [-CH (OH) -CH-OR (-CONH-R2-NH-) -CO-] .
12. Method according to any one of claims 1 to 11, wherein mingling said first compound with a catalyst is provided for.
13. Method according to any one of claims 1 to 12, wherein amalgamating said first compound with anhydrous DMF is provided for.
14. Method according to claim 12, or 13 as appended to claim 12, wherein said mingling precedes said mixing.
15. Method according to claim 13, or 14 as appended to claim 13, wherein said amalgamating precedes said mixing.
16. Method according to any one of claims 13 to 15, as claim 13 is appended to claim 12, wherein said amalgamating is subsequent to said mingling.
17. Method for obtaining co-polyamides having a general formula [-CO-R3-CONH-R2-NHCO-R^-NH-R2-NH-] comprising mixing with first compound having a general formula Ri(COOH)2 with a second compound having a general formula Rs(COOH)2 and further mixing with further compound having a general formula R2(NCO)2 to bring about the polymerisation reaction, wherein Ri is a radical provided with at least an alcoholic function.
18. Method according to claim 17, wherein adding said first compound in molar quantities comprised between 10% and 80% is provided for.
19. Method according to claim 17, wherein adding said first compound in molar quantities comprised between 35% and 45% is provided for.
20. Method according to claim 17, wherein adding said first compound in molar quantities of the order of approximately 25% is provided for.
21. Method according to any one of claims 17 to 20, wherein adding said further compound in molar quantities comprised between 10% and 80% is provided for.
22. Method according to any one of claims 17 to 20, wherein adding said further compound in molar quantities comprised between 40% and 60% is provided for.
23. Method according to any one of claims 17 to 20, wherein adding said further compound in molar quantities of the order of approximately 50% is provided for.
24. Method according to any one of claims 17 to 23, wherein further adding said second compound in molar quantities comprised between 10% and 80% is provided for.
25. Method according to any one of claims 17 to 23, wherein further adding said second compound in molar quantities comprised between 35% and 45% is provided for.
26. Method according to any one of claims 17 to 23, wherein further adding said second compound in molar quantities of the order of approximately 25% is provided for.
27. Method according to claim 17, wherein adding said first compound and said second compound in quantities that are equimolar to one another is provided for.
28. Method according to any one of claims 16 to 27, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost linear structure .
29. Method according to any one of claims 17 to 28, wherein said mixing said first compound comprises adding a compound comprising a radical Ri having the same formula as R'i.
30. Method according to any one of claims 17 to 29, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost branched and/or cross-linked structure.
31. Method according to any one of claims 17 to 30, wherein the radical R' i of said co-polyamide is a radical comprising in the formula thereof the radical R2 of said further compound.
32. Method according to any one of claims 17 to 31, wherein the radical R' 1 of said co-polyamide is a radical having a general formula [-CH (OH) -CH-OR (-CONH-R2-NH-) -CO-] .
33. Method according to any one of claims 17 to 32, wherein said further mixing precedes said mixing.
34. Method according to any one of claims 17 to 33, wherein mingling said first compound with a catalyst is provided for.
35. Method according to any one of claims 17 to 34, wherein amalgamating said first compound with anhydrous DMF is provided for.
36. Method according to claim 34, as appended to claim 33, or to claim 35 as appended to claim 33, or 34 as appended to claim 33, wherein said mingling is subsequent to said further mixing.
37. Method according to claim 34, as appended to claim 33, or to claim 35 as appended to claim 33, or 34 as appended to claim 33, or according to claim 35, wherein said mingling precedes said mixing.
38. Method according to claim 35 as appended to claim 33, or 34 as appended to claim 33, wherein said amalgamating is subsequent to said further mixing with and precedes said mixing.
39. Method for obtaining co-poly (amide esters) comprising a first phase wherein glycolic acid (OH-CH2-CO-OH) is made to react with lactic acid (OH-CH2- (CH3) -CO-OH) and succinic anhydride (C4H4O3) to obtain a poly (lactic glycol carboxy terminated) acid having a general formula [-OH-CO-C2H4-CO- [OR-CH2-CO-OR-CH2- (CH3) -CO-OR-] n- H] and a second phase wherein mixing the product obtained following the reaction of the first phase with a first compound having a general formula Ri(COOH)2, and further mixing with a further compound having a general formula R2 (NCO) 2 to bring about the polymerisation reaction, obtaining polyesters having a general formula [-NH- R2-NH-CO-R' !-CO-NH-R2-NH-CO-C2H4-CO- [OR-CH2- CO-OR-CH2- (CH3) -CO-OR-In-ICH2-CO-OR-CH2- (CH3) -CO-] m is provided, wherein Ri is a radical provided with at least an alcoholic function.
40. Method according to claim 39, wherein said poly (lactic glycol carboxy terminated) acid is obtained from glycolic acid, lactic acid and succinic anhydride.
41. Method according to claim 39, or 40, wherein adding said first compound in molar quantities comprised between 10% and 80% is provided for.
42. Method according to claim 39, or 40, wherein adding said first compound present in molar quantities comprised between 35% and 45% is provided for.
43. Method according to claim 39, or 40, wherein adding said first compound in molar quantities of the order of approximately 25% is provided for.
44. Method according to any one of claims 39 to 43, wherein adding said further compound in molar quantities comprised between 10% and 80% is provided for.
45. Method according to any one of claims 39 to 43, wherein adding said further compound in molar quantities comprised between 40% and 60% is provided for.
46. Method according to any one of claims 39 to 43, wherein adding said further compound in molar quantities of the order of approximately 50% is provided for.
47. Method according to any one of claims 39 to 46, wherein further adding said poly (lactic glycol carboxy terminated) acid in molar quantities comprised between 10% and 80% is provided for.
48. Method according to any one of claims 39 to 46, wherein further adding said poly (lactic glycol carboxy terminated) acid in molar quantities comprised between 35% and 45% is provided for.
49. Method according to any one of claims 39 to 46, wherein further adding said poly (lactic glycol carboxy terminated) acid in molar quantities of the order of approximately 25% is provided for.
50. Method according to claim 39, wherein said mixing comprises mixing said first compound and said poly (lactic glycol carboxy terminated) acid in quantities that are equimolar to one another.
51. Method according to any one of claims 39 to 50, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost linear structure .
52. Method according to any one of claims 39 to 51, wherein said mixing said first compound comprises adding a compound comprising a radical Ri having the same formula as R'i.
53. Method according to any one of claims 39 to 52, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost branched and/or cross-linked structure.
