CA2033944A1 - Multilayered structures comprising polycarbonate layers and functionalized polyamide layer - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Multilayered structures comprising polycarbonate layers and functionalized polyamide layers exhibit adhesion to each other without the use of a tie layer. The multilayered structures are useful in containers requiring the combined properties of high impact strength and chemical resistance and/or oxygen barrier resistance.

Description

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08C!E!0 473 5 LAYERS AND FUNCTIONALIZED POLYAllIDE IAYER
G. Fred Wi 11 ard BA~KfiR~UN~QE~ NVENTIOII
Fi el d o~ th~ I nvent~
The present i nventi on rel ates to mul tilayere~
s~ructures having polycarbonate and polyamide layers; and, more particularly, relates ~o mul ti 1 ayered structures havi ng a functi onal i zed polyamide layer and a polycarbonate resin layer.
Descri~tiQn of _~Lated Art Multilayered structures having a polycarbonate layer and a polyamide layer have been employed in the past ~ see for exampl e Col 1 i ns, U . S . Patent No .
4, 513, 037 ) wherei n i s di 5cl osed a mul ~i 1 ayered lo structure havi ng a polysarbonate outer 1 ayer, a polycarbonate inner layer, and a polyamide intermediate layer between the two polycarbonate layers. The polycarbonate layers provide the structure with good impact strength, but typieally 15 l ack desi red l evel s of oxygen barri er properti QS .
The polyamide layer, in particular amorphous polyamides, provides the structure with the desired levels of oxygen barrier properties, bu~ typieally 1 ack~ adequate impact strength . The mul ti pl e 1 ayer 20 structure of Collins combines the desired properties of the polyearbonate l ayer and the polyami de l ayer to obtai n a structure havi ng both adequa~e i mpact stren~th and ade~uate oxygen barrier properties.
Mul ti pl e l ayered structures of a pol yearbonate 25 l ayer and a polyami de l ayer general ly l ack desi red levels of adhesion and require the use of tie layers i f adhesi on i s t~ be obtai ned between the l ayers .
Tie layers however can add addi~ional processing re~ui rements i n the creati on of the structure.

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Multiple layered structures consisting of polycarbonate layers and polyamide layers in direct contact with each other which do not employ a tie layer have generally resulted in laminates which delaminate under stress. Thus, it is an object of the present invention to provide a multilayered structure having good direct adhesion between the polyamide layer and the polycarbonate layer comprising layers of a polycarbonate resin layer ~nd lo an amine functionalized polyamide resin in direct adhering contact with each other.
SUMMARY QE THE I~VENTI~N
The present invention relates to multilayered structures comprising a polycarbonate layer and an amine functionali2ed polyamide layer. The multilayered structures exhibit good direct contact adhesion between the layers of a polycarbonate resin and a polyamide resin in direct contac~ wi~h each other and bonded to each other without the use of a tie layer between the polycarbonate layer and the polyamide layer. Exemplary multilayered structures include laminates and shaped articles, such as bot~les.
DETAILED DE$~RIPTI~N OF THE INVENTI~N
The present invention relates to multilayered structures comprising a polycarbonate layer in direct contact with a polyamide layer and bonded thereto without the use of a ~ie layer therebe~ween.
The multilayered struc~ures of the presen~ invention comprise a layer of a functionalized polyamide which is derived from a dicarboxylic acid, a diamine and a polyamine.
Polycarbonates for use in the structures of the present invention are high molecular weight, thermoplastic, aromatic polymers and include ~3~

a8CT04735 homopolycarbonates, copolycarbonates and copolyestercarbonates and mixtures thereo~ which have average molecular weights of about 8,000 to more than 200,000, preferably of about 20,000 to 80,000 and an I.Y. of 0.40 ~o 1.0 dl/g as measured in methylene chloride at 25C~ In one embodiment, the polycarbonates are deriYed from dihydric phenols and carbonate precursors and generally contain recurring structural units of the formula:

. O _ Y--O--~

where Y i s a di val ent aromati c radi cal of ~he di hydri c phenol empl oyed i n the polycarbonate prsduci ng reacti on .
Suitable dihydric phenols for producing lS polycarbonates include the dihydric phenols such as, for example, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4-bis(4-hydroxyphenyl)-heptane, 2,2~(3,5,3',5'-tetrachloro-4,4/-dihydroxy~
20 phenyl)propane, 2,2-(3,$,3',5'-tetrabromo-4,4'-dihydroxyphenyl~propane, and 3,3'-di-chloro-4,4' dihydroxydiphenyl)methane. Other dihydric phenols which are also suitable for use in the preparation of the above polycarbonates are disclosed in U.S.
Paten~ Nos. 2,999,835, 3,038,365, 3,334,154, and 4,131,575, incorporated herein by reference.
It is of course possible to employ two or more differen~ dihydrio phenols or a copolymer of a dihydric phenol with a glycol or with a hydroxy- or acid- terminated polyester, or with a dibasic acid in the event a carbonate copolymer or interpolymer rather than a homopolymer is desired fsr use in the Ç~J3~L

