GB2073224A - Amino-polyamides and derivatives thereof useful as plastisol adhesion improvers - Google Patents
Amino-polyamides and derivatives thereof useful as plastisol adhesion improvers Download PDFInfo
- Publication number
- GB2073224A GB2073224A GB8109281A GB8109281A GB2073224A GB 2073224 A GB2073224 A GB 2073224A GB 8109281 A GB8109281 A GB 8109281A GB 8109281 A GB8109281 A GB 8109281A GB 2073224 A GB2073224 A GB 2073224A
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- United Kingdom
- Prior art keywords
- resins
- acids
- epoxy
- polyaminoamide
- ketoimines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001944 Plastisol Polymers 0.000 title claims abstract description 28
- 239000004999 plastisol Substances 0.000 title claims abstract description 28
- 239000004952 Polyamide Substances 0.000 title abstract 2
- 229920002647 polyamide Polymers 0.000 title abstract 2
- 239000002253 acid Substances 0.000 claims abstract description 30
- 150000007513 acids Chemical class 0.000 claims abstract description 23
- 150000002576 ketones Chemical class 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 6
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000768 polyamine Polymers 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 68
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 27
- 239000004593 Epoxy Substances 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002318 adhesion promoter Substances 0.000 claims description 9
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 6
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000013638 trimer Substances 0.000 claims description 4
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical class OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011087 fumaric acid Nutrition 0.000 claims description 2
- 150000002238 fumaric acids Chemical class 0.000 claims description 2
- 150000002689 maleic acids Chemical class 0.000 claims description 2
- 159000000032 aromatic acids Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 125000002636 imidazolinyl group Chemical group 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 abstract 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 17
- 239000000194 fatty acid Substances 0.000 description 17
- 229930195729 fatty acid Natural products 0.000 description 17
- 150000004665 fatty acids Chemical class 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 hexahydrophthalic Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/54—Amino 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
-
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Polyamides (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
1 to 2 equivalents of polyamines H2N(CH2)x-(NH(CH2)g)n-NH2, wherein x, g and n are each independently at least 2, are homo- or co-polymerised with (a) 1 to 0.5 equivalents of dicarboxylic acids and (b) 0 to 0.5 equivalents of polymeric fat acids. They may be reacted with epoxy resins or converted to ketomines by treatment with ketones. The adhesion of plastisols to adhesion-rejecting surfaces can be improved by adding to plastisols, e.g. of PVC, compounds the above polyamides or reaction products which afford a high content of amine groups, amide bridges as such or as imidazoline rings in comparatively small concentrations relative to the plastisols concerned so as to improve adhesion while leaving the other physical properties of the plastisols unaltered.
Description
SPECIFICATION
Plastisol adhesion improvers
It is known that the plastisols are essentially comprised of a liquid dispersion of a powdered polymer in a plasticizer in which the polymer must not be appreciably soluble at room temperature.
When the plastisols are subjected to the action of heat, a dissolution of the polymer in the plasticizer is experienced with the attendant formation of a more or less elastic homogeneous mass.
The plastisols are mainly used as heat-insulating and noise-insulating layers, for example in the automotive industry, by applications onto metal surfaces of different kinds, the adhesion properties of which are, however, very poor. It is known long since that, according to the common experience, such adhesion is improved if plastisols are supplemented by polyamide resins capable of being homogeneously dispersed therethrough. According to the known art, the most adapted to the purpose have proven to be the polyaminoimide and polyamineamido imidazoline resins prepared by condensation of aliphatic polyamines with polycarboxylic acids as obtained by polymerization of unsaturated fatty acids, the adducts with epoxy resins obtained thereby and the ketoimines which can be prepared by treating said resins with ketones.
The aliphatic polyamines referred to above have the general formula: H2N(CH2)x(NH(CH2)y)nNH2 wherein x, y and n are integers, equal to or different from one another and higher than 2.
Said polycarboxylic acids, as obtained by polymerization of unsaturated fatty acids, are composed by mixture of polymers of unsaturated fatty acids having 1 8 carbon atoms, having a composition lying in the following ranges: 0% to 2% of monomers, 58% to 98% of dimers and 2% to 40% of trimers.