54. Method according to any one of claims 39 to 53, wherein the radical R' i of said co-polyamide is a radical comprising in the formula thereof the radical R2 of said further compound.
55. Method according to any one of claims 39 to 54, wherein the radical R' 1 of said co-polyamide is a radical having a general formula [-CH (OH) -CH-OR (-CONH-R2-NH-) -CO-] .
56. Method according to any one of claims 39 to 55, wherein mingling said first compound with a catalyst is provided for.
57. Method according to any one of claims 39 to 56, wherein amalgamating said first compound with anhydrous DMF is provided for.
58. Method according to claim 56, or 57 as appended to claim 56, wherein said mingling is subsequent to said mixing.
59. Method according to claim 56, or 57 as appended to claim 56, or 58, wherein said mingling precedes said further mixing.
60. Method according to claim 57, or according to claim 58, or 59, and appended to claim 57, wherein said amalgamating is subsequent to said mixing.
61. Method according to claim 57, or according to claim 58, or 59, if appended to claim 57, wherein said amalgamating precedes said further mixing.
62. Method for obtaining co-poly (amide urethanes) having a general formula [-NH-R2-NH-CO-RI-CONH-R2-NH-CO-(OR-CH2- CH2-) X- (OR-CH (CH3) -CH2-) Y- (OR-CH2-CH2-) z-0R-C0-] comprising mixing with first compound having a general formula Ri(COOH)2 with a fourth compound having a general formula H- (OR-CH2-CH2-) x- (OR-CH (CH3) -CH2-) γ- (OR-CH2-CH2- ) z-OH and further mixing with a further compound having a general formula R2(NCO)2 to bring about a polymerisation reaction, wherein Ri is a radical provided with at least an alcoholic function.
63. Method according to claim 62, wherein said mixing comprises mixing with said first compound a compound chosen from a group comprising the co-polymers with poly (ethylene glycols) -poly (propylene glycol) -poly
(ethylene glycols) (PEG-PPG-PEG) blocks.
64. Method according to claim 62, wherein said mixing comprises mixing with said first compound a compound chosen from the poloxamer-type compounds .
65. Method according to claim 62, wherein said mixing comprises mixing the poloxamer 1100 with said first compound.
66. Method according to any one of claims 62 to 65, wherein said mixing comprises mixing said first compound and said fourth compound in quantities such that their reciprocal weighted ratio is comprised between 4 and 0.5.
67. Method according to any one of claims 62 to 65, wherein said mixing comprises mixing said first compound and said fourth compound in quantities such that their reciprocal weighted ratio is equal approximately to 1.
68. Method according to any one of claims 62 to 67, wherein said further mixing comprises adding said further compound in molar quantities comprised between 10% and 80% of the stoichiometric ratio.
69. Method according to any one of claims 62 to 67, wherein said further mixing comprises adding said further compound in molar quantities comprised between 40% and 60% of the stoichiometric ratio.
70. Method according to any one of claims 62 to 67, wherein said further mixing comprises adding said further compound in molar quantities of the order of approximately 50% of the stoichiometric ratio.
71. Method according to any one of claims 62 to 70, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost linear structure.
72. Method according to any one of claims 62 to 71, wherein said mixing said first compound comprises adding a compound comprising a radical Ri having the same formula as R'i.
73. Method according to any one of claims 62 to 72, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost branched and/or cross-linked structure.
74. Method according to any one of claims 62 to 73, wherein the radical R' i of said co-polyamide is a radical comprising in the formula thereof the radical R2 of said further compound.
75. Method according to any one of claims 62 to 74, wherein the radical R' 1 of said co-polyamide is a radical having a general formula [-CH (OH) -CH-OR (-CONH-R2-NH-) -CO-] .
76. Method according to any one of claims 62 to 75, wherein mingling said first compound with a catalyst is provided for.
77. Method according to any one of claims 62 to 76, wherein amalgamating said first compound with anhydrous DMF is provided for.
78. Method according to claim 76, or 77 as appended to claim 76, wherein said mingling is subsequent to said mixing.
79. Method according to claim 76, or 77 as appended to claim 76, or 78, wherein said mingling precedes said further mixing.
80. Method according to claim 77, or according to claim 78, or 79, if appended to claim 77, wherein said amalgamating is subsequent to said mixing.
81. Method according to claim 77, or according to claim 78, or 79, and appended to claim 77, wherein said amalgamating precedes said further mixing.
82. Method for obtaining co-poly (amide urethanes) having a general formula [-NH-R2-NH-CO-RI-CONH-R2-NH-CO-(OR-CH2-
CH2-) n-0R-C0-] comprising mixing a first compound having a general formula Ri(COOH)2 with a fifth compound having a general formula H- (OR-CH2-CH2-) n-0H and further mixing with a further compound having a general formula R2(NCO)2 to bring about a polymerisation reaction, wherein Ri is a radical provided with at least an alcoholic function.
83. Method according to claim 82, wherein said mixing comprises mixing with said first compound a compound chosen from the oligomers of the poly (ethylene glycols) .
84. Method according to claim 82, or 83, wherein said mixing comprises mixing with said first compound a compound that has a molecular weight comprised between approximately 500 and approximately 5000.
85. Method according to claim 82, or 83, wherein said mixing comprises mixing with said first compound a compound that has a molecular weight comprised between approximately 1000 and approximately 4000.
86. Method according to any one of claims 82 to 85, wherein said mixing comprises mixing said first compound and said fifth in molar quantities such that their reciprocal ratio is comprised between approximately 4 and approximately 0.5.
87. Method according to any one of claims 82 to 85, wherein said mixing comprises mixing said first compound and said fifth compound are present in molar quantities such that their reciprocal ratio is equal approximately to 1.
88. Method according to any one of claims 82 to 87, wherein said further mixing comprises further mixing said further compound in molar quantities comprised between 10% and 80% of the stoichiometric ratio.
89. Method according to any one of claims 82 to 87, wherein said further mixing comprises further mixing said further compound in molar quantities comprised between 40% and 60% of the stoichiometric ratio.
90. Method according to any one of claims 82 to 87, wherein said further mixing comprises further mixing said further compound in molar quantities of the order of approximately 50% of the stoichiometric ratio.
91. Method according to any one of claims 82 to 90, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost linear structure.
92. Method according to any one of claims 82 to 91, wherein said mixing said first compound comprises adding a compound comprising a radical Ri having the same formula as R'i.
93. Method according to any one of claims 82 to 92, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost branched and/or cross-linked structure.
