Plasticiser for sealants, plastisols and adhesives

Abstract

A plasticizer composition for mastics, plastisols and adhesives is disclosed. The plasticizer includes at least one hydrocarbon-containing cut or a cut originating from biomass conversion and at least one fatty acid monoester. The plasticizer is free of phthalates.

Claims

1. A composition comprising: a) at least one polymer selected from the group consisting of a polyether comprising two silane-type terminal functions, a polyurethane comprising two silane-type terminal functions, an ethylene-vinyl acetate copolymer, a polyethylene, a polypropylene, a polyamide, or a mixture thereof; b) a plasticizer comprising: i) at least one hydrocarbon-containing cut or a cut originating from a conversion of a biomass, said cuts having a boiling point comprised between 230 and 400 C.; ii) at least one fatty acid monoester, the at least one fatty acid monoester comprising a C14-18fatty acid methyl ester; iii) less than 1% by weight of phthalates; and c) at least one compound selected from the group consisting of a thickener, a filler, a cross-linking agent, a cross-linking catalyst and a tackifier resin, and mixtures thereof.

2. The composition according to claim 1, in which the plasticizer comprises at least one hydrocarbon-containing cut.

3. The composition according to claim 1, in which the hydrocarbon-containing cut is a hydrotreated, hydrocracked or catalytically cracked hydrocarbon-containing cut.

4. The composition according to claim 1, in which the hydrocarbon-containing cut is a de-aromatized and/or desulphurized hydrocarbon-containing cut.

5. The composition according to claim 1, in which the hydrocarbon-containing cut has a kinematic viscosity at 40 C. comprised between 2 and 22 mm.sup.2/s according to the standard ASTM D445.

6. The composition according to claim 1, in which the hydrocarbon-containing cut has a pour point ranging from 50 to +10 C. according to the standard ASTM D97.

7. The composition according to claim 1, in which the hydrocarbon-containing cut has a content of aromatic compounds measured by UV less than 300 ppm.

8. The composition according to claim 1, in which the mass ratio of the fatty acid monoester comprising a C14-C18 fatty acid methyl ester to the hydrocarbon-containing cut or the cut originating from biomass conversion is comprised between 5:95 and 75:25.

9. A composition, which is a mastic composition, comprising: a) at least one polymer selected from the group consisting of a polyether comprising two silane-type terminal functions, a polyurethane comprising two silane-type terminal functions, and mixtures thereof; and b) a plasticizer comprising: i) at least one hydrocarbon-containing cut or a cut originating from a conversion of a biomass, said cuts having a boiling point comprised between 230 and 400 C.; ii) at least one fatty acid monoester; iii) less than 1% by weight of phthalates; and c) at least one cross-linking agent and optionally at least one compound selected from the group consisting of a thickener, a filler, a cross-linking catalyst and a tackifier resin, and mixtures thereof.

10. A composition, which is an adhesive composition, comprising: a) i) at least one polypropylene; ii) an ethylene-vinyl acetate copolymer; and b) a plasticizer comprising: i) at least one hydrocarbon-containing cut or a cut originating from a conversion of a biomass, said cuts having a boiling point comprised between 230 and 400 C.; ii) at least one fatty acid monoester; iii) less than 1% by weight of phthalates; and c) a tackifier resin and optionally at least one compound selected from the group consisting of a thickener, a filler, a cross-linking agent and a cross-linking catalyst, and mixtures thereof.

11. The composition according to claim 9, in which the fatty acid monoester is a C14-18 fatty acid methyl ester.

12. The composition according to claim 10, in which the fatty acid monoester is a C14-18 fatty acid methyl ester.

13. The composition according to claim 9, in which the mass ratio of the fatty acid monoester to the hydrocarbon-containing cut or the cut originating from biomass conversion is comprised between 5:95 and 75:25.

14. The composition according to claim 10, in which the mass ratio of the fatty acid monoester to the hydrocarbon-containing cut or the cut originating from biomass conversion is comprised between 5:95 and 75:25.