The epoxy adducts deriving from the resins aforementioned are obtained by reacting such resins with the products containing end epoxy groups, such as the polyglycidyl ethers of polyhydroxyl phenols.
The ketoimines are obtained by treating the above indicated resins with ketones, so as to convert the primary amine groups into ketoimine groups with water withdrawal, according to the following reaction pattern:
It has been experimentally ascertained, however, that with the polyaminoamide and the polyaminoamidoimidazoline resins which are known and of the kind referred to above, and with the adducts and the ketoimines obtained thereby, poor results because, while the adhesive force of plastisol is increased as the quantity of the added resin is increased, such a quantity cannot exceed, in practice, a certain levei beyond which certain properties of the plastisol, such as applicability and cohesion of the end coating product would be altered.In addition it should be considered that the use of such resins in high amounts would be economically objectionable.
The property of exaltation of the adhesion of plastisol by polyaminoamide resins and polyaminoamidoimidazoline resins and their adducts with epoxy resins has been discovered by trial and error by testing a number of different products.
This invention has matured from the theoretical consideration that, in actual practice, the adhesive properties of the resins are a function of their content of amine groups and amide bridges, as such and converted into imidazoline rings, such as in the case of the polyaminoamidoimidazoline resins and that consequently the activity of such compounds as adhesion-promoters for such resins is a specific function of their content of amine groups, amide bridges and imidazoline bridges. On this basis, the present invention thus aims at preparing polyaminoamide resins, or polyaminoamidoimidazoline resins, characterized by a high number of amine groups and amide bridges, as such or in the form of imidazoline bridges, which are dispersable in the plastisols, thereby imparting thereto high adhesion properties even if such promoters are present in low concentrations.
By virtue of such an idea one would solve the problem of using the resins of the kind referred to above, even though, in general, such resins should be used in great amounts to achieve satisfactory resuits as to the improvements of adhesion, but, as outlined above, such high amounts of resins would impair other basic properties of the plastisols irremediably.
To achieve this object, the present invention suggests polyaminoamide and polyaminoamidoimidazoiine resins principally suitable for use as plastisol adhesion promoters, characterized by a high content of amide groups, amide bridges as such or in the form of imidazoline rings, as obtained by condensing:
a) from 0 to 0.5 equivalents of polycarboxylic acids deriving from the polymerization of unsaturated fatty acids having a composition lying within the following ranges: 0% to 2% of monomers; 58% to 98% of dimers and 2% to 40% of trimers, and
b) from 0.5 to 1 equivalent of aliphatic, saturated or unsaturated bicarboxylic acids, having a straight or a branched chain of not more than 12 carbon atoms and/or saturated and unsaturated bicarboxylic cycloaliphatic acids and/or aromatic bicarboxylic acids with:
-from 1 to 2 equivalents of aliphatic polyamines having the general formula: H2N(CH2)x(NH(CH2)v)nNH2 wherein x, y and n are integers, equal to or different from one another, and higher than 2.
The resins according to this invention are thus characterized in that they are condensation derivatives of bicarboxylic acids. If these acids are in admixture with fatty acids which have been polymerized according to point a) as defined hereinbefore, such bicarboxylic acids are present in the admixture in an amount equal to at least the 50% of equivalents of such fatty acids.
Those bicarboxylic acids can be: aliphatic, with a straight or branched, saturated or unsaturated chain, having not more than 12 carbon atoms, such as oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, trimethyladipic, maleic and fumaric acids; or they can be saturated or unsaturated bicarboxylic acids, such as hexahydrophthalic, tetrahydrophthalic acids, or aromatic bicarboxylic acids such as phthalic, isophthalic and terephthalic acids.
The invention also relates to epoxy adducts, as obtained by treating with epoxy resins such as the diglycidyl ether of the p.p'-isopropylidenebiphenol, said polyaminoamide or polyaminoamidoimidazoline resins. The invention also encompasses the corresponding ketoimines as obtained by treating said resins with ketones such as methylethylketone.
Resins, and their adducts and ketoimine derivatives, according to this invention, can be employed as adhesion promoters for plastisols, both as such and in solution. Both the concentration of the solution and the type of the solvent used can be varied consistently with the viscosity of the resins and its solubility.