94. Method according to any one of claims 82 to 93, wherein the radical R' i of said co-polyamide is a radical comprising in the formula thereof the radical R2 of said further compound.
95. Method according to any one of claims 82 to 94, wherein the radical R' 1 of said co-polyamide is a radical having a general formula [-CH (OH) -CH-OR (-CONH-R2-NH-) -CO-] .
96. Method according to any one of claims 82 to 95, wherein mingling said first compound with a catalyst is provided for.
97. Method according to any one of claims 82 to 96, wherein amalgamating said first compound with anhydrous DMF is provided for.
98. Method for obtaining co-polyesters having a general formula [ [ (-0R- (CH2-) 5-C0) H1-OR-CH2-CH2-OR-CH2-CH2-OR- (-C0- (CH2-) 5-OR) m] n-CO-Ri-CO-] comprising mixing a first compound having a general formula Ri(COOH)2 with a sixth compound having a general formula [ (-0R- (CH2-) 5-C0) m-0R- CH2-CH2-OR-CH2-CH2-OR- (-CO- (CH2-) 5-OR) m]n to bring about a polymerisation reaction, wherein Ri is a radical provided with at least an alcoholic function.
99. Method according to claim 98, wherein said mixing comprises mixing with said first compound a compound chosen amongst the caprolactone polymers .
100. Method according to claim 98, or 99, wherein said mixing comprises mixing said first compound and said sixth compound in molar quantities such that the reciprocal ratio between such quantities is comprised between approximately 4 and approximately 0.2.
101. Method according to claim 98, or 99, wherein said mixing comprises mixing said first compound and said sixth compound in molar quantities that are stoichiometric to one another.
102. Method according to any one of claims 98 to 101, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost linear structure.
103. Method according to any one of claims 98 to 102, wherein said mixing said first compound comprises adding a compound comprising a radical Ri having the same formula as R' i .
104. Method according to any one of claims 98 to 103, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost branched and/or cross-linked structure.
105. Method according to any one of claims 98 to 104, wherein the radical R' i of said co-polyamide is a radical comprising in the formula thereof the radical R2 of said further compound.
106. Method according to any one of claims 98 to 105, wherein the radical R' 1 of said co-polyamide is a radical having a general formula [-CH (OH) -CH-OR (-CONH- R2-NH-) -CO-] .
107. Method according to any one of claims 98 to 106, wherein mingling said first compound with a catalyst is provided for.
108. Method according to any one of claims 98 to 107, wherein amalgamating said first compound with anhydrous
DMF is provided for.
109. Method according to claim 107, or 108 as appended to claim 107, wherein said mingling is subsequent to said mixing.
110. Method according to claim 107, or 108 as appended to claim 107, or 109, wherein said mingling precedes said further mixing.
111. Method according to claim 108, or according to claim 109, or 110, and appended to claim 108, wherein said amalgamating is subsequent to said mixing.
112. Method according to claim 108, or according to claim 109, or 110, if appended to claim 108, wherein said amalgamating precedes said further mixing.
113. Method according to any one of claims 1 to 112, wherein said mixing said first compound comprises adding a compound wherein said radical Ri comprises a plurality of alcoholic functions .
114. Method according to any one of claims 1 to 113, wherein said mixing said first compound comprises adding a compound wherein said radical Ri comprises two alcoholic functions (-0H) .
115. Method according to any one of claims 1 to 114, wherein said mixing said first compound comprises adding a compound wherein said radical Ri is selected from a group comprising the aliphatic radicals, the radicals containing double bonds, the radicals with a linear or branched, or cross-linked, or aromatic chain.
116. Method according to any one of claims 1 to 115, wherein said mixing said first compound comprises adding a compound chosen from the dihydroxy acids .
117. Method according to any one of claims 1 to 116, wherein said mixing said first compound comprises adding tartaric acid, or a compound similar thereto.
118. Method according to any one of claims 1 to 117, wherein said mixing said further compound comprises adding a compound wherein the radical R2 comprises an aliphatic radical, with linear, or branched, or cross-linked, or cyclical, or aromatic chain, and/or provided with double bonds .
119. Method according to any one of claims 1 to 118, wherein said mixing said further compound comprises adding a compound provided with a plurality of functions (-NCO) characteristic of the isocyanates.
120. Method according to any one of claims 1 to 119, wherein said mixing said further compound comprises adding a compound provided with two functions (-NCO) characteristic of the isocyanates.
121. Method according to any one of claims 1 to 120, wherein said mixing said further compound comprises adding a compound of the family of diisocyanates .
122. Method according to any one of claims 1 to 121, wherein said mixing said further compound comprises adding a terminal diisocyanate .
123. Method according to any one of claims 1 to 122, wherein said mixing said further compound comprises adding a diisocyanate that can be chosen between the aliphatic- chain diioscyanates, or provided with double bonds, or with linear, or branched, or cross-linked, or cyclical, or aromatic chain.
124. Method according to any one of claims 1 to 123, wherein said mixing said further compound comprises adding a compound that can be chosen from a group comprising diisocyanatohexane (HMDI), 1,8 diisocyanatooctane (OMDI), 1,12 diisocyanatododecane (DMDI).
125. Method according to any one of claims 1 to 124, wherein catalysing said reaction using an organometal compound is provided for.
126. Method according to any one of claims 1 to 125, wherein catalysing said reaction using dibutyl tin laurate (DBLT) is provided for.
127. Method according to any one of claims 1 to 125, wherein catalysing said reaction using dibutyl tin oxide (DBTO) is provided for.
128. Method according to any one of claims 1 to 127, wherein amalgamating said first compound with DMF anhydrous
(N, N-dimethylformamide) is provided for.
129. Method according to any one of claims 1 to 128, wherein, after said further mixing, for approximately 3 hours heating the reaction mixture obtained is provided for.
130. Method according to claim 129, wherein, after said heating, precipitating a reaction product is provided for.
131. Method according to claim 130, wherein, after said precipitating, washing said reaction product is provided for.
132. Method according to claim 131, wherein, after said washing, filtering said reaction product is provided for.
133. Method according to claim 132, wherein, after said filtering, further washing said reaction product with methanol is provided for.
134. Method according to claim 133, wherein, after said further washing, still further washing said reaction product with ethanol is provided for.
135. Method according to claim 134, wherein, after said still further washing, drying said reaction product is provided for.
136. Method according to any one of claims 1 to 135, wherein supplying nitrogen during said polymerisation reaction is provided for.
