CA1099447A - Copolyamide resins having improved creep resistance - Google Patents
Copolyamide resins having improved creep resistanceInfo
- Publication number
- CA1099447A CA1099447A CA300,268A CA300268A CA1099447A CA 1099447 A CA1099447 A CA 1099447A CA 300268 A CA300268 A CA 300268A CA 1099447 A CA1099447 A CA 1099447A
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- Canada
- Prior art keywords
- acid
- piperazine
- diamine
- long
- chain
- Prior art date
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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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)
- Adhesives Or Adhesive Processes (AREA)
- Polyamides (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Copolyamides derived from a mixture of short-chain and long-chain saturated aliphatic dicarboxylic acids, piperazine and a polyoxyalkylene diamine are excellent hot melt adhesives useful with a variety of sub-strates. These thermoplastic copolyamide resins are particularly useful adhesives for vinyl materials especially plasticized vinyl substrates and are resistant to creep.
Copolyamides derived from a mixture of short-chain and long-chain saturated aliphatic dicarboxylic acids, piperazine and a polyoxyalkylene diamine are excellent hot melt adhesives useful with a variety of sub-strates. These thermoplastic copolyamide resins are particularly useful adhesives for vinyl materials especially plasticized vinyl substrates and are resistant to creep.
Description
1~99447 ~nis invention rela~es to ther~oplas~ic copolyamide adhesive resins.
¦ Polyamides derived from polymeric fatty acids, e.~. dimer acid, are well known and are highly useul a&esives for numerous applications with a wide variety of substrates. For example, polyamides derived from polymeric fatty acids and piperazine or dipiperidyl type diamines, and which optionally contain other dibasic acids or diamines, are described in U. S. Patent 3,377,303. Ihese polyamide resins are useful for hot melt bonding vinyl substrates. U. S. Patent 3,738,950 discloses adipic acid modified polyamide resins derived from polymeric fatty acids and piperazine.
; ~here maximum vinyl a&esion is desired it is generally considered advantageous to incorporate as high a level of piperazine as possible in the polyamide without detracting from the other desirable characteristics of the resin. The weight percentage of piperazine present in polymeric fatty acid derived polyamides, however, is significantly less than it could be if it were possible to employ short-chain dibasic acids in place of all or a large portion of the polymeric fatty acid. It would bethighly desirable therefore to prepare piperazine-containing thermoplastic polyamide resins which are not derived from polymeric fatty acids but which exhibit good overall characteristics making them suitable for hot melt bonding of -various substrates. It would be even more advantageous if such resins contained larger than usual amounts of piperazine so that improved vinyl adhesion was obtained.
Ether diamines are also known to be useful reactants for the preparation of polyamides. British Patent 1,319,807, for example, discloses copolyamide resins derived from polymeric fatty acids and low molecular weight aliphatic ether diamines. Similarly, U. S. Patent 2,499,853 discloses thermoplastic adhesives derived from relatively low molecular weight ether diamines, by themselves or in combination with ethylene diamine, and polymeric fatty acids.
_ 9944~ `
More recently, the reaction of al:iphatic ether diamines with short-chain aliphatic dicarboxylic acids has },een shown. German Offenlengungsschrift 25 52 518 discloses thermoplastic adhesive ccmpositions derived from a polyoxypropylene p~lyamine and an aliphatic or aromatic dicarboxylic acid hclving from 4 to 20 carkon atoms. German Offenlegungsschrift 25 52 455 further describes thermoplastic polyamide compositions which additionally contain piperazine with the polyo~ypropylene polyamine and aliphatic or aromatic dicarboxylic acid and indicates these resins are useful adhesives particularly with epoxy materials.
It has now quite unex~pectedly been discovered that, by reacting a mixture of ali-phatic dicarboxylic acids with piperazine and polyoxyaLky- ~
lene diamine, it is possible to obtain markedly improved thermoplastic co- r polyamide adhesives useful for konding a variety of substrates. Ib obtain these copolyamides very specific reactants must be employed within well de-fined limits. me resinous products of aspects of this invention exhibit superior adjesion to plasticized vinyl substrates. Quite unexpectedly the copolyamide adhesives have marked resistance to creep.
By one aspect of this invention, a thermoplastic cop~lyamide adhesive resin is provided having improved creep resistance comprising the reaction product of essentially stoichiometric amounts of (a) a mixture of saturated aliphatic dicarboxylic acids containing a short-chain dicarboxy-lic acid having from 2 to 7 carbon atoms and a long-chain dicarbox~lic acid having from 8 to 14 carbon atoms; tb) piperazine; and (c) a polyoxyalkylene diamine of the general formula CH3 I fH3 H2N-cHcH2~ocHcH2~mocH2cH-NH2 ere R is hydrogen or a methyl group and m is a positive integer such that the average n~lecular weight of the polyoxyalkylene dic~l-Lne is between 200 and 800; the equivalents ratio of the long~ to short-chain dicarboxylic acids ranging from 0.5:0.5 to 0.9:0.1 and the equivalents ratio of the piperazine to polyoxyalkylene diamine ranging from 0.7:0.3 to 0.95:0.05.
By one variant thereof, the resin additionally contains up to 20%, based on equivalents, of an aliphatic, cycloaliphatic or aromatic diamine having 2 to 10 carbon atcms, a dipiperidyl type diamine selected from the group consisting of 1,3-di(4-piperidyl~propane, 1,4-di~4-piperidyl)butane and 1,2-di(4-piperidyl)ethane or an N-substituted piperazine or dipiperidyl type diamine wherein the substituent is an aminoalkyl or hydroxyalkyl radi-cal having from 1 to 4 carbon atoms.
By still another variant, the resin is further characterized byhaving an acid value less than 10, an amine value less than 20 and soften-ing point in the range 100C to 200C.
By one variation thereof, the polyoxyaLkylene diamine has an average molecular weight from 300 to 600 and the equivalents ratio of piper-azine to polyoxyaLkylene diamine is between 0.75:0.25 and 0.90:0.10. t~
By another variation, the polyoxyalkylene diamine is a polyoxy-propylene diamine, the long-chain dicarboxylic acid has from ~ to 12 carbon atoms, the sh~rt-chain dicarboxylic acid has from 4 to 6 carbon atoms and the equivalents ratio of long- to short-chain dicarboxylic acids is between 0.65;0.35 and 0.80:0.20.
By still another variation, the resin is further characterized by having an acid value less than 7, amlne value less than 13 and softening point in the range 120C to 170C.
By yet another variation, the short-chain dicarboxylic acid is adipic acid and the long-chain dicarboxylic acid is azelaic acid.
By a further variation, the resin is further characterized by having a softening point in the range 135C to 155C, 190C viscosity in the range 125 poise to 300 poise, tensile strength of 1400-1650 psi and elongation of 300-550%.