15. The composition according to claim 9, in which the plasticizer comprises at least one hydrocarbon-containing cut.

16. The composition according to claim 10, in which the plasticizer comprises at least one hydrocarbon-containing cut.

17. The composition according to claim 9, in which the hydrocarbon-containing cut is a hydrotreated, hydrocracked or catalytically cracked hydrocarbon-containing cut.

18. The composition according to claim 10, in which the hydrocarbon-containing cut is a hydrotreated, hydrocracked or catalytically cracked hydrocarbon-containing cut.

19. The composition according to claim 9, in which the hydrocarbon-containing cut is a de-aromatized and/or desulphurized hydrocarbon-containing cut.

20. The composition according to claim 10, in which the hydrocarbon-containing cut is a de-aromatized and/or desulphurized hydrocarbon-containing cut.

21. A composition comprising: a) at least one polymer selected from the group consisting of a polyether comprising two silane-type terminal functions, a polyurethane comprising two silane-type terminal functions, an ethylene-vinyl acetate copolymer, a polyethylene, a polypropylene, a polyamide, or a mixture thereof; b) a plasticizer comprising: i) at least one hydrocarbon-containing cut or a cut originating from a conversion of a biomass, said cuts having a boiling point comprised between 230 and 400 C.; ii) at least one fatty acid methyl monoester; iii) less than 1% by weight of phthalates; and c) at least one compound selected from the group consisting of a thickener, a filler, a cross-linking agent, a cross-linking catalyst and a tackifier resin and mixtures thereof.

22. The composition according to claim 21, in which the plasticizer comprises at least one hydrocarbon-containing cut.

23. The composition according to claim 21, in which the hydrocarbon-containing cut is a hydrotreated, hydrocracked or catalytically cracked hydrocarbon-containing cut.

24. The composition according to claim 21, in which the hydrocarbon-containing cut is a de-aromatized and/or desulphurized hydrocarbon-containing cut.

25. The composition according to claim 21, in which the hydrocarbon-containing cut has a kinematic viscosity at 40 C. comprised between 2 and 22 mm2/s according to the standard ASTM D445.

26. The composition according to claim 21, in which the hydrocarbon-containing cut has a pour point ranging from 50 to +10 C. according to the standard ASTM D97.

27. The composition according to claim 21, in which the hydrocarbon-containing cut has a content of aromatic compounds measured by UV less than 300 ppm.

28. The composition according to claim 21, in which the fatty acid methyl monoester is a C14-18 fatty acid methyl ester.

29. The composition according to claim 21, in which the mass ratio of the fatty acid methyl monoester to the hydrocarbon-containing cut or the cut originating from biomass conversion is comprised between 5:95 and 75:25.

Description

DETAILED DESCRIPTION

(1) The plasticizer according to the invention comprises at least one hydrocarbon-containing cut or a cut originating from biomass conversion. Preferably, the plasticizer according to the invention comprises at least one hydrocarbon-containing cut. By hydrocarbon-containing cut according to the invention, is meant a cut originating from the distillation of crude oil, preferably originating from the atmospheric distillation and/or vacuum distillation of crude oil, preferably originating from atmospheric distillation followed by vacuum distillation.

(2) The hydrocarbon-containing cut according to the invention is also preferably subjected to stages of hydrotreatment, hydrocracking or catalytic cracking. The hydrocarbon-containing cut according to the invention is also preferably subjected to stages of de-aromatization and optionally desulphurization. The hydrocarbon-containing cut according to the invention can also preferably be subjected to a stage of hydrodewaxing.

(3) Preferably, the feedstock obtained after the distillation stage or stages is a gas oil feedstock, this gas oil feedstock being subjected to the stages of hydrotreatment, hydrocracking, catalytic cracking or hydrodewaxing, optionally followed by stages of de-aromatization and optionally of desulphurization. The hydrocarbon-containing cut can be a mixture of hydrocarbon-containing cuts subjected to the stages described above.