137. Method according to any one of claims 1 to 136, wherein stirring said polymerisation reaction is provided for.
138. Method for obtaining co-poly (amide urethanes) having a general formula [-NH-R2-NH-CO-RI-CONH-R2-NH-CO-(O-CH2-
CH2-) n-0-C0-] comprising mixing a first compound having a general formula Ri(COOH)2 with a seventh compound having a general formula H-[O-CH-(CH3)- CH2Jn-OH and further mixing with a further compound having a general formula R2(NCO)2 to bring about a polymerisation reaction, in which Ri is a radical provided with at least an alcoholic function.
139. Method according to claim 138, wherein said mixing comprises mixing with said first compound a compound chosen from a group comprising the co-polymers with poly (propylene glycols), (PPG) blocks.
140. Method according to claim 139, wherein said mixing comprises mixing with said first compound a compound chosen from the PPG-type compounds .
141. Method according to any one of claims 138 to 140, wherein said mixing comprises mixing said first compound and said seventh compound in quantities such that their reciprocal weighted ratio is comprised between 4 and 0.5.
142. Method according to any one of claims 138 to 141, wherein said mixing comprises mixing said first compound and said seventh compound in quantities such that the weighted ratio of said seventh compound is about 20% on the total weight of the reactants .
143. Method according to any one of claims 138 to 142, wherein said mixing comprises mixing said first compound and said seventh compound in quantities such that the weighted ratio of said seventh compound is about (first compound+ further compound) *20/100= seventh compound.
144. Method according to any one of claims 138 to 143, wherein said further mixing comprises adding said further compound in molar quantities comprised between 10% and 80% of the stoichiometric ratio.
145. Method according to any one of claims 138 to 144, wherein said further mixing comprises adding said further compound in molar quantities comprised between 40% and 60% of the stoichiometric ratio.
146. Method according to any one of claims 138 to 145, wherein said further mixing comprises adding said further compound in molar quantities of the order of approximately 50% of the stoichiometric ratio.
147. Method according to any one of claims 138 to 146, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost linear structure.
148. Method according to any one of claims 138 to 147, wherein said mixing said first compound comprises adding a compound comprising a radical Ri having the same formula as R' i .
149. Method according to any one of claims 138 to 148, wherein said bring about the polymerisation reaction is such as to obtain a plastic material with an almost branched and/or cross-linked structure.
150. Method according to any one of claims 138 to 149, wherein the radical R' i of said co-polyamide is a radical comprising in the formula thereof the radical R2 of said further compound.
151. Method according to any one of claims 138 to 150, wherein the radical R' 1 of said co-polyamide is a radical having a general formula [-CH (OH) -CH-OR (-CONH- R2-NH-) -CO-] .
152. Method according to any one of claims 138 to 151, wherein mingling said first compound with a catalyst is provided for.
153. Method according to any one of claims 138 to 142, wherein amalgamating said first compound with anhydrous DMF is provided for.
154. Method according to claim 152, or 153, as appended to claim 152, wherein said mingling is subsequent to said mixing.
155. Method according to claim 152, or 153 as appended to claim 152, or 154, wherein said mingling precedes said further mixing.
156. Method according to claim 153, or according to claim 154, or 155, if appended to claim 154, wherein said amalgamating is subsequent to said mixing.
157. Method according to claim 153, or according to claim 154, or 155, and appended to claim 153, wherein said amalgamating precedes said further mixing.
158. Method according to claim 153, or according to any one of claims 154 to 157 as appended to claim 153, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that said DMF is present in quantities comprised between about 30% and about 60% by weight on the weight of the total reactants .
159. Method according to claim 153, or according to any one of claims 154 to 157 as appended to claim 153, or according to claim 158, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that said DMF is present in quantities of about 45% by weight on the weight of the total reactants .
160. Method according to claim 153, or according to any one of claims 154 to 157 as appended to claim 153, or according to claim 158, or 159, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that said the reciprocal weight ratio is about (first compound+ further compound+ seventh compound) *55/45= DMF.
161. Method according to any one of claims 13 to 16, as claim 14 is appended to claim 13, or according to claim 35, or 38, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that said DMF is present in quantities comprised between about 10% and about 65% by weight on the weight of the total reactants .
162. Method according to any one of claims 13 to 16, as claim 14 is appended to claim 13, or according to claim 35, or 38, or according to claim 161, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that said DMF is present in quantities comprised between about 30% and about 50% by weight on the weight of the total reactants .
163. Method according to any one of claims 13 to 16, as claim 14 is appended to claim 13, or according to claim
35, or 38, or according to claim 161, or 162, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that said DMF is present in quantities of about 40% by weight on the weight of the total reactants .
164. Method according to any one of claims 13 to 16, as claim 14 is appended to claim 13, or according to claim 35, or 38, or according to claim 161, or 162, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that said DMF is present in quantities of about 60% by weight on the weight of the total reactants .
165. Method according to any one of claims 1 to 164, wherein said mixing comprises mixing said first compound and said further compound so that the reciprocal molar ratio first compound: further compound is comprised between about 1 : 2 and 1:0.8.
166. Method according to any one of claims 1 to 164, wherein said mixing comprises mixing said first compound and said further compound so that the reciprocal molar ratio first compound: further compound is comprised between about 1:1.8 and 1:0.9.
167. Method according to any one of claims 1 to 164, wherein said mixing comprises mixing said first compound and said further compound so that the reciprocal molar ratio first compound: further compound is comprised between about 1:1.6 and 1:1.
168. Method according to any one of claims 1 to 164, wherein said mixing comprises mixing said first compound and said further compound so that the reciprocal molar ratio is first compound: further compound = 1:1.05.
169. Method according to any one of claims 1 to 164, wherein said mixing comprises mixing said first compound and said further compound so that the reciprocal molar ratio is first compound: further compound = 1:1.1.
170. Method according to any one of claims 1 to 164, wherein said mixing comprises mixing said first compound and said further compound so that the reciprocal molar ratio is first compound: further compound = 1:1.2.
171. Method according to any one of claims 1 to 164, wherein said mixing comprises mixing said first compound and said further compound so that the reciprocal molar ratio is first compound: further compound = 1:1.4.
172. Method according to any one of claims 1 to 164, wherein said mixing comprises mixing said first compound and said further compound so that the reciprocal molar ratio is first compound: further compound = 1:1.6.
173. Method according to any one of claims 168 to 170, wherein said bring about comprises obtaining thermoplastic polymeric material.
174. Method according to any one of claims 168 to 170, and further comprising measuring the viscosity of the polymers obtained from said polymerisation reaction.