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,...... l~9g~4'7 By another variation, tJle short-chain dicarboxylic acid is adipic acid and the long-chain dicarboxylic acid is sebacic acid. t - By another aspec-t of this invention, an improvement is provided -in a process for the preparation of thermoplastic copolyamide adhesive resins by the reaction of essentially stoichiomieitric amounts of (a) a mix-ture of adipic acid and a long-chain aliphatic saturated dicarboxylic acid having 8 to 14 carbon atoms, (b~ piperazine and tc) a polyoxyalkylene dia-mine of the general formula CH, R CH3 H2~l--CH(,H2 (OCHCH2tmOCH2CH-NH2 where R is hydrogen or a methyl group and m is a positive intefer such that theiaverage molecular weight of the polyoxyalkylene diamine is between 200 rand 800, the improvement which comprises heating the adipic acid, long-chain aliphatic saturated dicarboxylic acid and polyoxyalkylene diamine at 160C to 220C with agitation under an inert atmosphere and adding pipera-zine at a rate substantially to avoid polymeric salt formation.
By one variant thereof, the long-chain aliphatic saturated dicar-boxylic acid is azelaic acid or sebacic acid, the polyoxyaLkyiene diamine ~.
is a polyo~ypropylene diamine having an average molecular weight from 300 to 600, the equivalents ratio of adipic acid to azelaic or sebacic acid ranges from 0.5:0.5 to 0.9:0.1 and the equivalents ratio of piperazine to poly-oxypropylene di D e ranges from 0.7:0.3 to 0.95:0.5.
By variants thereof, the piperazine may be added as an anhydrous melt, or in an aqueous solution. ~ -As referred to above, the copolyamide resins of one aspect of this ~ -invention are generally obtained by the reaction of essentially stoichiome-tric amounts of a mixed acid com~onent consisting of a mixture of a long-chain saturated aliphatic di OE boxylic acid having from 8 to 14 car~on atQms and a shorter-cham saturated aliphatic dicarboxylic acid having from 2 to - - 3 b -. .
to 7 carbon atoms with piperazine cmd polyoxyalkylene diamine having an average molecular weight between 200 and 800. Especially useful adhesive resins are obtained with short-chain dicarboxylic acids having from 4 to 6 carbon atoms and long-chain dicarboxylic acids having from 9 to 12 carbon atoms. The equivalents ratio of long- to short-chain dicarboxylic acids ranges from 0.5:0.5 to 0.9:0.1. Polyoxyprop~lene diamines of average mole-cular weight 300 to 600 are preferred and the equi ~lents ratio of the pi- L
perazine to polyozyalkylene diamine will range from 0.7:0.3 to 0.95:0.05.
Up to 10% excess of acid or amine components can be employed for the pre-paration of these copolyamides and small amounts of other aliphatic, cyclo-aliphatic, or aromatic diamines or mixtures thereof included with the piperazine and polyoxyalkylene diamine. he copolyamide resins have acid values less than 10, amine values less than 20, softening points in the range 120-170C and exhibit excellent resistance to creep.
The improved copolyamides of aspects of this invention are gener- S
ally derived from a mixture of long-chain and short-chain saturated ali- ~-phatic dicarboxylic acids, piperazine and a polyoxyalkylene diamine. Op~
tionally, a small amount of other diamine may be present.
Necessarily present with the piperazine to form the amine camr ponent is a polyoxyalkylene diamine corresponding to the general formNla ., . H2N-CHCHz-~OCEICH23mOCH2C~NHz where R is hydrogen or a methyl group and m is a positive integer such that the average molecular weight of the polyoxyalkylene diamine is between 200 and 800. Especially useful polyoxyalkylene diamines for this invention are polyoxypropylene diamines having average molecular weights from 300 to 600.
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- ~' lU994~7 ~ e acid component is generally a ~xture of saturated aliphatic dicarboxylic acids consisting of a short-chain dicarboxylic acid having from 2 to 7 carbon atoms and a longer-chain dicarboxylic acid having from 8 to 14 carbon atoms. This acid mixture is essential to obtain the improved creep-resistant copolyamide compositions of aspects of this invention.
Especially useful short-chain i-L
.:
- 4 a -- ~ :
.. . ~ .
999L~
dicarboxylic acids will have 4 to 6 carbon atoms and include succinic, glutaric and adipic acids. The longer-chain saturated acids will preferably have 9 to 12 carbon atoms with azelaic acid and sebacic acid being S especially useful. By reacting the acid mixture, wherein the short-chain and long-chain dicarboxylic acids are present in specified ratios, with the piperazine and polyoxyalkylene diamine it is possible to obtain superior copolyamide adhesive resins which exhibit little or no plastic creep.
Essentially stoichometric amounts of the mixed acid component and the amine component consisting of piperazine and the polyoxyalkylene diamine are reacted to obtain these thermoplastic copolyamide resins. Not more than a 10% excess of either the acid or amine component should be present for the reaction and typically if an excess is to be employed it is preferable that the amine component be present in excess.
Generally the combination of adipic acid and piperazine~in a homopolymer or copolymer system at low to moderate temperatures of 20C to 160C
will result in the formation of high-melting adipic-piperazine polymeric salt which is quite difficult to satisfactorily transform into the polyamide -or copolyamide by elimination of water. If these conditions are used, low molecular weight polyamide segments and incompletely transformed polymeric organic salt ~that is present as an insoluble or incompatible suspension) will be obtained so as to detract from the appearance and the utility of the final pro,duct. To avoid this problem and still utilize adipic acid with .perazine, it has been found that techniques which limit the formation of the I ~, .
polymeric adipic-piperazine salt could be developed by restricting the concentration of piperazine or adipic acid during amidation. This is accomplished by introducing anhydrous or~ aqueous piperazine slowly to the hot (160-220C) mixture containing adipic acid so as to avoid the immediate f~4~tion o :he pcl ~ ric salt ~hile rapi~ly decomp ~in~ the ca- cx~l-rich ~ 1~994~7 salt system to form amide. By use of this technique no polymerie salt that resists amide formation will occur and little if anyloss~of adipic aeid is seen. The reverse of this proceS~ slow addition of molten or aqueous solutions of adipic acid to a hot (160-220C) amino-termunated prepolymer o~
azelaic or other dibasic acids and piperazine with or without other diamines has been found to yield similar results but is less desirable because of the tendency of anhydrous molten adipic acid to degrade and the larger volumes of water needed to prepare aqueous adipie aeid solutions.