preparation of the articles of the invention.
Blends of any of the above materials can also be employed to provide the aromatic polycarbonate. In addition, branched polycarbonates such as are 5 described in U.S. Patent No. 4,001,184, can also be utilized in the practice of this invention, as can blends of a linear polycarbonate and a branched polycarbonate.
The carbonate precursor employed can be either n a carbonyl halide, a carbonate ester or a haloformate. The carbonyl halides which can be employed are carbonyl bromide, carbonyl chloride and mixtures thereof. Typical of the carbonate esters which can be employed are diphenyl carbonate, a di(halophenyl~carbonate such as di(chlorophenyl)carbonate, di~bromophenyl)carbonate, di(trichlorophenyl)carbonate, di~tribromophenyl)-carbonate, etc., di(alkylphenyl)carbonate such as di(tolyl)carbonate, etc.~ di(naphthyl)carbonate, di(chloronaphthyl~carbonate, etc., or mixtures thereof. The suitable haloformates include bis-haloformates of dihydric phenols (bischlorofQrmates of hydroquinone, etc.~ or glycols (bishaloformates of ethylene glycol, neopentyl glycol, polyethylene glycol, etc~). While other carbonate precursors wi 11 occur to those ski 11 ed i n the art, carbonyl chloride, also known as phosgene, is preferred.
The polycarbonate may also be a copolyestercarbonate as described in Clay~on B.
Quinn in U~S. Patent No . 4, 430, 484 and the references cited ~herein, incorpara~ed herein by reference. Preferred polyestercarbonates are those derived from the dihydric phenols and carbonate precursors described above and aromatic dicarboxylic ~33~

_ ~ _ acids or their relative derivatives~ such as the acid dihalides, e.g., dichlorides. A quite useful class of aromatic polyestercarbonates are those derived from bisphenol A; terephthalic acid, 5 i.sophthalic acid or a mixture thereof or their respective acid chlorides; and phosgene, If a mixture of ~erephthalic acid and isophthalic acid is employed, the weight ratio of terephthalic acid to isophthalic acid may be from about 5:95 to about 95:5. Another polycarbonate which may be used has from about 70 to about 95 weight percent ester content and a range of terephthalate groups of from 2 ~o about 15 weight percent of the total ester sontent. The remaining ester units are isoph~halate 15 units. These polycarbonates are more commonly known as polyphth~late carbonates and are described, for example, by Miller, et. al., U.S. Patent No.
4,465,820, herein incorporated by reference in its entirety.
The polycarbonates used to form the present invention can be manufactured by known processes, such as, for example, by reacting a dihydric phenol with a carbonate precursor such as diphenyl carbonate or phosgene in accordance with the me~hods Z5 set forth in the above-cited lit*rature and U.S.
Patent NosO 4,018,750 and 4,l23~43~, or by ~ransesterification processes such as are disclosed in U.S. Pa~ent NoO 3,153~008 as well as other processes known to those skilled in the art.
The aromatic polycarbonates are typically prepared by employing a molecular weight regulator, an acid accep~or and a catalys~. The molecular weight regulators which can be employed include phenol, cyclohexanol, methanol, alkylated phenols, such as octrylphenol, paratertiary-butyl-phenol, 6~

08C!T04735 etc. Preferably, phenol or an al kyl ated phenol i s employed as the molecular weight regulator.
The acid acceptor can be either an organio or an inorganic acid a~ceptor. A suitable organic acid acceptor is a tertiary amine and includes such materials as pyridine, triethylamine, dimethylaniline, tributylamine, etc. The inorganic acid acceptor can be one which can be either a hydroxide, a carbonate, a bicarbonate, or a phosphate or an alkali or alkaline earth metal.
The catalyst which can be empl oyed are those that typically aid the polymerization of the monomer with phosgene. Suitable catalysts include tertiary amines such as triethylamine, tri propyl ami ne, S N,N-dimethylaniline, quaternary ammonium bromider cetyl triethyl ammonium bromide, tetra n-heptyl ammonium iodide, tetra-n-propyl am~onium bromide~
tetramethyl ammonium chloride, tetra-methyl ammonium hydroxide, tetra-n-butyl ammsnium iodide, 20 benzyltrimethyl ammonium chloride and quaternary phosphonium compounds such as, for example, n-butyltriphenyl phosphonium brom~de and methyltriphenyl phosphonium bromide.
Also included are branched polycarbonates wherein a polyfunctional aromatic com~ound is reacted with the monomer and carbonate precursor to provide a thermoplastlc randomly branched polycarbonate. The polyfunctional aromatic compounds contain at least three functional groups which are carboxyl, carboxylic anhydride, haloformyl, or mixtures thereof. Illustrative polyfunctional aromatic compounds which can be employed include trimellitic anhydride, trimellitic acid, trimellityl trichloride, 4-chloroformyl phthalic anhydride, pyromellitic acid, pyromellitic ~3~