(4) The hydrocarbon-containing cut as described above, has a distillation range DR (in C.) such that 230DR400 and more preferably such that 250DR380. The hydrocarbon-containing cut can comprise one or more fractions with distillation ranges comprised within that of said cut. The hydrocarbon-containing cut according to the invention generally comprises more than 60% by weight of paraffinic compounds, preferably more than 65%, even more preferably more than 70%.

(5) The hydrocarbon-containing cut according to the invention is generally constituted by a majority of isoparaffins and a minority of normal paraffins. Preferably the hydrocarbon-containing cut contains more than 50% by weight of isoparaffins and less than 20% by weight of normal paraffins. The hydrocarbon-containing cut according to the invention generally comprises less than 50% by weight of naphthenic compounds, preferably less than 40%, even more preferably less than 30%.

(6) The hydrocarbon-containing cut according to the invention is preferably free of aromatics. By free is meant, preferably, a hydrocarbon-containing cut comprising less than 300 ppm of aromatics, preferably less than 200 ppm, even more preferably less than 100 ppm measured by UV spectrometry.

(7) Preferably, the hydrocarbon-containing cut according to the invention, has a sulphur content less than 10 ppm and preferably less than 2 ppm. The hydrocarbon-containing cut according to the invention generally has a kinematic viscosity at 40 C. comprised between 2 and 22 mm.sup.2/s, preferably between 2 and 15 mm.sup.2/s and more preferably between 3 and 13 mm.sup.2/s according to the standard ASTM D445. The hydrocarbon-containing cut according to the invention has a pour point according to the standard ASTM D97 comprised between 50 and +10 C., preferably comprised between 40 and 0 C., even more preferably comprised between 30 and 10 C.

(8) The cut originating from biomass conversion can be produced from biological raw materials selected from the group consisting of vegetable oils, animal fats, fish oils and mixtures thereof. The appropriate biological raw materials comprise the following: oil from oilseed rape, canola oil, rapeseed oil, tall oil, sunflower oil, soya oil, hemp oil, olive oil, linseed oil, mustard oil, palm oil, groundnut oil, castor oil, coconut oil, animal fats such as pig fat, tallow or flare fat, recycled edible fats, raw materials originating from genetic engineering and biological raw materials produced by microorganisms such as algae and bacteria. Condensation products, esters or other derivatives obtained from raw biological materials can also serve as raw materials.

(9) A solvent of biological origin is then produced using for example a process which comprises firstly a stage of hydrodeoxygenation (HDO) in order to break down the structure of the constitutive biological esters or triglycerides and in order to remove the compounds containing oxygen, phosphorus and sulphur whilst at the same time producing the hydrogenation of the olefinic bonds. This is followed by isomerization of the product thus obtained leading to the branching of the hydrocarbon chain and to an improvement in the properties of the paraffin at low temperatures. It is for example possible to fractionate the product in order to obtain the desired cuts.

(10) The hydrocarbon-containing cut according to the invention also has the advantage of being easily available on the market, being relatively economical within the chain of oil distillation or biomass conversion products. The plasticizer according to the invention also comprises at least one fatty acid monoester. It is understood that it can also be a mixture of several fatty acids, each of the fatty acids being mono-esterified.

(11) The esters of fatty acids are obtained by esterification of free fatty acids or by transesterification of animal and/or vegetable oils (or triglycerides of fatty acids) with an alcohol. During the esterification or transesterification, small quantities of fatty acids may remain in the form of monoglyceride, diglyceride, triglyceride or of fatty acids in the free form. Thus, even if the fatty acid monoester according to the invention is very predominantly in the form of monoester, it can comprise negligible quantities of fatty acids in the form of monoglyceride, diglyceride, triglyceride or in the free form.

(12) The fatty acid monoester according to the invention is in the form of monoester amounting to more than 80% by mass, preferably between 90 and 100%, more preferably between 95 and 98%. The quantities of fatty acids in the form of monoglyceride, diglyceride, triglyceride or in the free form are negligible and represent no more than 15% by mass of the fatty acid monoester according to the invention, preferably no more than 10%, more preferably no more than 6%, even more preferably no more than 4%.