The acid and aminecomponents are then reacted at maximum temperatures up to ;~240C until the desired acid and amine values are aehieved. It usually requires several hours to complete the reaction whieh is eonveniently followed by measuring the amount of water evolved. The reaction is preferably conducted under an inert atmosphere, e-g- nitrogen, and during the final stages of the reaction a vacuum may be applied to facilitate removai of the final traces of water and other volatiles present in the system.
he ratio of the long-chain dicarboxylic acid to short-chain dicarboxylic acid will range fro~ 0.5:0.5 to 0.9:0.1 based on equivalents. The equivalents ratio of piperazine to polyoxyalkylene diamine will range from 0.7:0.3 to 0.95:0.05. Superior resins which are especially useful for adhesion of vinyl substrates and which exhibit little or no plastic creep are obtained when the equivalents ratio of long- to short-chain acid is between 0.65:0.35 and 0.80:0.20 and the equivalents ratio of the piperazine to polyoxyalkylene diamine is between 0.75:0.25 and 0-90:0.10.
:
Aliphatie, eycloaliphatic or aromatic diamines containing up to 20 carbon atoms and more preferably from 2 to 10 carbon atoms e.g.
, I _ . . .
9944~7 ethylenediamine, hexamethylenedialnine, xylenedia~une, bis(aminoethyl) benzene, methylene-or isopro~ylid~ne-biscyclohexylamine, 1,4-piperazine- i~
bispropylamine and the like can be employed at low levels. Also useful are dipiperidyl type diamines e.g. 1,3-di(4-piperidyl)prppane, 1.4-di(4-piperi-dyl)butane and 1,2-di(4-piperidyl)ethane and N-substituted piperazine or dipiperidyl type diamines wherein the substituent consists of an aminoalkyl or hydroxyal~yl radical containing from 1 to 4 carbon atoms e.g. N-amino- r ethylpiperazine, N-aminopropylpiperazine and the like. While these dia-mines may constitute up to 20%, based on equivalents, of the total amine component they are typically present in amounts not greater than 10%.
The resins of aspects of this invention, formed from the above- r described reactants in the defined ratios, typically have an acid value ~! ' (A.O.C.S. Method Te la-64) less than 10 and amine value (ASTM Method D2074-66~ v~lue less than 20. Preferably the acid value of the resin will be less than 7 and amine value less than 13. ~hile the softening point (ASTM
Method E-28) can range from 100C to 200C it is preferable for most appli-cations that the softening point fall between 120 and 170C. In an especi-ally preferred e~bodiment of an aspect of this invention, w~ere the mixed acid ccmponent oonsisting of a mixture of azelaic acid and adipic acid (equivalents ratio of 0.65-0.75:00.35-).25) is reacted with 0.80 to 0.95 equivalent piperazine and 0.15 to 0.25 equivalent polyoxypropylene diamine having an average molecular weight of 350-450, a copolyamide having excel-lent vinyl adjesion and resistant to plastic creep and having the following general specification is obtained:
Softening Point (C) 135-155 190C Viscosity (poise) 125-300 TensiIe Strength (psi) 1400-1650 Elongation (%) 300-550 - 1(399~7 It has already been indicated tha~- one of the highly desirable features of the present copolyamides of aspec-~s of this invention which is quite unex~ f pected is their resistance to plastic creep. While other polyamide resins derived from piperazine and polyoxyalkylene diamines exhibi-t good adhesive properties it is onlv with the use of the muxed aliphatic dicarboxylic acid component with the piperazine and polyoxyalkylene diam me in the prescribed ratios that resins which exhibit little or no plastic creep can be obtained.
miS feature is highly desirable for many hot melt adjesive applications, particularly with difficulty bondable plasticized vinyl resin compositions, since it assures a permanent and fixed arrangement of the bonded assembly.
In other words the bonded materials retain the same relative position so ~;
long as the assembly is not exposed to temperatures near or akove the melt point or softening point of the resin.
~le copolyamide resins of aspects of this invention are ~seful as hot melt adllesives with a wide varietv of substrates. They can be used as such with both rigid or flexible, natural or synthetic, materials and are particularly useful for bonding vinyl materials. They may be employed to adhere leather, suede, and both woven and non-w~ven fabrics obtained from cotton, wool, silk, sisal, hemp, jute, rayon ~nd synthetic fibers, e.g., nylons, acrylics, polyesters, polyolefins and the like. They are also use-ful with natural rubber, polyurethanes, neoprene, styrene-butadiene copoly-mers, polybutadiene, AES and other polymeric materials. The present resin compositions are similarly useful for hot melt bonding rigid materials, e.g.
metals, including aluminum, steel, etc., wood, paper products, phenolics, cork, pressboard, glass and the like. The copolyamide resins are applied using conventional hot melt application proceduresj e.g. spraying, printing, ~-dipping, spreading, rolling, an~ the like and the film thickness can range from less than one mil up to fifty mils. While for most oonstructions the resin is applied to only one side of the substrate it may be applied to both sides in order to form a sandwich-type construction. me copolyamides .
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:
1~\99447 o~_asp~ects of this invention may be also be blended with other polyamide and polyester adhesive resins to obtain a wide variety of additional compositions useful for hot melt bonding. The present copolyamides may constitute as little as 0.5 weight percent of the total resins or, if other resins or additives are added thereto, can constitute as much as 99.9 weight percent of the total composition.
The invention is more fully illustrated by the following examples. All parts and percentages in these examples are on a weight basis unless otherwise indicated.
E~AMPLE I
Azelaic acid, adipic acid, piperazine and a polyoxypropylene diamine having an average molecular weight of 400 were reacted to obtain a copolyamide adhesive resin. The reactant charge was as follows:
Parts , Azelaic Acid 105 Adipic Acid 27 Piperazine 57 Polyoxypropylene Diamine 59 . .
The ratioof equivalents (azelaic acid:adipic acid:piperazine:polyoxyal~ylene diamine) for the above charge was 0.7:0.25:0.88:0.20. Azelaic and adipic acid and polyoxypropylene diamine were first charged to the reactor and heated under a nitrogen atmosphere to about 200-210C. Piperazine dissolved in hot water (60~ aqueous solution) was then added slowly but at a steady rate with agitation so that foam-over was avoided and the temperature did not drop below 200C. When the addition was complete the reaction was continued and the temperature increased to 220C. After the bulk of the theoretical amount of water was collected a vacuum of 5 Torr was 1~9~447 applied to remove the final traces of water. The resulting copolyamide resin (acid value <3 and amine value <20) had the following properties: 190C
viscosity (Brookfield Thermosel) 200 poise, softening point of 145C, Gardner color 3; tensile strength 1500 psi; and elongation at break 450~.
The above-prepared thermoplastic oopolyamide resin was used to bond a variety of substrates. Various materials were bonded and the shear strength of the resulting bond determined in accordance with ASTM Test Procedure D 1002-72. The results obtained were as follows:
MaterialShear Strength (psi) i Aluminum 1280 Steel 1570 Wood 500 Phenolic Resin 550*
ABS Resin 90 *Designates failure of substrate.