The solvents which are adapted to this purpose can be selected from among a wide range of organic compounds, such as hydrocarbons, their chlorinated or nitrous derivatives, alcohols, polyols, esters, ketones, amines and amides. A preferred solvent is benzyl alcohol.
In order that the resins according to the invention may be more comprehensively described, a few examples of preparation thereof are reported hereinafter, these examples being numbered from 6 to 12, which are given by way of illustration only.
Before these examples from 6 to 12, the examples numbered from 1 to 5 are concerned with the preparation of resins according to the conventional art so that examples from 1 to 5 hereof must be intended as merely comparative examples to permit a comparison with the resins the subject of this invention, as will be expounded in more detail hereinafter.
EXAMPLE 1 (COMPARATIVE EXAMPLE)
A polyaminoamide resin from polymerized fatty acids. - 285 parts by weight (1 equivalent) of polymerized fatty acids (obtained from unsaturated fatty acids having 18 carbon atoms and having the following composition: 1% of monomers, 77% of dimers and 22% of trimers, by wt) are heated with stirring with 131.4 parts by wt (1.8 equivalents) of triethylenetetramine, until reaching a temperature of 2200C and they are maintained at such a temperature until 18 parts by weight of water are dispelled, whereafter heating is discontinued. The resin thus obtained is dissolved in 1 70 parts by weight of benzyl alcohol in order to lower the viscosity and rendering the resin readily and homogeneously dispersible in the plastisol.
EXAMPLE 2 (COMPARATIVE EXAMPLE)
An epoxy adduct of a polyaminoamide resin from polymerized fatty acids. - 100 parts by weight of the solution obtained according to the procedure of Example 1 hereof are supplemented with 3.5 parts by weight of the diglycidyl ether of the p.p'-isopropylidenebiphenol and 1.5 parts by wt of benzyl alcohol. Thereafter, the mass is maintained for at least one hour at a temperature of about 100 C.
EXAMPLE 3 (COMPARATIVE EXAMPLE)
A ketoimine of a polyaminoamide resin from polymerized fatty acids. - A polyaminoamide resin is prepared with the same raw materials, quantities and conditions as in
Example 1 hereof. Prior to proceeding with the dissolution in benzyl alcohol, there are added 288 parts by wt (4 mol) of methylethylketone and 74 parts by wt of cyclohexane (water-entrainer). The mass is brought to a boil and the distillate recirculated so as to separate water as it is being formed. The operation is continued until the formation of water is over, whereafter the excess of methylethylketone and the cyclohexane are distilled off. The product is then dissolved in 1 87 parts by wt of benzyi alcohol.
EXAMPLE 4 (COMPARATIVE EXAMPLE)
A polyaminoamidoimidazoline resin from polymerized fatty acids. - 285 parts by wt (1 equivalent) of polymerized fatty acids (such as described in Example 1 hereof) are heated, with stirring, with 131.4 parts by wt (1.8 equivalent) of triethylenetetramine, until attaining a temperature of 2600C and such a temperature is maintained until 27 parts of water, by wt, are eliminated: thereafter heating is discontinued. The resin thus obtained is dissolved in 165 parts by wt of benzyl alcohol.
EXAMPLE 5 (COMPARATIVE EXAMPLE)
An epoxy adduct of a polyaminoamidoimidazoline resin. - The solution as obtained according to the procedure of Example 4 hereof is treated in the same way as disclosed in Example 2 hereof.
EXAMPLE 6 (INVENTION)
A polyaminoamide resin from polymerized fatty acids and an aliphatic bicarboxylic acid. - 85.5 parts by wt (0.3 equivalent) of polymerized fatty acids (such as described in Example 1 hereof) and 51.1 parts by wt (0.7 equivalent) of adipic acid with 131.4 parts by wt (1.8 equivalent) of triethylenetetramine are treated in the manner described in Example 1 hereof. The resin thus obtained is dissolved in 107 parts by wt of benzyl alcohol.
EXAMPLE 7 (INVENTION)
An epoxy adduct of a polyaminoamide resin from polymerized fatty acids and an aliphatic bicarboxylic acid. - The solution as obtained according to what has been disclosed in Example 6 hereof, is treated in the same way as described in Example 2 hereof.