(13) In particular, the fatty acid monoester according to the invention comprises no more than 5% by mass of fatty acids in the form of monoglyceride, preferably no more than 1%. In particular, the fatty acid monoester according to the invention comprises no more than 5% by mass of fatty acids in the form of diglyceride, preferably no more than 2%. In particular, the fatty acid monoester according to the invention comprises no more than 5% by mass of fatty acids in the form of triglyceride, preferably no more than 1%. In particular, the fatty acid monoester according to the invention comprises no more than 6% by mass of fatty acids in the free form, preferably no more than 3%.

(14) The fatty acids of the fatty acid monoester according to the invention, are generally fatty acids comprising from 6 to 24 carbon atoms, preferably from 14 to 22 carbon atoms, more preferably from 16 to 18 carbon atoms, the fatty acids comprising 18 carbon atoms, being the majority of the fatty acids. According to an embodiment, the fatty acid ester is not selected from the glycerol and tall oil fatty acid esters. The fatty acid monoester according to the invention can be a C.sub.1-C.sub.4 alkyl monoester, such as a methyl monoester, an ethyl monoester, an n-propyl monoester, an i-propyl monoester, an n-butyl monoester, an s-butyl monoester, a t-butyl monoester. Preferably, the monoester is a methyl monoester.

(15) The preferred fatty acid monoester is a fatty acid methyl ester registered under CAS number 67762-26-9. Preferably, the plasticizer according to the invention comprises from 5 to 75% by weight of fatty acid monoester, more preferably from 10 to 60%, even more preferably from 20 to 45%, even more preferably from 30 to 40%. According to an embodiment, the plasticizer comprises from 20 to 60% by weight of fatty acid monoester.

(16) According to an embodiment, the plasticizer comprises from 45 to 75% of a hydrocarbon-containing cut or a cut originating from biomass conversion. Preferably, the plasticizer composition comprises from 25% to 95% by weight of hydrocarbon-containing cut or cut originating from biomass conversion, more preferably from 40 to 90%, even more preferably from 55 to 80%, even more preferably from 60 to 70%. Preferably, the mass ratio of the fatty acid monoester to the hydrocarbon-containing cut or the cut originating from biomass conversion is comprised between 5:95 and 75:25, preferably between 10:90 and 60:40, more preferably between 20:80 and 45:55, even more preferably between 30:70 and 40:60.

(17) The plasticizer according to the invention is free of phthalate-type compounds. By free according to the invention, is meant a plasticizer comprising less than 1% by mass of phthalates, relative to the mass of plasticizer, preferably less than 0.5%, more preferably less than 0.1%, even more preferably less than 0.01%. The plasticizer according to the invention generally has a kinematic viscosity at 40 C. ranging from 5 to 22 mm.sup.2/s, preferably ranging from 5 to 15 mm.sup.2/s according to the standard ASTM D445.

(18) The invention also relates to a mastic composition comprising at least one polymer selected from the group consisting of a polyether comprising two silane-type terminal functions, a polyurethane comprising two silane-type terminal functions, or a mixture thereof, the plasticizer composition as described above and at least one cross-linking agent. Preferably, the polymer is a polyether comprising two silane-type terminal functions. Advantageously the mastic composition comprises from 10 to 50% by weight of said polymer, preferably from 20 to 30%. Advantageously the mastic composition comprises from 10 to 30% by weight of said plasticizer composition, preferably from 10 to 25%. In order to satisfy the mechanical and physico-chemical requirements, the mastic composition also comprises in a standard manner at least one thickener, filler, cross-linking agent and/or catalyst.

(19) The invention also relates to a plastisol composition comprising at least one polymer selected from the group consisting of a polyvinyl chloride and an ethylene-vinyl acetate or EVA the plasticizer composition as described above and a filler. A subject of the invention is also an adhesive composition, preferably a thermoplastic adhesive composition, comprising at least one polymer consisting of a polyethylene, a polypropylene or a polyamide, an ethylene-vinyl acetate copolymer, the plasticizer composition according to the above description and a tackifier resin.