dianhydride, mellitic acid, mellitic anhydride, benzophenone-tetracarboxylic anhydride, and the like. The preferred polyfunctional aromatic compounds are trimellitic anhydride and trimellitic 5 aoid or their acid halide derivatives.
Polyamides for use in the production of the multilayered structures of the present invention are produced from the reactiQn products of a diamine and a carboxylic acid or a reactive diester thereof wherein the polyamide is chemically modified by substituting a polyfunctional monomer for a portion of the diamine in the synthesis step. Preferably, the polyamides have an amine number of at least 105 meq/kg to facilitate adhesion between the layers.
Suitable diamines for use in the production of the polyamides are of the general formula: :
(I) H2N--Rl--~H2 wherein Rl is an aliphatic, aromatic, unsaturated, or branched hydrocarbon having from 1 to 20 carbon atoms, and mixtures thereof. Examples of suitable diamines include ethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylenehexamethylene diamine, p- or m-xylylene diamine, bis-(4-amino cyclohexyl)-2s methane, 3-amino methyl-3,5,5-~rime~hyl cyclohexyl amine or 1,4-diaminamethyl eyclohexane.
A particularly preferred diamine for use in the present invention is hexamethylenediamine of the formula:
(II) H2N ~ 2)6 NH~ .

~ ~1 3 ~
û8CT04735 Suitable dicarboxylic acids for use in the present invention are of the ~eneral formula:
(III) O O
Il ll wherein R~ i 5 an aliphatic, aromatic, unsaturated, or mixtures of hydrocarbons having from 1 to 20 carbon atoms. Examples of suitable dicarboxylic acids include sebacic acid, heptadecaniodicarboxylic acid, adipic acid~ 2,2,4- or 2,4,4-trimethyl adipic acid, and terephthalic acid. Blends of dicarboxylic o aeids may also be employed.
A particularly preferred dicarboxylic acid ~or use in the present invention is isophthalic acid which has the formula:
(~V) O O
HO ~ C ~ C - OH

;5 Also preferred are blends of isophthalic acid and terephthalic acid, for example, 6~ mole% isophthalic acid and 35% terephthalic acid.
The term dicarboxylic acid is meant to inelude reaetiYe diesters of a d k arboxylic aeid such as those represented by the ~ormula:
( O O
R40 _ ~ - R3 ~ _ o - R5 2~33~

_ 9 _ wherein R3, R4 and R5 are the same or different aliphatic, aromatic or unsaturated hydrocarbons having from 1 to 20 hydrocarbons.
A particularly suitable diester of a 5 di carboxyl i G aci d i s di phenyl i sophthal ate of the formul a:
(VI j ~O-~C-O~

Also preferred are blends of diesters of di carboxyl i c aci ds such as bl ends of i sophthal i c 10 aci d and ~:erephthal i c aci d .
If a diaryl ester of a dicarboxyl~c acid is employed, then phenol may be produced as a byproduc~
in the production of the polyamide. Excess phenol shoul d be removed from the polyamide because the 15 presence of phenol will inhibit adhesion between the polyamide and polycarbonate layers.
Suitable multifunctional monomers ~or use in the present invention are polyamines of ~he general ~ormula:
(VII~

H2N - ~R6)n - ~ - (R7~m ~ NH2 wherein R6 and R7 are the same or different aliphatic, aromatic, or unsaturated hydrocarbons, n is an integer from 1 ~o 6, and m is an integer from 1 to 6.

.

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It is important that the internal amine is less reactive than the amine endgroups to prevent unduly large viscosity increases that can result from undesired crosslinking during ~ormation of th~
functionalized polyamide. It is also important that at least a slight excess of amine ~for example 1%
based on tota, moles of acid) be employed in the reaction so that the internal amine does not become capped by reacting with excess dicarboxylic acid.
Particularly suitable multifunctional monomers for use in the present invention include diethylenetriamine of the formula:
- (VIII) H2N - (C~2~2 - N ~ 2)2 - N~2 3,3'-iminobispropylamine of the formula:
(IX) H2N ~H2~3--~-- (CH2)3--NH2 and bishexamethylene triamine of the formula:
(X~