~ : ~
The adhesive resins were also evaluated in accordance with ASTM Test Procedure D 1876-72 to determine the peel or stripping strength of various adhesive bonds. Cotton duck, fabric-backed vinyland an unsupported vinyl/ABS -blend were employed for this test. The peel strengths observed for theserespective materlals were 18 lbs./in., 15 lbs./in. and 20 lbs./in. In all instances substrate failure occurred before failure of the adhesive bond.
Additionally, resistance to plastic creep of the adhesive resin was determined by bonding three inches of a 1" x 5" strip of the unsupported vinyl/ABS material to a 6" x 6" piece of pressboard. The bonded assembly was then placed in a 70C oven in an inverted horizontal position with a 100 gram weight attached to the 2" unbonded "tail". The extent of delamina-tion over a four hour period was observed. If 2 1/2" or more is pulled away -10- .
l ,,,,__ 1-~99447 from the pressboard in four hour-; or :Less this is considered to be a failure.
Anything less than 2 1/2" after four hours is acceptable. The less delamination the better the creep resistance of the adhesive resin. When the copolyamide of this example was evaluated for plastic creep no delamina-tion was obtained after the four hour test period.
In another procedure to evaluate resistance to creep 1" steel strips are bonded with a 1/2" lap joint. The assembly is hung in an oven with a one pound weight suspended from the bottom. The temperature is increased at a rate of 5C/30 minutes until the bond fails. The copolyamide of;this example withstood a temperature of 130C before failure.
EXAMPLE II
To demonstrate the unexpected improvement in creep resistance obtained when mixed saturated aliphatic dicarboxylic acids are employed with piperazin and the polyoxypropylene diamine (M. W. 400) the following reactions were conducted. For this example two copolyamides were prepared.~ In the first experiment (A) a mixture of adipic acid and azelaic acid was used whereas for the second reaction (B) azelaic was the sole dicarboxylic acid. ~he equivalents ratio of reactants and the properties of the resulting adhesive resins were as follows:
A B
Azelaic Acid 0.8 1.0 -Adipic Acid 0.2 ---Piperazine 0.85 0.85 Polyoxypropylene Diamine 0.15 0.15 Acid VaLue 9.5 6.2 Amine Value 11.3 10.0 Sofiening Point (C) 126-139 130-133 ~ . _ . .
1~99447 Both copolyamides exhibited good adhesion to vinyl and other substrates ¦¦ including leather, me-tal and w~od. ~lowever, copolyamide ~, the product of ¦¦ an aspect of this invention, also exhibited superior creep resistance.
~is product did not fail the plastic creep test even after 72 hours at 70C. On the other hand, Product s failed the plastic creep test within 15 minutes at 70C. The above data ~learly demonstrates the superiority of the products of aspects of this inv~ ~ion.
EXAMPLES III - V
To demonstrate the ability to vary the ratio of reactants the following experiments were conducted. The table sets forth the equivalents ratio of the reactants and the properties of the resulting copolyamide resin:
Ex. III Ex. IV Ex. V
Azelaic Acid 0.5 0.75 0.7 Adipic Acid 0.5 0.25 0.3 Piperazine 0.8 0.8 0.85 Polyoxypropylene Diamine 0.2 0.2 0.15 (M. W. 400) Acid Value 4 3.2 4 Amine Value 15 9.1 11 Softening Point tC) 212 147-162 170-175 Vinyl Adhesion Excellent Excellent Excellent Plastic Creep (in.) 0 0 0 While all the resins passed the plastic creep test, the resins of Example IV
did not fail even after 72 hours at 70C.
Similar results are obtained when pimelic acid is substituted for adipic acid, when sebacic acid ordodecanedioic acid is substituted for azelaic acid andwhen a polyoxypropylene diamine having an average molecular weight of 230 is substituted for the 400 molecular weight material.
' _ - .__
¦ Polyamides derived from polymeric fatty acids, e.~. dimer acid, are well known and are highly useul a&esives for numerous applications with a wide variety of substrates. For example, polyamides derived from polymeric fatty acids and piperazine or dipiperidyl type diamines, and which optionally contain other dibasic acids or diamines, are described in U. S. Patent 3,377,303. Ihese polyamide resins are useful for hot melt bonding vinyl substrates. U. S. Patent 3,738,950 discloses adipic acid modified polyamide resins derived from polymeric fatty acids and piperazine.
; ~here maximum vinyl a&esion is desired it is generally considered advantageous to incorporate as high a level of piperazine as possible in the polyamide without detracting from the other desirable characteristics of the resin. The weight percentage of piperazine present in polymeric fatty acid derived polyamides, however, is significantly less than it could be if it were possible to employ short-chain dibasic acids in place of all or a large portion of the polymeric fatty acid. It would bethighly desirable therefore to prepare piperazine-containing thermoplastic polyamide resins which are not derived from polymeric fatty acids but which exhibit good overall characteristics making them suitable for hot melt bonding of -various substrates. It would be even more advantageous if such resins contained larger than usual amounts of piperazine so that improved vinyl adhesion was obtained.
Ether diamines are also known to be useful reactants for the preparation of polyamides. British Patent 1,319,807, for example, discloses copolyamide resins derived from polymeric fatty acids and low molecular weight aliphatic ether diamines. Similarly, U. S. Patent 2,499,853 discloses thermoplastic adhesives derived from relatively low molecular weight ether diamines, by themselves or in combination with ethylene diamine, and polymeric fatty acids.
_ 9944~ `
More recently, the reaction of al:iphatic ether diamines with short-chain aliphatic dicarboxylic acids has },een shown. German Offenlengungsschrift 25 52 518 discloses thermoplastic adhesive ccmpositions derived from a polyoxypropylene p~lyamine and an aliphatic or aromatic dicarboxylic acid hclving from 4 to 20 carkon atoms. German Offenlegungsschrift 25 52 455 further describes thermoplastic polyamide compositions which additionally contain piperazine with the polyo~ypropylene polyamine and aliphatic or aromatic dicarboxylic acid and indicates these resins are useful adhesives particularly with epoxy materials.
It has now quite unex~pectedly been discovered that, by reacting a mixture of ali-phatic dicarboxylic acids with piperazine and polyoxyaLky- ~
lene diamine, it is possible to obtain markedly improved thermoplastic co- r polyamide adhesives useful for konding a variety of substrates. Ib obtain these copolyamides very specific reactants must be employed within well de-fined limits. me resinous products of aspects of this invention exhibit superior adjesion to plasticized vinyl substrates. Quite unexpectedly the copolyamide adhesives have marked resistance to creep.