(20) The compositions of mastics, plastisols and adhesives according to the invention have the remarkable characteristic of containing less than 0.1% by weight of phthalates relative to the mass of the composition, preferably less than 0.05%, more preferably less than 0.01%, even more preferably less than 0.001%. The compositions of thermoplastic mastics, plastisols and adhesives as described are without phthalates and with a low VOC content in order to satisfy the current regulatory requirements. Finally, a subject of the invention is the use of the plasticizer composition according to the invention in mastics, plastisols and adhesives.

EXAMPLES

(21) In the remainder of the present description, examples of the present invention are given by way of illustration and are in no case intended to limit its scope.

(22) Different hybrid mastic formulations based on silyl modified polymers (or SMPs) were assessed. These SMP mastics include the ST-PE (Silane terminated Polyether) and ST-PU (Silane terminated Polyurethane) product families. The following examples describe the SMP mastic compositions comprising the different plasticizers below: a hydrocracked hydrocarbon-containing cut such as the HYDROSEAL G3H or HYDROSEAL G400H marketed by TOTAL FLUIDES, comparative example 1, a hydrodewaxed hydrocarbon-containing cut such as the HYDROSEAL G340H marketed by TOTAL FLUIDES, comparative example 2, di-isodecyl phthalate (or DIDP) as a reference for the phthalates, comparative example 3, a mixture of fatty acid methyl esters (FAMEs) +HYDROSEAL G3H or HYDROSEAL G340H or HYDROSEAL G400H, examples according to the invention 4, 5, 6 and 7 in different proportions.

(23) Table 1 summarizes the chemical characteristics of the ST-PE mastic used for the different evaluations.

(24) TABLE-US-00001 TABLE 1 Formulation % by mass Chemical Nature/Properties Polymer MS 203H 15 ST-PE/Polymer Polymer MS 303H 10 ST-PE/Polymer Plasticizer 17 Cf. mixtures described in Table 2 below Crayvallac SLX 4.5 PA-wax/thickener Carbital 110S 51.1 Chalk/filler SLX Activation; T > 70 C. Cooling to T < 40 C. Dynasilan VTMO 0.8 Vinyltrimethoxysilane/drying agent Drying of the additives for 1 hour Dynasilan AMMO 1.1 3-Aminopropylmethoxysilane/cross- linking agent Cooling down to T < 30 C., Cross-linking over 30 minutes TIB Kat 223 0.3 Dioctyltindiethanolate/Catalyst Catalyst TIB Kat 422 0.2 Dioctyltin-silane-blend/Catalyst

(25) Table 2 summarizes the results obtained for the different mastic formulations.

(26) TABLE-US-00002 TABLE 2 Plasticizer constituents Surface Example Plasticizer ratio Hardening.sup.(1) Bleeding .sup.(2) Appearance .sup.(3) 1 17% HYDROSEAL ok yes (3 d) dry comparative G3H 2 17% HYDROSEAL ok yes, strong wet comparative G340H after 1 day (1 d) 3 17% DIDP ok no dry comparative 4 8.5% EMAG/8.5% 50/50 ok no dry HYDROSEAL G340H 5 8% EMAG/9% 47/53 ok no dry HYDROSEAL G340H 6 5% EMAG/12% 29/71 ok no dry HYDROSEAL G3H 7 7% EMAG/10% 41/59 ok no dry HYDROSEAL G400H .sup.(1)The hardening of the mastic is assessed by touch 24 hours after its application, .sup.(2) In order to assess bleeding, the mastic is applied to an Exacompta 13308E-type index card. After hardening, the card is checked periodically in order to see whether the oil migrates towards the index card. .sup.(3) The mastic surface moisture is assessed visually.

(27) The results of Table 2 show that the properties of the mastic composition are all just as good or even better with a plasticizer comprising a hydrocarbon-containing fluid mixed with a fatty acid monoester. The hardening of the mastic is satisfactory, no moisture and no bleeding are noted.