175. Method according to any claim 171, or 172, wherein said bring about comprises obtaining thermosettable polymeric material.
176. Method according to any one of claims 1 to 175, wherein said bring about comprises keeping the temperature between about 2O0C and 8O0C.
177. Method according to any one of claims 1 to 176, wherein said bring about comprises keeping the temperature between about 250C and 6O0C.
178. Method according to any one of claims 1 to 177, wherein said bring about comprises keeping the temperature at about 4O0C.
179. Method according to any one of claims 1 to 178, wherein said keeping comprises using an ice bath regulating the temperature of the reaction system.
180. Method according to any one of claims 1 to 179, wherein extracting a polymer obtained from said polymerisation reaction it is provided for.
181. Method according to claim 180, wherein said extracting comprises almost completely removing a solvent form said polymer obtained from said polymerisation reaction.
182. Method according to claim 180, or 181, wherein said extracting comprises increasing the glass transition temperature of said polymer obtained from said polymerisation reaction.
183. Method according to any one of claims 170 to 182, wherein said extracting comprises increasing the molecular weight of said polymer obtained from said polymerisation reaction.
184. Method according to any one of claims 170 to 183, wherein said extracting comprises further removing at least some of the oligomers of said polymer obtained from said polymerisation reaction.
185. Method according to any one of claims 170 to 184, wherein said extracting comprises extracting said polymer obtained from said polymerisation reaction with a "Kumagawa extractor" .
186. Method according to any one of claims 62 to 81, wherein said mixing comprises mixing said first compound with said fourth compound so that said fourth compound is present in a weight percent of comprised between about 30% and 70% calculated over the total weight of the reactants of the polymerisation reaction.
187. Method according to any one of claims 62 to 81, wherein said mixing comprises mixing said first compound with said fourth compound so that said fourth compound is present in a weight percent of comprised between about 20% and 40% calculated over the total weight of the reactants of the polymerisation reaction.
188. Method according to any one of claims 62 to 81, or according to claim 163, or 164, wherein said mixing comprises mixing said first compound with said fourth compound so that said fourth compound is present in a weight percent of about 20% calculated over the total weight of the reactants of the polymerisation reaction.
189. Method according to any one of claims 62 to 81, or according to any one of claims 163 to 165, wherein said mixing and said further mixing comprise mixing said fourth compound so that said weight reciprocal ratio is about first compound: further compound * 20/100= fourth compound.
190. Method according to any one of claims 62 to 81, or according to any one of claims 163 to 165, wherein said mixing and said further mixing comprise mixing said fourth compound so that said weight reciprocal ratio is about first compound: further compound * 40/100= fourth compound.
191. Method according to any one of claims 77 to 81, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that said DMF is present in quantities comprised between about 30% and about 80% by weight on the weight of the total reactants .
192. Method according to any one of claims 77 to 81, or according to claim 191, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that said DMF is present in quantities comprised between about 40% and about 70% by weight on the weight of the total reactants .
193. Method according to any one of claims 77 to 81, or according to claim 191, or 192, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that said DMF is present in quantities of about 65-67% by weight on the weight of the total reactants .
194. Method according to any one of claims 77 to 81, or according to any one of claims 191 to 193, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that the weight percent of said DMF is about (first compound + further compound + fourth compound)* 65/35.
195. Method according to any one of claims 77 to 81, or according to any one of claims 191 to 194, wherein said amalgamating comprises amalgamating said first compound to said anhydrous DMF so that the weight percent of said DMF is about (first compound + further compound + fourth compound)* 67/33.
196. Method according to any one of claims 1 to 195 and further comprises almost continuously modulating the properties of the polymer obtained by said polymerisation reaction by varying the composition of the reaction system.
197. Method according to any one of claims 1 to 196 and further comprises almost continuously modulating the properties of the polymer obtained by said polymerisation reaction by varying the reciprocal molar or weight ratio of the reactants .
198. Method according to any one of claims 1 to 197 and further comprising adding a colouring agent for colouring the polymer obtained by said polymerisation reaction
199. Biodegradable polyamide having a general formula [-C0- R' 1-CONH-R2-NH-] obtained from a first compound Ri(COOH)2 and from a further compound R2(NCO)2, wherein Ri comprises a radical provided with at least an alcoholic function.
200. Polyamide according to claim 199, wherein said first compound is present in quantities comprised between 30% and 70%.
201. Polyamide according to claim 199, wherein said first compound is present in quantities of the order of approximately 50%.
202. Polyamide according to any one of claims 199 to 201, wherein said further compound is present in quantities comprised between 30% and 70%.
203. Polyamide according to any one of claims 199 to 201, wherein said further compound is present in quantities is of the order of approximately 50%.
204. Polyamide according to any one of claims 199 to 201, wherein said first compound and said further compound are mixed in quantities that are stoichiometric to one another.
205. Polyamide according to any one of claims 199 to 204, wherein said polyamide has an almost linear structure.
206. Polyamide according to any one of claims 199 to 205, wherein R' i is a radical having the same formula as Ri.
207. Polyamide according to any one of claims 199 to 206, wherein said polyamide has a branched and/or cross- linked structure.
208. Polyamide according to any one of claims 199 to 207, wherein R' i is a radical comprising in the formula thereof the radical R2.
209. Polyamide according to any one of claims 199 to 208, wherein R' 1 is a radical having a general formula [- CH(OH) -CH-OR (-CONH-R2-NH-) -CO-] .
210. Biodegradable polyamide having a general formula [-C0- R3-CONH-R2-NHCO-R' 1-NH-R2-NH-] obtained from a first compound Ri(COOH)2 and from a further compound R2(NCO)2, and from a second compound Rs(COOH)2, wherein Ri comprises a radical provided with at least an alcoholic function.
211. Polyamide according to claim 210, wherein said first compound is present in molar quantities comprised between 10% and 80%.
212. Polyamide according to claim 210, wherein said first compound is present in molar quantities comprised between 35% and 45%.
213. Polyamide according to claim 210, wherein said first compound is present in molar quantities of the order of approximately 25%.
214. Polyamide according to any one of claims 210 to 213, wherein said further compound is present in molar quantities comprised between 10% and 80%.
215. Polyamide according to any one of claims 210 to 213, wherein said further compound is present in molar quantities comprised between 40% and 60%.
216. Polyamide according to any one of claims 210 to 213, wherein said further compound is present in molar quantities of the order of approximately 50%.
217. Polyamide according to any one of claims 210 to 216, wherein said second compound is present in molar quantities comprised between 10% and 80%.