By one aspect of this invention, a thermoplastic cop~lyamide adhesive resin is provided having improved creep resistance comprising the reaction product of essentially stoichiometric amounts of (a) a mixture of saturated aliphatic dicarboxylic acids containing a short-chain dicarboxy-lic acid having from 2 to 7 carbon atoms and a long-chain dicarbox~lic acid having from 8 to 14 carbon atoms; tb) piperazine; and (c) a polyoxyalkylene diamine of the general formula CH3 I fH3 H2N-cHcH2~ocHcH2~mocH2cH-NH2 ere R is hydrogen or a methyl group and m is a positive integer such that the average n~lecular weight of the polyoxyalkylene dic~l-Lne is between 200 and 800; the equivalents ratio of the long~ to short-chain dicarboxylic acids ranging from 0.5:0.5 to 0.9:0.1 and the equivalents ratio of the piperazine to polyoxyalkylene diamine ranging from 0.7:0.3 to 0.95:0.05.
By one variant thereof, the resin additionally contains up to 20%, based on equivalents, of an aliphatic, cycloaliphatic or aromatic diamine having 2 to 10 carbon atcms, a dipiperidyl type diamine selected from the group consisting of 1,3-di(4-piperidyl~propane, 1,4-di~4-piperidyl)butane and 1,2-di(4-piperidyl)ethane or an N-substituted piperazine or dipiperidyl type diamine wherein the substituent is an aminoalkyl or hydroxyalkyl radi-cal having from 1 to 4 carbon atoms.
By still another variant, the resin is further characterized byhaving an acid value less than 10, an amine value less than 20 and soften-ing point in the range 100C to 200C.
By one variation thereof, the polyoxyaLkylene diamine has an average molecular weight from 300 to 600 and the equivalents ratio of piper-azine to polyoxyaLkylene diamine is between 0.75:0.25 and 0.90:0.10. t~
By another variation, the polyoxyalkylene diamine is a polyoxy-propylene diamine, the long-chain dicarboxylic acid has from ~ to 12 carbon atoms, the sh~rt-chain dicarboxylic acid has from 4 to 6 carbon atoms and the equivalents ratio of long- to short-chain dicarboxylic acids is between 0.65;0.35 and 0.80:0.20.
By still another variation, the resin is further characterized by having an acid value less than 7, amlne value less than 13 and softening point in the range 120C to 170C.
By yet another variation, the short-chain dicarboxylic acid is adipic acid and the long-chain dicarboxylic acid is azelaic acid.
By a further variation, the resin is further characterized by having a softening point in the range 135C to 155C, 190C viscosity in the range 125 poise to 300 poise, tensile strength of 1400-1650 psi and elongation of 300-550%.
- 3 a -.
,...... l~9g~4'7 By another variation, tJle short-chain dicarboxylic acid is adipic acid and the long-chain dicarboxylic acid is sebacic acid. t - By another aspec-t of this invention, an improvement is provided -in a process for the preparation of thermoplastic copolyamide adhesive resins by the reaction of essentially stoichiomieitric amounts of (a) a mix-ture of adipic acid and a long-chain aliphatic saturated dicarboxylic acid having 8 to 14 carbon atoms, (b~ piperazine and tc) a polyoxyalkylene dia-mine of the general formula CH, R CH3 H2~l--CH(,H2 (OCHCH2tmOCH2CH-NH2 where R is hydrogen or a methyl group and m is a positive intefer such that theiaverage molecular weight of the polyoxyalkylene diamine is between 200 rand 800, the improvement which comprises heating the adipic acid, long-chain aliphatic saturated dicarboxylic acid and polyoxyalkylene diamine at 160C to 220C with agitation under an inert atmosphere and adding pipera-zine at a rate substantially to avoid polymeric salt formation.
By one variant thereof, the long-chain aliphatic saturated dicar-boxylic acid is azelaic acid or sebacic acid, the polyoxyaLkyiene diamine ~.
is a polyo~ypropylene diamine having an average molecular weight from 300 to 600, the equivalents ratio of adipic acid to azelaic or sebacic acid ranges from 0.5:0.5 to 0.9:0.1 and the equivalents ratio of piperazine to poly-oxypropylene di D e ranges from 0.7:0.3 to 0.95:0.5.
By variants thereof, the piperazine may be added as an anhydrous melt, or in an aqueous solution. ~ -As referred to above, the copolyamide resins of one aspect of this ~ -invention are generally obtained by the reaction of essentially stoichiome-tric amounts of a mixed acid com~onent consisting of a mixture of a long-chain saturated aliphatic di OE boxylic acid having from 8 to 14 car~on atQms and a shorter-cham saturated aliphatic dicarboxylic acid having from 2 to - - 3 b -. .
to 7 carbon atoms with piperazine cmd polyoxyalkylene diamine having an average molecular weight between 200 and 800. Especially useful adhesive resins are obtained with short-chain dicarboxylic acids having from 4 to 6 carbon atoms and long-chain dicarboxylic acids having from 9 to 12 carbon atoms. The equivalents ratio of long- to short-chain dicarboxylic acids ranges from 0.5:0.5 to 0.9:0.1. Polyoxyprop~lene diamines of average mole-cular weight 300 to 600 are preferred and the equi ~lents ratio of the pi- L
perazine to polyozyalkylene diamine will range from 0.7:0.3 to 0.95:0.05.
Up to 10% excess of acid or amine components can be employed for the pre-paration of these copolyamides and small amounts of other aliphatic, cyclo-aliphatic, or aromatic diamines or mixtures thereof included with the piperazine and polyoxyalkylene diamine. he copolyamide resins have acid values less than 10, amine values less than 20, softening points in the range 120-170C and exhibit excellent resistance to creep.
The improved copolyamides of aspects of this invention are gener- S
ally derived from a mixture of long-chain and short-chain saturated ali- ~-phatic dicarboxylic acids, piperazine and a polyoxyalkylene diamine. Op~
tionally, a small amount of other diamine may be present.
Necessarily present with the piperazine to form the amine camr ponent is a polyoxyalkylene diamine corresponding to the general formNla ., . H2N-CHCHz-~OCEICH23mOCH2C~NHz where R is hydrogen or a methyl group and m is a positive integer such that the average molecular weight of the polyoxyalkylene diamine is between 200 and 800. Especially useful polyoxyalkylene diamines for this invention are polyoxypropylene diamines having average molecular weights from 300 to 600.
;~ :
.~ .
- ~' lU994~7 ~ e acid component is generally a ~xture of saturated aliphatic dicarboxylic acids consisting of a short-chain dicarboxylic acid having from 2 to 7 carbon atoms and a longer-chain dicarboxylic acid having from 8 to 14 carbon atoms. This acid mixture is essential to obtain the improved creep-resistant copolyamide compositions of aspects of this invention.
Especially useful short-chain i-L
.:
- 4 a -- ~ :
.. . ~ .
999L~
dicarboxylic acids will have 4 to 6 carbon atoms and include succinic, glutaric and adipic acids. The longer-chain saturated acids will preferably have 9 to 12 carbon atoms with azelaic acid and sebacic acid being S especially useful. By reacting the acid mixture, wherein the short-chain and long-chain dicarboxylic acids are present in specified ratios, with the piperazine and polyoxyalkylene diamine it is possible to obtain superior copolyamide adhesive resins which exhibit little or no plastic creep.