(28) Table 3 contains the results obtained for other mastic formulations with the phthalates reference as plasticizer (comparative Example 1a) and a plasticizer according to the invention (Example 8 according to the invention). The formulation of Example 1a contains 17% of a plasticizer which is Jayflex DIDP. The formulation of Example 8 contains 17% of a plasticizer which is a mixture of Hydroseal G340H and fatty acid methyl esters (FAMEs). The percentages by mass of Hydroseal G340H and fatty acid methyl esters (FAMEs) are 8% and 9% respectively, with respect to the mass of the formulation.

(29) TABLE-US-00003 TABLE 3 Example 1a Example 8 DIDP EMAG/Hydroseal composition G340H composition Chemical nature/Properties (in % by mass) (in % by mass) Polymer MS Polyether with silane-type 15 15 203H terminal functions/Polymer Polymer MS Polyether with silane-type 10 10 303H terminal functions/Polymer Irganox 1076 sterically hindered 0.2 0.2 phenolic anti-oxidant Jayflex DIDP Di-isodecyl phthalate/ 17 Plasticizer Hydroseal Hydroseal/Plasticizer 8 G340H EMAG Fatty acid methyl ester/ 9 Plasticizer Crayvallac PA-wax/thickener 5.5 5.5 SLX Carbital 110S Chalk/filler 49.9 49.9 Dynasilan Vinyltrimethoxysilane/ 0.8 0.8 VTMO drying agent Dynasilan 3-Aminopropylmethoxysilane/ 1.1 1.1 AMMO cross-linking agent Tegokat 223 Dioctyltindiethanolate/ 0.3 0.3 Catalyst Tegokat 422 Dioctyltin-silane-blend/ 0.2 0.2 Catalyst TOTAL 100 100

(30) TABLE-US-00004 TABLE 4 Mechanical properties Example 1a Example 8 Characteristics DIDP EMAG/G340H Viscosity after 0 day/56 day (in Pa .Math. s) 6150/4800 4650/3450 (Internal method) Skin-formation time (smoothing time) 8/10 13/14 after 0 day/56 days (in min) (Internal method) Shore A hardness after 28 days at ambient temperature 28 28 (DIN ISO 7619) Shear strength (application of the mastic to a wooden 0.795 0.717 substrate) EN 281 after 3 days (in N/mm.sup.2) (DIN EN 14293) Shear strength (application of the mastic to a wooden 2.0 0.9 substrate) EN 281 after 3 days (in mm) (DIN EN 14293) Elasticity modulus at 100% (2 mm film) 0.44/0.46 0.33/0.40 3 days/28 days (in N/mm.sup.2) (DIN 53504, S2) Tensile strength (2 mm film) 1.13/1.16 0.92/1.10 3 days/28 days (in N/mm.sup.2) (DIN 53504, S2) Elongation at break at 3 days/28 days (in %) 1150/1150 1050/1000 (DIN 53504, S2) Elasticity modulus at 100% (cement cycle A) at ambient 0.536 0.527 temperature (in N/mm.sup.2) (DIN 52455-1) Elasticity modulus at 100% (aluminium cycle A) at ambient 0.518 0.494 temperature (in N/mm.sup.2) (DIN 52455-1) Elasticity modulus at 100% (cement B) at ambient 0.461 0.461 temperature (in N/mm.sup.2) (DIN 52455-1) Elasticity modulus at 100% (cement cycle B) at 20 C. 0.513 0.728 (in N/mm.sup.2) (DIN 52455-1) Elasticity modulus at 100% (aluminium cycle B) at ambient 0.511 0.474 temperature (in N/mm.sup.2) (DIN 52455-1) Elastic recovery at ambient temperature (in %) 64 78 (DIN EN ISO 7389-B)

(31) It should be noted that the mechanical properties of the ST-PE mastic containing the composition EMAG/Hydroseal G340H as plasticizer are just as good as or even better than those of a mastic containing DIDP as plasticizer.