218. Polyamide according to any one of claims 210 to 216, wherein said second compound is present in molar quantities comprised between 35% and 45%.
219. Polyamide according to any one of claims 210 to 216, wherein said second compound is present in molar quantities of the order of approximately 25%.
220. Polyamide according to any one of claims 210 to 219, wherein said first compound and said second compound are mixed in quantities that are equimolar to one another.
221. Polyamide according to any one of claims 210 to 220, wherein said polyamide has an almost linear structure.
222. Polyamide according to any one of claims 210 to 221, wherein R' i is a radical having the same formula as Ri.
223. Polyamide according to any one of claims 210 to 222, wherein said polyamide has a branched, and/or cross- linked structure.
224. Polyamide according to any one of claims 210 to 223, wherein R' i is a radical comprising in the formula thereof the radical R2.
225. Polyamide according to any one of claims 210 to 224, wherein R' 1 is a radical having a general formula [- CH (OH) -CH-OR (-CONH-R2-NH-) -CO-] .
226. Co-poly (amide ester) biodegradable having a general formula [-NH-R2-NH-CO-R' !-CO-NH-R2-NH-CO-C2H4-CO- [OR-CH2- CO-OR-CH2- (CH3) -CO-OR-] n-iCHz-CO-OR-CHz- (CH3) -CO-] m, obtained from a first compound having a general formula Ri(COOH)2, a compound of the type with a poly (lactic glycol carboxy terminated) acid having a general formula OH-CO-C2H4-CO- [OR-CH2-CO-OR-CH2- (CH3) -CO-OR-] n-, and a further compound having a general formula R2(NCO)2, wherein Ri is a radical provided with at least an alcoholic function.
227. Co-poly (amide ester) according to claim 226, wherein the poly (lactic glycol carboxy terminated) acid is obtained from glycolic acid, lactic acid and succinic anhydride .
228. Co-poly (amide ester) according to claim 226, or 227, wherein said first compound is present in molar quantities comprised between 10% and 80%.
229. Co-poly (amide ester) according to claim 226, or 227, wherein said first compound is present in molar quantities comprised between 35% and 45%.
230. Co-poly (amide ester) according to claim 226, or 227, wherein said first compound is present in molar quantities of the order of approximately 25%.
231. Co-poly (amide ester) according to any one of claims 226 to 230, wherein said further compound is present in molar quantities comprised between 10% and 80%.
232. Co-poly (amide ester) according to any one of claims 226 to 230, wherein said further compound is present in molar quantities comprised between 40% and 60%.
233. Co-poly (amide ester) according to any one of claims 226 to 230, wherein said further compound is present in molar quantities of the order of approximately 50%.
234. Co-poly (amide ester) according to any one of claims 226 to 233, wherein said poly (lactic glycol carboxy terminated) acid is present in molar quantities comprised between 10% and 80%.
235. Co-poly (amide ester) according to any one of claims 226 to 233, wherein said poly (lactic glycol carboxy terminated) acid is present in molar quantities comprised between 35% and 45%.
236. Co-poly (amide ester) according to any one of claims 226 to 233, wherein said poly (lactic glycol carboxy terminated) acid is present in molar quantities of the order of approximately 25%.
237. Co-poly (amide ester) according to any one of claims 226 to 236, wherein said first compound and said poly (lactic glycol carboxy terminated) acid are mixed in quantities that are equimolar to one another.
238. Co-poly (amide ester) according to any one of claims 226 to 237, wherein said co-poly (amide ester) has an almost linear structure.
239. Co-poly (amide ester) according to any one of claims 226 to 238, wherein R' i is a radical having the same formula as Ri .
240. Co-poly (amide ester) according to any one of claims 226 to 239, wherein said co-poly (amide esters) has a branched and/or cross-linked structure.
241. Co-poly (amide ester) according to any one of claims 226 to 240, wherein R' i is a radical comprising in the formula thereof the radical R2.
242. Co-poly (amide ester) according to any one of claims 226 to 241, wherein R' 1 is a radical having a general formula [-CH (OH) -CH-OR (-CONH-R2-NH-) -CO-] .
243. Biodegradable co-poly (amide urethane) having a general formula [-NH-R2-NH-CO-RI-CONH-R2-NH-CO- (OR-CH2-CH2-) x (OR-CH(CH3) -CH2-) Y - (OR-CH2-CH2-) z -OR-CO-] obtained from a first compound having a general formula Ri(COOH)2, a fourth compound having a general formula H- (OR-CH2-CH2- ) x- (OR-CH (CH3) -CH2-) Y- (OR-CH2-CH2-) z-OH, and a further compound having a general formula R2(NCO)2, wherein Ri is a radical provided with at least an alcoholic function.
244. Co-poly (amide urethane) according to claim 243, wherein said fourth compound is selected from a group comprising the co-polymers with poly (ethylene glycols) -poly (propylene glycol) -poly (ethylene glycols) (PEG-PPG-PEG) blocks.
245. Co-poly (amide urethane) according to claim 243, wherein said fourth compound is selected from compounds of the poloxamer type.
246. Co-poly (amide urethane) according to claim 243, wherein said fourth compound is the poloxamer 1100.
247. Co-poly (amide urethane) according to any one of claims 243 to 246, wherein said first compound and said fourth compound are present in quantities such that their reciprocal weighted ratio is comprised between 4 and 0.5.
248. Co-poly (amide urethane) according to any one of claims 243 to 246, wherein said first compound and said fourth compound are present in quantities such that their reciprocal weighted ratio is equal approximately to 1.
249. Co-poly (amide urethane) according to any one of claims 243 to 248, wherein said further compound is present in molar quantities comprised between 10% and 80% of the stoichiometric ratio.
250. Co-poly (amide urethane) according to any one of claims 243 to 248, wherein said further compound is present in molar quantities comprised between 40% and 60% of the stoichiometric ratio.
251. Co-poly (amide urethane) according to any one of claims 243 to 248, wherein said further compound is present in molar quantities of the order of approximately 50% of the stoichiometric ratio.
252. Co-poly (amide urethane) biodegradable having a general formula [-NH-R2-NH-CO-RI-CONH-R2-NH-CO- (OR-CH2-CH2-) n-0R- CO-] obtained from a first compound having a general formula Ri(COOH)2, a fifth compound having a general formula H- (OR-CH2-CH2-) n-0H, and a further compound having a general formula R2 (NCO) 2, wherein Ri is a radical provided with at least an alcoholic function.
253. Co-poly (amide urethane) according to claim 252, wherein said fifth compound is chosen from the oligomers of the poly (ethylene glycols) .