EXAMPLE 8 (INVENTION)
A ketoimine of a polyaminoamide resin from polymerized fatty acids and a bicarboxylic aliphatic acid.
A polyaminoamide resin is prepared with the same raw materials, quantities and conditions as suggested in Example 6 hereof. Prior to proceeding with the dissolution in benzyl alcohol, the ketoimination procedure of Example 3 hereof is proceeded with, whereafter the resultant product is dissolved in 123 parts by wt of benzyl alcohol.
EXAMPLE 9 (INVENTION)
A polyaminoamidoimidazoline resin from polymerized fatty acids and an aliphatic bicarboxylic acid. - The same amounts of substances as listed in Example 6 hereof are treated according to the procedure as described in Example 4 hereof. The resin thus obtained is dissolved in 99 parts by wt of benzyl alcohol.
EXAMPLE 10 (INVENTION)
An epoxy adduct of a polyaminoamidoimidazoline resin from polymerized fatty acids and an aliphatic bicarboxylic acid. - The solution as obtained according to Example 9 hereof is treated in the same way as disclosed in
Example 2 hereof.
EXAMPLE 11 (INVENTION)
A polyaminoamide resin from polymerized fatty acids and an aromatic bicarboxylic acid. - 85.5 parts by wt (0.3 equivalent) of polymerized fatty acids (as described in Example 1 hereof) and 58.1 parts by wt (0.7 equivalent) of isophthalic acid, with 131.4 parts bywt (1.8 equivalent) of triethylenetetramine are treated in the same way as described in Example 1 hereof. The resin thus obtained is dissolved in 110 parts by wt of benzyl alcohol.
EXAMPLE 12 (INVENTION)
An epoxy adduct of a polyaminoamide resin from polymerized fatty acids and an aromatic bicarboxylic acid. - The solution as obtained according to what has been disclosed in Example 9 is treated in the same way as described in Example 2 hereof.
Ail the products of the Examples hereof are comprised of solutions of resins or adducts at 70% concentration in benzyl alcohol, the latter acting both as a solvent and a dispersing agent.
Comparative tests have been carried out in order to evaluate the magnitude of the adhesion promotion of the resins with respect to plastisols (adhesion-promoting action): the resins have been prepared according to the Examples set forth hereinbefore.
All tests have been conducted on a plastisol having the following percentage composition, on a weight basis:
Polyvinyl chloride 33%
Dioctyl phthalate 34%
Titanium dioxide 8%
Kaolin 10%
Colloidal silica 0.5%
Diglycidyl ether of 1.4-butanediol 0.4%
An adhesion promoter 1% The tests have been conducted by subjecting to the tensile shear stress test two steel slabs having
the size of 100 by 25 mm roughened with emery cloth and glued with a layer of the plastisol being
tested having a thickness of 2 mm the surface being 250 mm2, the plastisols having been cured at 140"C for 30 mins.
The results obtained with the products which had been prepared in the Examples hereof from 1 to
12, are tabulated in the attached Table.
TABLE
Average Tensile Shear Stress
Adhesion-Promoter (Average of 5 tests) Kg/cm2
Example No. 1 3.6
Example No. 2 4.1
Example No. 3 7.5
Example No. 4 4.6
Example No. 5 4.8
Example No. 6 17.5
Example No.7 18.1
Example No. 8 28.2
Example No. 9 18.9
Example No. 10 19.5
Example No. 11 17.3
Example No. 12 17.9
The above tabulated data show that the products according to the invention, that is the adhesion
promoters of the Examples from 6 to 12 inclusive hereof impart to the plastisol a tensile shear stress
resistance which is considerably improved over that which is experienced with the products according
to the conventional art (that is, those of Examples hereof from 1 to 5 inclusive), the dosages of
adhesion-promoter relative to the plastisol being the same for all the Examples indiscriminately.
The facts set forth above show that the resins made according to the invention, as well as their
epoxy and ketoimine derivatives, are capable of improving to a degree the adhesion of the plastisols to
the metallic surfaces, even in low concentrations, at which no hazard exists of jeopardizing the other
properties of the plastisols, such as applicability and cohesion of the final coatings.