Essentially stoichometric amounts of the mixed acid component and the amine component consisting of piperazine and the polyoxyalkylene diamine are reacted to obtain these thermoplastic copolyamide resins. Not more than a 10% excess of either the acid or amine component should be present for the reaction and typically if an excess is to be employed it is preferable that the amine component be present in excess.
Generally the combination of adipic acid and piperazine~in a homopolymer or copolymer system at low to moderate temperatures of 20C to 160C
will result in the formation of high-melting adipic-piperazine polymeric salt which is quite difficult to satisfactorily transform into the polyamide -or copolyamide by elimination of water. If these conditions are used, low molecular weight polyamide segments and incompletely transformed polymeric organic salt ~that is present as an insoluble or incompatible suspension) will be obtained so as to detract from the appearance and the utility of the final pro,duct. To avoid this problem and still utilize adipic acid with .perazine, it has been found that techniques which limit the formation of the I ~, .
polymeric adipic-piperazine salt could be developed by restricting the concentration of piperazine or adipic acid during amidation. This is accomplished by introducing anhydrous or~ aqueous piperazine slowly to the hot (160-220C) mixture containing adipic acid so as to avoid the immediate f~4~tion o :he pcl ~ ric salt ~hile rapi~ly decomp ~in~ the ca- cx~l-rich ~ 1~994~7 salt system to form amide. By use of this technique no polymerie salt that resists amide formation will occur and little if anyloss~of adipic aeid is seen. The reverse of this proceS~ slow addition of molten or aqueous solutions of adipic acid to a hot (160-220C) amino-termunated prepolymer o~
azelaic or other dibasic acids and piperazine with or without other diamines has been found to yield similar results but is less desirable because of the tendency of anhydrous molten adipic acid to degrade and the larger volumes of water needed to prepare aqueous adipie aeid solutions.
The acid and aminecomponents are then reacted at maximum temperatures up to ;~240C until the desired acid and amine values are aehieved. It usually requires several hours to complete the reaction whieh is eonveniently followed by measuring the amount of water evolved. The reaction is preferably conducted under an inert atmosphere, e-g- nitrogen, and during the final stages of the reaction a vacuum may be applied to facilitate removai of the final traces of water and other volatiles present in the system.
he ratio of the long-chain dicarboxylic acid to short-chain dicarboxylic acid will range fro~ 0.5:0.5 to 0.9:0.1 based on equivalents. The equivalents ratio of piperazine to polyoxyalkylene diamine will range from 0.7:0.3 to 0.95:0.05. Superior resins which are especially useful for adhesion of vinyl substrates and which exhibit little or no plastic creep are obtained when the equivalents ratio of long- to short-chain acid is between 0.65:0.35 and 0.80:0.20 and the equivalents ratio of the piperazine to polyoxyalkylene diamine is between 0.75:0.25 and 0-90:0.10.
:
Aliphatie, eycloaliphatic or aromatic diamines containing up to 20 carbon atoms and more preferably from 2 to 10 carbon atoms e.g.
, I _ . . .
9944~7 ethylenediamine, hexamethylenedialnine, xylenedia~une, bis(aminoethyl) benzene, methylene-or isopro~ylid~ne-biscyclohexylamine, 1,4-piperazine- i~
bispropylamine and the like can be employed at low levels. Also useful are dipiperidyl type diamines e.g. 1,3-di(4-piperidyl)prppane, 1.4-di(4-piperi-dyl)butane and 1,2-di(4-piperidyl)ethane and N-substituted piperazine or dipiperidyl type diamines wherein the substituent consists of an aminoalkyl or hydroxyal~yl radical containing from 1 to 4 carbon atoms e.g. N-amino- r ethylpiperazine, N-aminopropylpiperazine and the like. While these dia-mines may constitute up to 20%, based on equivalents, of the total amine component they are typically present in amounts not greater than 10%.
The resins of aspects of this invention, formed from the above- r described reactants in the defined ratios, typically have an acid value ~! ' (A.O.C.S. Method Te la-64) less than 10 and amine value (ASTM Method D2074-66~ v~lue less than 20. Preferably the acid value of the resin will be less than 7 and amine value less than 13. ~hile the softening point (ASTM
Method E-28) can range from 100C to 200C it is preferable for most appli-cations that the softening point fall between 120 and 170C. In an especi-ally preferred e~bodiment of an aspect of this invention, w~ere the mixed acid ccmponent oonsisting of a mixture of azelaic acid and adipic acid (equivalents ratio of 0.65-0.75:00.35-).25) is reacted with 0.80 to 0.95 equivalent piperazine and 0.15 to 0.25 equivalent polyoxypropylene diamine having an average molecular weight of 350-450, a copolyamide having excel-lent vinyl adjesion and resistant to plastic creep and having the following general specification is obtained:
Softening Point (C) 135-155 190C Viscosity (poise) 125-300 TensiIe Strength (psi) 1400-1650 Elongation (%) 300-550 - 1(399~7 It has already been indicated tha~- one of the highly desirable features of the present copolyamides of aspec-~s of this invention which is quite unex~ f pected is their resistance to plastic creep. While other polyamide resins derived from piperazine and polyoxyalkylene diamines exhibi-t good adhesive properties it is onlv with the use of the muxed aliphatic dicarboxylic acid component with the piperazine and polyoxyalkylene diam me in the prescribed ratios that resins which exhibit little or no plastic creep can be obtained.
miS feature is highly desirable for many hot melt adjesive applications, particularly with difficulty bondable plasticized vinyl resin compositions, since it assures a permanent and fixed arrangement of the bonded assembly.
In other words the bonded materials retain the same relative position so ~;
long as the assembly is not exposed to temperatures near or akove the melt point or softening point of the resin.
~le copolyamide resins of aspects of this invention are ~seful as hot melt adllesives with a wide varietv of substrates. They can be used as such with both rigid or flexible, natural or synthetic, materials and are particularly useful for bonding vinyl materials. They may be employed to adhere leather, suede, and both woven and non-w~ven fabrics obtained from cotton, wool, silk, sisal, hemp, jute, rayon ~nd synthetic fibers, e.g., nylons, acrylics, polyesters, polyolefins and the like. They are also use-ful with natural rubber, polyurethanes, neoprene, styrene-butadiene copoly-mers, polybutadiene, AES and other polymeric materials. The present resin compositions are similarly useful for hot melt bonding rigid materials, e.g.
metals, including aluminum, steel, etc., wood, paper products, phenolics, cork, pressboard, glass and the like. The copolyamide resins are applied using conventional hot melt application proceduresj e.g. spraying, printing, ~-dipping, spreading, rolling, an~ the like and the film thickness can range from less than one mil up to fifty mils. While for most oonstructions the resin is applied to only one side of the substrate it may be applied to both sides in order to form a sandwich-type construction. me copolyamides .