H2N - (CH2~6 - N - (CH2J6 - NH2 H

The multifunctional monomer is preferably present at a level of from about 3 percent to about g9 percent by mole based on the combined total moles of multifunctional msnomer and moles of diamine and more preferably from about 5 percent to about 20 mole percent thereof, and most preferably about 10 ~3~ 3 ~

percen~ thereof. It was found that adhesisn of the polyamide to the polycarbonate was only success~l when excess amine groups were present in the reaction mixture so that the internal functional amine groups are not capped by excess acid groups.
High ratio amine can be achieved by either the addition of an amine chain stopper or by employing the multifunctional monomer in excess of the dicarboxylic acid or the diester of the dicarboxylic acid. An example of a suitable chain stopper is docadecylamine.
The preferred embodiment of the present invention comprises reacting diphenyl isophthalate, hexamethylenediamine and diethylenetriamine according to the generalized reaction scheme:
(XI3 01~ ~ H2N(CH2)6NH2 H2N ( C~2 ) 2NH ( ~2) 2NH -~

o o o o ll ll ~
- ~ C_ NH(CH2)6N~ 90~ -c ~ ~ NH(cH~)2NH(cH2)2N~ lC%

+ ~ H

Preferably the diethylenetriamine is present at about 10% mole based on the total moles of hexamethylenediamine and diethylenetriamine. It has been found that when the dicarboxylic acid is a diester derivative, the phenol should be removed from the polyamide before the polyamide and the polycarbonate are adhered to each other. Suitable polyamides may be obtained from reaction mixtures of hexamethylenediamin@, a polyamine, isophthalic acid and terephthalic acid.
The polyamides and polycarbonates can be adhered to each other by sui~able methods r such as coextrusion or by pressing the films or sheets together under high pressure and heat. The polyamide and polycarbonate layer~ should each be at 1 east a hal f mi 1 thi ck . The resul ti ng mul ti l ayered 15 structures can be used to form 1 ami nates and shaped articles, such as bottlesO
Al though the desi red thi ckness of each 1 ayer wi 11 depend on the desi red properti es o~ the parti cul ar structure, a sui tabl e bottl e structllre 20 could have the polyamide layer preferably being a ~hickness of from 1 mil to 60 mils, more pre~erably from 2 mils to 30 mils and most preferably about 10 mils, and the polycarbonate layer preferably being a thickness of from 1 mil to 60 mils, more preferably from 2 mils to 30 mils and most preferably about 10 mils.
The term multilayered is mean~ to include structures havin~ two or more layers.
The fol 1 owi ng exampl es are set forth to 30 j 1 1 ustrate the presellt i nventi on and are not to be construed as limitiny the scopg of the invention thereto.

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Claims (14)

1. A multilayered structure comprising:
(a) an aromatic polycarbonate resin layer; and (b) a polyamide resin layer, said polyamide resin comprising the reaction product of:
(i) a dicarboxylic acid, (ii) a diamine, and (iii) a multi functional monomer of the general formula:

wherein R6 and R7 are independently selected from aliphatic, aromatic, and unsaturated hydrocarbons and n is an integer from 1 to 6, and m is an integer from 1 to 6.

2. A multilayered structure comprising:
(a) an aromatic polycarbonate layer, and (b) a polyamide layer said polyamide layer comprising a polyamide consisting essentially of the following moieties:

and wherein R2 is independently selected from aliphatic, aromatic, and unsaturated hydrocarbon groups having from 1 to 20 carbon atoms, R1 is independently selected from aliphatic, aromatic, and unsaturated hydrocarbon groups having from 1 to 20 carbon atoms, and R6 and R7 are independently selected from aliphatic, aromatic, and unsaturated hydrocarbons having from 1 to 6 carbon atoms.

3. The multilayered structures of claim 1 wherein said polyamide layer is at least 1 mil thick.

4. The multilayered structures of claim 2 wherein said polyamide layer is at least 1 mil thick.

5. The multilayered structure of claim 1 wherein said acid is diphenylisophthalate of the formula:

6. The multilayered structure of claim 2 wherein said acid is diphenylisophthalate of the formula:

7. The multilayered structure of claim 1 wherein said diamine is hexamethylenediamine.

8. The multilayered structure of claim 2 wherein said diamine is hexamethylenediamine.

9. The multilayered structure of claim 1 wherein said multifunctional monomers are from the group consisting of:
(a) diethylene triamine (b) 3,3'-iminobispropylamine, and (c) bis(hexamethylene)triamine.

10. The multilayered structure of claim 1 wherein said structure is a hollow container.

11. The multilayered structure of claim 2 wherein said structure is a hollow container.

12. The multilayered structure of claim 1 wherein said dicarboxylic acid is a mixture of isophthalic and terephthalic acid.

13. The multilayered structure of claim 2 wherein said polyamide is derived from isophthalic acid, terephthalic acid, hexamethylene diamine and a polyamine.

14. The invention as defined in any of the preceding claims including any further features of novelty disclosed.