Claims (17)
1. Polyaminoamide resins and polyaminoamidoimidazoline resins characterized in that they are obtained by condensing:
a) from 0 to 0.5 equivalent of polycarboxylic acids derived from the polymerization of unsaturated fatty acids having a composition lying within the following ranges: 0 to 2% of monomers, 58% to 98% of dimers and 2% to 40% of trimers, and
b) from 0.5 to 1 equivalent of bicarboxylic acids, with from 1 to 2 equivalents of aliphatic polyamines having the general formula: H2N(CH2)x(NH(CH2)y)nNH2 wherein x, y and n are integers, equal to or different from one another and higher than 2.
2. Resins according to Claim 1, characterized in that said bicarboxylic acids are aliphatic acids, saturated or unsaturated, with a straight or a branched chain of not more than 12 carbon atoms.
3. Resins according to Claim 1, characterized in that said bicarboxylic acids are cycloaliphatic, saturated or unsaturated acids.
4. Resins according to Claim 1, characterized in that said bicarboxylic acids are aromatic acids.
5. Resins according to Claim 2, characterized in that said aliphatic bicarboxylic acids are members selected from the group consisting of: adipic, oxalic, malonic, succinic, glutaric, pimeiic, suberic, azemaic, sebacic, trimethyladipic, maleic and fumaric acids.
6. Resins according to Claim 3, characterized in that said cycloaliphatic bicarboxylic acids are members selected from the group consisting of: hexahydrophthalic and tetrahydrophthalic acids.
7. Resins according to Claim 4, characterized in that said aromatic bicarboxylic acids are members selected from the group consisting of: phthalic, isophthalic and tetraphthalic acids.
8. Epoxy adducts as obtained by treating with epoxy resins any of the polyaminoamide and polyaminoamidoimidazoline resins as claimed in Claim 1.
9. Adducts according to Claim 8, characterized in that said epoxy resin is the diglycidyl ether of the p.p' -isopropylidenebiphenol.
1 0. Ketoimines as obtained by treating with ketones any of the polyaminoamide and polyaminoamidoimidazoline resins as claimed in Claim 1.
11. Ketoimines according to Claim 10, characterized in that said ketone is methylethylketone.
12. Polyaminoamide resins and polyaminoamidoimidazoline resins, their epoxy adducts and ketoimines according to the preceding Claims, characterized in that they are dissolved in an organic solvent.
13. Resins, epoxy adducts and ketoimines according to Claim 12, characterized in that they are dissolved in a concentration comprised between 10% and 95% on a weight basis.
14. Resins, epoxy adducts and ketoimines according to Claim 12, characterized in that said solvent is benzyl alcohol.
1 5. Resins, epoxy adducts and ketoimines substantially as hereinbefore described with reference to the Examples from 6 to 12 hereof.
1 6. Adhesion-promoters for plastisols characterized in that they consist of a polyaminoamide or a polyaminoamidoimidazoline resin or any of their epoxy adducts or a corresponding ketoimine as claimed in any of the preceding Claims.
17. Plastisols characterized in that they contain as an adhesion-promoter a resin or an epoxy adduct thereof or a corresponding ketoimine as claimed in any of the preceding Claims.