254. Co-poly (amide urethane) according to claim 252, wherein said fifth compound has a molecular weight comprised between approximately 500 and approximately 5000.
255. Co-poly (amide urethane) according to claim 252, wherein said fifth compound has a molecular weight comprised between approximately 1000 and approximately 4000.
256. Co-poly (amide urethane) according to any one of claims 252 to 255, wherein said first compound and said fifth are present in molar quantities such that their reciprocal ratio is comprised between approximately 4 and approximately 0.5.
257. Co-poly (amide urethane) according to any one of claims 252 to 255, wherein said first compound and said fifth are present in molar quantities such that their reciprocal ratio is equal approximately to 1.
258. Co-poly (amide urethane) according to any one of claims 252 to 257, wherein said further compound is present in molar quantities comprised between 10% and 80% of the stoichiometric ratio.
259. Co-poly (amide urethane) according to any one of claims
252 to 257, wherein said further compound is present in molar quantities comprised between 40% and 60% of the stoichiometric ratio.
260. Co-poly (amide urethane) according to any one of claims 252 to 257, wherein said further compound is present in molar quantities of the order of approximately 50% of the stoichiometric ratio.
261. Biodegradable co-polyester having a general formula
[ [ (-0R- (CH2-J5-CO)1n-OR-CH2-CH2-OR-CH2-CH2-OR- (-CO- (CH2-) 5- OR) m] n-CO-Ri-CO-] obtained from a first compound having a general formula Ri(COOH)2, and from a sixth compound having a general formula [ (-0R- (CH2-) 5-CO) m-OR-CH2-CH2- OR-CH2-CH2-OR- (-CO- (CH2-) 5-OR)1n] n, wherein R1 is a radical provided with at least an alcoholic function.
262. Co-polyester according to claim 261, wherein said sixth compound is chosen from caprolactone polymers.
263. Co-polyester according to claim 261, wherein said first compound and said sixth compound are present in molar quantities such that the reciprocal ratio between such quantities is comprised between approximately 4 and approximately 0.2.
264. Co-polyester according to claim 261, wherein said first compound and said sixth compound are present in quantities that are stoichiometric to one another.
265. Biodegradable co-poly (amide urethane) having a general formula [-NH-R2-NH-CO-RI-CONH-R2-NH-CO- (0-CH2-CH2-) X- (0-
CH- (CH3) -CH2]Y- (0-CH2-CH2-) z-O-CO] obtained from a first compound having a general formula Ri(COOH)2, a seventh compound having a general formula H- [O-CH- (CH3) -CH2] n- OH, and a further compound having a general formula R2(NCO)2, in which Ri is a radical provided with at least an alcoholic function.
266. Co-poly (amide urethane) according to claim 265, wherein the seventh compound is chosen between the polymers of the poly (propylene glycol), PPG.
267. Co-poly (amide urethane) according to claim 265, or 266, wherein the seventh compound comprises poly (propylene glycol) having a molecular weight comprised between about 100 and 1000.
268. Co-poly (amide urethane) according to any one of claims 265 to 267, wherein the seventh compound comprises poly (propylene glycol) having a molecular weight of about 400.
269. Co-poly (amide urethane) according to any one of claims 265 to 268, wherein said first compound and said seventh compound are present in quantities such that their reciprocal weighted ratio is comprised between 4 and 0.5.
270. Co-poly (amide urethane) according to any one of claims 265 to 269, wherein said first compound and said seventh compound are present in quantities such that the weighted ratio of said seventh compound is about 20% on the total weight of the reactants .
271. Co-poly (amide urethane) according to any one of claims 265 to 270, wherein said first compound and said seventh compound are present in quantities such that the weighted ratio of said seventh compound is about (first compound+ further compound) *20/100= seventh compound.
272. Co-poly (amide urethane) according to any one of claims 265 to 271, wherein said further compound is present in molar quantities comprised between 10% and 80% of the stoichiometric ratio.
273. Co-poly (amide urethane) according to any one of claims 265 to 272, wherein said further mixing comprises adding said further compound in molar quantities comprised between 40% and 60% of the stoichiometric ratio .
274. Co-poly (amide urethane) according to any one of claims 265 to 273, wherein said further compound is present in molar quantities of the order of approximately 50% of the stoichiometric ratio.
275. Co-poly (amide urethane) according to any one of claims 265 to 274, wherein said co-poly (amide urethane) is a plastic material with an almost linear structure.
276. Co-poly (amide urethane) according to any one of claims
265 to 275, wherein said first compound comprises a compound in which a radical Ri have the same formula as
R'i.
277. Co-poly (amide urethane) according to any one of claims 265 to 276, wherein said co-poly (amide urethane) is a plastic material with an almost branched and/or cross- linked structure.
278. Co-poly (amide urethane) according to any one of claims 265 to 277, wherein the radical R' i of said co-polyamide is a radical comprising in the formula thereof the radical R2 of said further compound.
279. Co-poly (amide urethane) according to any one of claims 265 to 278, wherein the radical R' 1 of said co-polyamide is a radical having a general formula [-CH (OH) -CH-OR (- CONH-R2-NH-) -CO-] .
280. Plastic material according to any one of claims 199 to 279, wherein the radical Ri comprises a plurality of alcoholic functions .
281. Plastic material according to any one of claims 199 to 280, wherein the radical Ri comprises two alcoholic functions (-0H) .
282. Plastic material according to any one of claims 199 to
281, wherein the radical Ri is selected from a group comprising the aliphatic radicals, the radicals containing double bonds, the radicals with a linear or branched, and/or linked chain.
283. Plastic material according to any one of claims 199 to
282, wherein said first compound is chosen from dihydroxy acids .
284. Plastic material according to any one of claims 199 to
283, wherein said first compound is tartaric acid, or a compound similar thereto.
285. Plastic material according to any one of claims 199 to
284, wherein the radical R2 comprises an aliphatic radical, or provided with linear or branched, and/or cross-linked or cyclical double bonds.
286. Plastic material according to any one of claims 199 to
285, wherein said further compound has a plurality of functions (-NCO) characteristic of the isocyanates.
287. Plastic material according to any one of claims 199 to 286, wherein said further compound has two functions (- NCO) characteristic of the isocyanates.
288. Plastic material according to any one of claims 199 to 287, wherein said further compound is a diisocyanate .
289. Plastic material according to any one of claims 199 to 288, wherein said further compound is a terminal diisocyanate .