. .
:
1~\99447 o~_asp~ects of this invention may be also be blended with other polyamide and polyester adhesive resins to obtain a wide variety of additional compositions useful for hot melt bonding. The present copolyamides may constitute as little as 0.5 weight percent of the total resins or, if other resins or additives are added thereto, can constitute as much as 99.9 weight percent of the total composition.
The invention is more fully illustrated by the following examples. All parts and percentages in these examples are on a weight basis unless otherwise indicated.
E~AMPLE I
Azelaic acid, adipic acid, piperazine and a polyoxypropylene diamine having an average molecular weight of 400 were reacted to obtain a copolyamide adhesive resin. The reactant charge was as follows:
Parts , Azelaic Acid 105 Adipic Acid 27 Piperazine 57 Polyoxypropylene Diamine 59 . .
The ratioof equivalents (azelaic acid:adipic acid:piperazine:polyoxyal~ylene diamine) for the above charge was 0.7:0.25:0.88:0.20. Azelaic and adipic acid and polyoxypropylene diamine were first charged to the reactor and heated under a nitrogen atmosphere to about 200-210C. Piperazine dissolved in hot water (60~ aqueous solution) was then added slowly but at a steady rate with agitation so that foam-over was avoided and the temperature did not drop below 200C. When the addition was complete the reaction was continued and the temperature increased to 220C. After the bulk of the theoretical amount of water was collected a vacuum of 5 Torr was 1~9~447 applied to remove the final traces of water. The resulting copolyamide resin (acid value <3 and amine value <20) had the following properties: 190C
viscosity (Brookfield Thermosel) 200 poise, softening point of 145C, Gardner color 3; tensile strength 1500 psi; and elongation at break 450~.
The above-prepared thermoplastic oopolyamide resin was used to bond a variety of substrates. Various materials were bonded and the shear strength of the resulting bond determined in accordance with ASTM Test Procedure D 1002-72. The results obtained were as follows:
MaterialShear Strength (psi) i Aluminum 1280 Steel 1570 Wood 500 Phenolic Resin 550*
ABS Resin 90 *Designates failure of substrate.
~ : ~
The adhesive resins were also evaluated in accordance with ASTM Test Procedure D 1876-72 to determine the peel or stripping strength of various adhesive bonds. Cotton duck, fabric-backed vinyland an unsupported vinyl/ABS -blend were employed for this test. The peel strengths observed for theserespective materlals were 18 lbs./in., 15 lbs./in. and 20 lbs./in. In all instances substrate failure occurred before failure of the adhesive bond.
Additionally, resistance to plastic creep of the adhesive resin was determined by bonding three inches of a 1" x 5" strip of the unsupported vinyl/ABS material to a 6" x 6" piece of pressboard. The bonded assembly was then placed in a 70C oven in an inverted horizontal position with a 100 gram weight attached to the 2" unbonded "tail". The extent of delamina-tion over a four hour period was observed. If 2 1/2" or more is pulled away -10- .
l ,,,,__ 1-~99447 from the pressboard in four hour-; or :Less this is considered to be a failure.
Anything less than 2 1/2" after four hours is acceptable. The less delamination the better the creep resistance of the adhesive resin. When the copolyamide of this example was evaluated for plastic creep no delamina-tion was obtained after the four hour test period.
In another procedure to evaluate resistance to creep 1" steel strips are bonded with a 1/2" lap joint. The assembly is hung in an oven with a one pound weight suspended from the bottom. The temperature is increased at a rate of 5C/30 minutes until the bond fails. The copolyamide of;this example withstood a temperature of 130C before failure.
EXAMPLE II
To demonstrate the unexpected improvement in creep resistance obtained when mixed saturated aliphatic dicarboxylic acids are employed with piperazin and the polyoxypropylene diamine (M. W. 400) the following reactions were conducted. For this example two copolyamides were prepared.~ In the first experiment (A) a mixture of adipic acid and azelaic acid was used whereas for the second reaction (B) azelaic was the sole dicarboxylic acid. ~he equivalents ratio of reactants and the properties of the resulting adhesive resins were as follows:
A B
Azelaic Acid 0.8 1.0 -Adipic Acid 0.2 ---Piperazine 0.85 0.85 Polyoxypropylene Diamine 0.15 0.15 Acid VaLue 9.5 6.2 Amine Value 11.3 10.0 Sofiening Point (C) 126-139 130-133 ~ . _ . .
1~99447 Both copolyamides exhibited good adhesion to vinyl and other substrates ¦¦ including leather, me-tal and w~od. ~lowever, copolyamide ~, the product of ¦¦ an aspect of this invention, also exhibited superior creep resistance.
~is product did not fail the plastic creep test even after 72 hours at 70C. On the other hand, Product s failed the plastic creep test within 15 minutes at 70C. The above data ~learly demonstrates the superiority of the products of aspects of this inv~ ~ion.
EXAMPLES III - V
To demonstrate the ability to vary the ratio of reactants the following experiments were conducted. The table sets forth the equivalents ratio of the reactants and the properties of the resulting copolyamide resin:
Ex. III Ex. IV Ex. V
Azelaic Acid 0.5 0.75 0.7 Adipic Acid 0.5 0.25 0.3 Piperazine 0.8 0.8 0.85 Polyoxypropylene Diamine 0.2 0.2 0.15 (M. W. 400) Acid Value 4 3.2 4 Amine Value 15 9.1 11 Softening Point tC) 212 147-162 170-175 Vinyl Adhesion Excellent Excellent Excellent Plastic Creep (in.) 0 0 0 While all the resins passed the plastic creep test, the resins of Example IV
did not fail even after 72 hours at 70C.
Similar results are obtained when pimelic acid is substituted for adipic acid, when sebacic acid ordodecanedioic acid is substituted for azelaic acid andwhen a polyoxypropylene diamine having an average molecular weight of 230 is substituted for the 400 molecular weight material.
' _ - .__
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A thermoplastic copolyamide adhesive resin having improved creep resistance comprising the reaction product of essentially stoichiometric amounts of:
(a) a mixture of saturated aliphatic dicarboxylic acids containing a short-chain dicarboxylic acid having from 2 to 7 carbon atoms and a long-chain dicarboxylic acid having from 8 to 14 carbon atoms;
(b) piperazine; and (c) a polyoxyalkylene diamine of the general formula where R is hydrogen or a methyl group and m is a positive integer such that the average molecular weight of the polyoxyalkylene diamine is between 200 and 800; the equivalents ratio of the long- to short-chain dicarboxylic acids ranging from 0.5:0.5 to 0.9:0.1 and the equivalents ratio of the piperazine to polyoxy-alkylene diamine ranging from 0.7:0.3 to 0.95:0.05.