1 8. A process for preparing the products according to the preceding Claims, substantialiy as described in the Examples attached to the specification.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT20888/80A IT1130078B (en) | 1980-03-25 | 1980-03-25 | POLYAMINO AMID RESINS, POLYAMINO AMIDOIMMIDAZOLINICHE, THEIR EPOXY ADDUCTS AND KETIMMINE DERIVATIVES, AND RELATED SOLUTIONS, PARTICULARLY FOR USE AS PLASTISOLS ADHESION PROMOTERS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2073224A true GB2073224A (en) | 1981-10-14 |
| GB2073224B GB2073224B (en) | 1984-01-25 |
Family
ID=11173596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8109281A Expired GB2073224B (en) | 1980-03-25 | 1981-03-25 | Amino-polyamides and derivatives thereof useful as plastisol adhesion improvers |
Country Status (8)
| Country | Link |
|---|---|
| BE (1) | BE888042A (en) |
| CH (1) | CH653042A5 (en) |
| DE (1) | DE3111815A1 (en) |
| ES (1) | ES8300346A1 (en) |
| FR (1) | FR2484423A1 (en) |
| GB (1) | GB2073224B (en) |
| IT (1) | IT1130078B (en) |
| NL (1) | NL189466C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440900A (en) * | 1982-06-05 | 1984-04-03 | Schering Ag | Method for making coatings and adhesive bonds with polyvinyl chloride plastisols having improved adhesion, and plastisols for said process |
| US5650482A (en) * | 1993-02-10 | 1997-07-22 | Air Products And Chemicals, Inc. | Adhesion promoters |
| US7163976B2 (en) | 2001-06-27 | 2007-01-16 | Henkel-Teroson Gmbh | Adhesion promoter for plastisols |
| GB2446267A (en) * | 2007-01-29 | 2008-08-06 | Afton Chemical Corp | Imidazoline compounds |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4123211C1 (en) * | 1991-07-12 | 1993-02-11 | Ems-Togo Ag, Romanshorn, Ch |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB845560A (en) * | 1959-02-13 | 1960-08-24 | Gen Mills Inc | Improvements in or relating to polyamide resins |
| FR1216834A (en) * | 1959-02-18 | 1960-04-27 | Gen Mills Inc | Polyamide resin |
| FR1561128A (en) * | 1966-11-14 | 1969-03-28 | ||
| US4182844A (en) * | 1974-01-02 | 1980-01-08 | The C.P. Hall Company | Preparation of polyaminoamide resin in the absence of water |
| US4049598A (en) * | 1976-07-06 | 1977-09-20 | General Mills Chemicals, Inc. | Amino-poly(amidazoline-amide) |
| FR2383209A1 (en) * | 1977-03-07 | 1978-10-06 | Unilever Emery | Polyamide(s) from polymeric fatty acid polymers and tri:amine(s) - used adhesives for wood, metals, paper and textiles |
| DK585378A (en) * | 1977-12-29 | 1979-06-30 | Unilever Emery | POLYAMIDE AND ITS PROCEDURES |
-
1980
- 1980-03-25 IT IT20888/80A patent/IT1130078B/en active
-
1981
- 1981-03-20 BE BE0/204198A patent/BE888042A/en not_active IP Right Cessation
- 1981-03-23 NL NLAANVRAGE8101412,A patent/NL189466C/en active Search and Examination
- 1981-03-24 ES ES500663A patent/ES8300346A1/en not_active Expired
- 1981-03-24 FR FR8105815A patent/FR2484423A1/en active Pending
- 1981-03-24 CH CH1970/81A patent/CH653042A5/en not_active IP Right Cessation
- 1981-03-25 DE DE19813111815 patent/DE3111815A1/en active Granted
- 1981-03-25 GB GB8109281A patent/GB2073224B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440900A (en) * | 1982-06-05 | 1984-04-03 | Schering Ag | Method for making coatings and adhesive bonds with polyvinyl chloride plastisols having improved adhesion, and plastisols for said process |
| US5650482A (en) * | 1993-02-10 | 1997-07-22 | Air Products And Chemicals, Inc. | Adhesion promoters |
| US7163976B2 (en) | 2001-06-27 | 2007-01-16 | Henkel-Teroson Gmbh | Adhesion promoter for plastisols |
| GB2446267A (en) * | 2007-01-29 | 2008-08-06 | Afton Chemical Corp | Imidazoline compounds |
| GB2446267B (en) * | 2007-01-29 | 2011-02-09 | Afton Chemical Corp | Imidazoline compounds and lubricating compositions containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3111815C2 (en) | 1991-08-29 |
| ES500663A0 (en) | 1982-11-01 |
| IT8020888A0 (en) | 1980-03-25 |
| DE3111815A1 (en) | 1982-02-25 |
| BE888042A (en) | 1981-07-16 |
| NL8101412A (en) | 1981-10-16 |
| CH653042A5 (en) | 1985-12-13 |
| FR2484423A1 (en) | 1981-12-18 |
| ES8300346A1 (en) | 1982-11-01 |
| NL189466C (en) | 1993-04-16 |
| IT1130078B (en) | 1986-06-11 |
| GB2073224B (en) | 1984-01-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19970325 |