290. Plastic material according to any one of claims 199 to 289, wherein said further compound is a diisocyanate that can be chosen between the aliphatic-chain diioscyanates, or provided with linear or branched, and/or cross-linked or cyclical double bonds.
291. Plastic material or according to any one of claims 199 to 290, wherein said further compound can be chosen from a group comprising diisocyanatohexane (HMDI), 1,8 diisocyanatooctane (OMDI), 1,12 diisocyanatododecane (DMDI) .
292. Plastic material according to any one of claims 199 to 291, wherein the reaction is catalysed by an organometal compound.
293. Plastic material according to any one of claims 199 to 292, wherein the reaction is catalysed by dibutyl tin laurate (DBLT) .
294. Plastic material according to any one of claims 199 to 293, wherein the reaction is catalysed by dibutyl tin oxide (DBTO) .
295. Plastic material according to any one of claims 199 to 294, wherein said first compound is amalgamated with anhydrous DMF (N,N-dimethylformamide) .
296. Plastic material according to any one of claims 199 to 295, wherein said first compound is amalgamated with quantities of anhydrous DMF (N,N-dimethylformamide) comprised between about 30% and about 60% by weight on the weight of the total reactants .
297. Plastic material according to any one of claims 199 to 296, wherein said first compound is amalgamated with quantities of anhydrous DMF (N,N-dimethylformamide) comprised of about 45% by weight on the weight of the total reactants .
298. Plastic material according to any one of claims 265 to 279, wherein said first compound is amalgamated with quantities of anhydrous DMF (N,N-dimethylformamide) so that said the reciprocal weight ratio is about (first compound+ further compound+ seventh compound) *55/45= DMF.
299. Plastic material according to any one of claims 199 to 298, wherein said first compound is amalgamated with quantities of anhydrous DMF (N,N-dimethylformamide) comprised between about 10% and about 65% by weight on the weight of the total reactants .
300. Plastic material according to any one of claims 199 to
299, wherein said first compound is amalgamated with quantities of anhydrous DMF (N,N-dimethylformamide) comprised between about 30% and about 50% by weight on the weight of the total reactants .
301. Plastic material according to any one of claims 199 to
300, wherein said first compound is amalgamated with quantities of anhydrous DMF (N,N-dimethylformamide) of about 40% by weight on the weight of the total reactants .
302. Plastic material according to any one of claims 199 to
301, wherein said first compound is amalgamated with quantities of anhydrous DMF (N,N-dimethylformamide) comprised of about 60% by weight on the weight of the total reactants .
303. Plastic material according to any one of claims 199 to
302, wherein said first compound and said further compound are present in quantities so that the reciprocal molar ratio first compound: further compound is comprised between about 1:2 and 1:0.8.
304. Plastic material according to any one of claims 199 to
303, wherein said first compound and said further compound are present in quantities so that the reciprocal molar ratio first compound: further compound is comprised between about 1:1.8 and 1:0.9.
305. Plastic material according to any one of claims 199 to
304, wherein said first compound and said further compound are present in quantities so that the reciprocal molar ratio first compound: further compound is comprised between about 1:1.6 and 1:1.
306. Plastic material according to any one of claims 199 to
305, wherein said first compound and said further compound are present in quantities so that the reciprocal molar ratio is first compound: further compound = 1:1.05.
307. Plastic material according to any one of claims 199 to
306, wherein said first compound and said further compound are present in quantities so that the reciprocal molar ratio is first compound: further compound = 1:1.1.
308. Plastic material according to any one of claims 199 to
307, wherein said first compound and said further compound are present in quantities so that the reciprocal molar ratio is first compound: further compound = 1:1.2.
309. Plastic material according to any one of claims 199 to
308, wherein said first compound and said further compound are present in quantities so that the reciprocal molar ratio is first compound: further compound = 1:1.4.
310. Plastic material according to any one of claims 199 to
309, wherein said first compound and said further are present in quantities so that the reciprocal molar ratio is first compound: further compound = 1:1.6.
311. Plastic material according to any one of claims 199 to
310, wherein said plastic material is a thermoplastic polymeric material.
312. Plastic material according to any one of claims 199 to 311, wherein said plastic material is a thermosettable polymeric material.
313. Plastic material according to any one of claims 199 to
311, wherein said plastic material show a certain swelling into water.
314. Plastic material according to any one of claims 199 to 311, wherein said plastic material show a certain swelling into water varying by varying the reciprocal ratio between said first compound, and said further compound and/or the other reactants .
315. Plastic material according to any one of claims 243 to 260, wherein said plastic material show a certain swelling into water varying with the ratio between said first compound, and respectively said fourth and said fifth compound.
316. Plastic material according to any one of claims 265 to 279, wherein said plastic material show a certain swelling into water varying with the ratio between said first compound, and said seventh compound.
317. Plastic material according to any one of claims 243 to 260, wherein water percentage increases of 5-20% were observed for a weight percentage comprised between about 20% to 40% respectively of said fourth and said fifth compound.
318. Composite material comprising at least a layer made from at least one of the plastic materials according to claims 199 to 317, and a further layer made in a further material .
319. Composite material according to claim 318, wherein said further material comprises a material selected from the group comprising aluminium, polyethylene, glass, LDPE, ordinary glass, silanised glass, silicone rubber, Teflon-butyl rubber, nylon sheets, PVC sheets, LDPE sheets, aluminium sheets, ceramics.
320. Polymeric blend obtained by mixing at least one of the plastic materials according to claims 199 to 317 with a further plastic material.
321. Polymeric blend according to claim 320, wherein said further plastic material is chosen from a group comprising polyesters, polyamides, polyurethanes, LDPE.
322. Polymeric blend according to claim 320, wherein said further plastic material is chosen from a group comprising polyadipates, polysuccinates, polycaprolactone, natural polysaccharides, starches, hemicellulose, or cellulose.
323. Polymeric blend according to any one of claims 320 to 317, and further comprising a material coupling agent suitable for improving the mixing between said plastic materials and said further plastic material.
324. Polymeric blend according to claim 323, wherein said material coupling agent comprises a co-polymer.
325. Polymeric blend according to claim 323, wherein said material coupling agent comprises a block co-polymer.
326. Use of at least one of the plastic materials according to claims 199 to 325 for making biodegradable objects.
327. Use of at least one of the plastic materials according to claims 199 to 325 for making biocompatible objects.
328. Use of at least one of the known plastic materials according to claims 199 to 325 to obtain pharmaceutical compositions .
PCT/EP2006/062906 2005-06-03 2006-06-05 Biodegradable plastic materials WO2006128918A1 (en)

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