(a) a mixture of saturated aliphatic dicarboxylic acids containing a short-chain dicarboxylic acid having from 2 to 7 carbon atoms and a long-chain dicarboxylic acid having from 8 to 14 carbon atoms;
(b) piperazine; and (c) a polyoxyalkylene diamine of the general formula where R is hydrogen or a methyl group and m is a positive integer such that the average molecular weight of the polyoxyalkylene diamine is between 200 and 800; the equivalents ratio of the long- to short-chain dicarboxylic acids ranging from 0.5:0.5 to 0.9:0.1 and the equivalents ratio of the piperazine to polyoxy-alkylene diamine ranging from 0.7:0.3 to 0.95:0.05.
2. The thermoplastic copolyamide adhesive resin of Claim 1 which additionally contains up to 20%, based on equivalents, of an aliphatic, cyclo-aliphatic or aromatic diamine having 2 to 10 carbon atoms, a dipiperidyl type diamine selected from the group consisting of 1,3-di(4-piperidyl)propane, 1,4-di(4-piperidyl)butane and 1,2-di(4-piperidyl)ethane or an N-substituted piperazine or dipiperidyl type diamine wherein the substituent is an amino-alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms.
3. The thermoplastic copolyamide adhesive resin of Claim 1 which is further characterized by having an acid value less than 10, an amine value less than 20 and softening point in the range 100°C to 200°C.
4. The thermoplastic copolyamide adhesive resin of Claim 3 wherein the polyoxyalkylene diamine has an average molecular weight from 300 to 600 and the equivalents ratio of piperazine to polyoxyalkylene diamine is between 0.75:0.25 and 0.90:0.10.
5. The thermoplastic copolyamide adhesive resin of Claim 4 wherein the polyoxyalkylene diamine is a polyoxypropylene diamine, the long-chain dicarboxylic acid has from 9 to 12 carbon atoms, the short-chain dicarboxylic acid has from 4 to 6 carbon atoms and the equivalents ratio of long- to short-chain dicarboxylic acids is between 0.65:0.35 and 0.80:0.20.
6. The thermoplastic copolyamide adhesive resin of Claim 5 which is further characterized by having an acid value less than 7, amine value less than 13 and softening point in the range 120°C to 170°C.
7. The thermoplastic copolyamide adhesive resin of Claim 5 wherein the short-chain dicarboxylic acid is adipic acid and the long-chain dicarboxylic acid is azelaic acid.
8. The thermoplastic copolyamide adhesive resin of Claim 7 which is further characterized by having a softening point in the range 135°C to 155°C, 190°C viscosity in the range 125 poise to 300 poise, tensile strength of 1400-1650 psi and elongation of 300-550%.
9. The thermoplastic copolyamide adhesive resin of Claim 5 wherein the short-chain dicarboxylic acid is adipic acid and the long-chain dicarboxylic acid is sebacic acid.
10. In a process for the preparation of thermoplastic copolyamide adhesive resins by the reaction of essentially stoichiometric amounts of (a) a mixture of adipic acid and a long-chain aliphatic saturated dicarboxylic acid having 8 to 14 carbon atoms, (b) piperazine and (c) a polyoxyalkylene diamine of the general formula where R is hydrogen or a methyl group and m is a positive integer such that the average molecular weight of the polyoxyalkylene diamine is between 200 and 800, the improvement which comprises heating the adipic acid, long-chain aliphatic saturated dicarboxylic acid and polyoxyalkylene diamine at 160°C to 220°C with agitation under an inert atmosphere and adding piperazine at a rate substantially to avoid polymeric salt formations.
11. The process of Claim 10 wherein the long-chain aliphatic saturated dicarboxylic acid is azelaic acid or sebacic acid, the polyoxyalkylene diamine is a polyoxypropylene diamine having an average molecular weight from 300 to 600, the equivalents ratio of adipic acid to azelaic or sebacic acid ranges from 0.5:0.5 to 0.9:0.1 and the equivalents ratio of piperazine to polyoxypropylene diamine ranges from 0.7:0.3 to 0.95:0.5.
12. The process of Claim 11 wherein the piperazine is added as an anhydrous melt.
13. The process of Claim 11 wherein the piperazine is added in an aqueous solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78392977A | 1977-04-04 | 1977-04-04 | |
| US783,929 | 1977-04-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1099447A true CA1099447A (en) | 1981-04-14 |
Family
ID=25130853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA300,268A Expired CA1099447A (en) | 1977-04-04 | 1978-04-03 | Copolyamide resins having improved creep resistance |
Country Status (7)
| Country | Link |
|---|---|
| BE (1) | BE865680A (en) |
| CA (1) | CA1099447A (en) |
| DE (1) | DE2814566A1 (en) |
| GB (1) | GB1598209A (en) |
| NL (1) | NL7803595A (en) |
| PH (1) | PH17252A (en) |
| SE (1) | SE7803741L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6960315B2 (en) | 2000-08-19 | 2005-11-01 | Henkel Kommanditgesellschaft Auf Aktien | Method for forming moldings from dimer fatty acid free polyamides |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH642982A5 (en) * | 1979-02-26 | 1984-05-15 | Inventa Ag | POLYAETHER POLYAMIDE. |
| FR2497518A1 (en) * | 1981-01-05 | 1982-07-09 | Ato Chimie | THERMOFUSIBLE ADHESIVE COMPOSITIONS BASED ON COPOLYETHERAMIDE SEQUENCES |
| GB2190388A (en) * | 1986-03-27 | 1987-11-18 | Coates Brothers Plc | Polyamides and thixotropic compositions containing them |
-
1978
- 1978-04-03 SE SE7803741A patent/SE7803741L/en unknown
- 1978-04-03 PH PH20971A patent/PH17252A/en unknown
- 1978-04-03 CA CA300,268A patent/CA1099447A/en not_active Expired
- 1978-04-04 BE BE186559A patent/BE865680A/en unknown
- 1978-04-04 NL NL7803595A patent/NL7803595A/en not_active Application Discontinuation
- 1978-04-04 GB GB13144/78A patent/GB1598209A/en not_active Expired
- 1978-04-04 DE DE19782814566 patent/DE2814566A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6960315B2 (en) | 2000-08-19 | 2005-11-01 | Henkel Kommanditgesellschaft Auf Aktien | Method for forming moldings from dimer fatty acid free polyamides |
Also Published As
| Publication number | Publication date |
|---|---|
| BE865680A (en) | 1978-10-04 |
| DE2814566A1 (en) | 1978-10-05 |
| NL7803595A (en) | 1978-10-06 |
| PH17252A (en) | 1984-07-03 |
| SE7803741L (en) | 1978-10-05 |
| GB1598209A (en) | 1981-09-16 |
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