Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2000-09-26
2004-07-06
Woodward, Ana (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S057000, C525S058000, C525S064000, C525S066000, C525S069000, C525S071000, C525S072000, C525S073000, C525S074000, C525S076000, C525S078000, C525S079000, C525S080000, C525S09200D, C525S125000, C525S131000, C525S155000, C525S166000, C525S175000, C525S176000, C525S191000, C525S199000, C525S227000
Reexamination Certificate
active
06759480
ABSTRACT:
FIELD OF THE INVENTIONS
The present invention relates to thermoplastic resins modified by copolymers based on heavy acrylates, such as, for example, ethylene/2-ethylhexyl acrylate/maleic anhydride copolymers or ethylene/2-ethylhexyl acrylate copolymers blended with functionalized impact modifiers. The thermoplastic resins are, for example, polyamides, PMMA, polycarbonate or ABS. These modified resins are used to manufacture articles having an improved impact strength. These resins are manufactured by melt blending the various constituents in extruders, mixers (for example, a BUSS® Ko-Kneader) or any other device for blending thermoplastics.
BACKGROUND OF THE INVENTION
EP 096,264 discloses polyamides having a viscosity of between 2.5 and 5, these being reinforced by ethylene/C
2
to C
8
alkyl (meth)acrylate/unsaturated acid or anhydride copolymers comprising 20 to 40% by weight of acrylate. The heaviest acrylate used in the examples is n-butyl acrylate.
U.S. Pat. No. 5,070,145 discloses polyamides reinforced by a blend of (i) a polyethylene or an ethylene/alkyl (meth)acrylate copolymer and of (ii) an ethylenelalkyl (meth)acrylate/maleic anhydride copolymer. As in the previous prior art, the heaviest acrylate used in the examples is n-butyl acrylate.
U.S. Pat. No. 4,174,358 discloses reinforced polyamides in the form of a polyamide matrix in which nodules smaller than 1 &mgr;m are dispersed, these nodules having a certain modulus which also has to be a fraction of the modulus of the polyamide. Very many reinforcing agents are described, some of them having epoxy functional groups. Most are polymers having neutralized acid or anhydride functional groups or are EPDM-based blends. In column 13, polymer 26 is an ethylene/2-ethylhexyl methacrylate/carbon monoxide copolymer, which is used to modify nylon-6,6.
It has now been discovered that if thermoplastic resins are modified by copolymers or blends of copolymers comprising both heavy acrylates and at least one functional group, then impact strengths are obtained which are markedly improved over the prior art. The functional group may be, for example, an anhydride, an acid, an epoxy or an amine.
SUMMARY OF THE INVENTION
The present invention relates to thermoplastic compositions comprising:
−40 to 97 parts of a thermoplastic polymer (M) forming a matrix, chosen from polyamides, polyamide block copolymers, fluoro polymers, polycarbonate, styrene resins, PMMA, thermoplastic polyurethanes (TPU), copolymers containing polyester blocks and polyether blocks, polycarbonate-polyester alloys, polyketones, PVC and ethylene-vinyl alcohol copolymers (EVOH),
−60 to 3 parts of (B) comprising:
either an ethylene-alkyl (meth)acrylate copolymer (B1), the alkyl having at least 5 carbon atoms, which copolymer (B1) carries a functional group
or a blend of an ethylene-alkyl (meth)acrylate copolymer (B2), the alkyl having at least 5 carbon atoms, which copolymer (B2) does not carry a functional group, and of an impact modifier which carries a functional group.
DETAILED DESCRIPTION OF THE INVENTION
The polymers (M) are firstly described; regarding the polyamides, a polyamide should be understood to mean the product of the condensation:
of one or more amino acids, such as aminocaproic, 7-aminoheptanoic, 11-aminoundecanoic and 12-aminododecanoic acids or of one or more lactams, such as caprolactam, oenantholactam and lauryllactam;
of one or more salts or mixtures of diamines, such as hexamethylenediamine, dodecamethylenediamine, metaxylylenediamine, bis-p(aminocyclohexyl)methane and trimethylhexamethylenediamine with diacids such as isophthalic, terephthalic, adipic, azelaic, suberic, sebacic and dodecane dicarboxylic acids;
or of mixtures of some of these monomers, thereby resulting in copolyamides, for example PA-6/12 by the condensation of caprolactam with lauryllactam.
Polymers having polyamide blocks and polyether blocks result from the copolycondensation of polyamide blocks having reactive end groups with polyether blocks having reactive end groups, such as, inter alia:
1) polyamide blocks having diamine chain ends with polyoxyalkylene blocks having dicarboxylic chain ends;
2) polyamide blocks having dicarboxylic chain ends with polyoxyalkylene blocks having diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic dihydroxylated alpha,omega-polyoxyalkylene blocks called polyetherdiols;
3) polyamide blocks having dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides.
The polyamide blocks having dicarboxylic chain ends come, for example, from the condensation of alpha,omega-aminocarboxylic acids, of lactams, or of dicarboxylic acids with diamines in the presence of a chain-stopper dicarboxylic acid. Advantageously, the polyamide blocks are nylon-12 or nylon-6 blocks.
The number-average molar mass of the polyamide blocks is between 300 and 15,000 and preferably between 600 and 5000. The mass of the polyether blocks is between 100 and 6000 and preferably between 200 and 3000.
The polymers having polyamide blocks and polyether blocks may also include randomly distributed units. These polymers may be prepared by the simultaneous reaction of the polyether and of the polyamiide-block precursors.
For example, polyetherdiol, a lactam (or an alpha,omega-amino acid) and a chain-stopper diacid may be reacted in the presence of a little water. A polymer is obtained which has essentially polyether blocks and polyamide blocks of very variable length, but also the various reactants which, having reacted randomly, are distributed randomly along the polymer chain.
These polymers having polyamide blocks and polyether blocks, whether they come from the copolycondensation of polyamide and polyether blocks prepared beforehand or from a one-step reaction, have, for example, Shore D hardnesses which may be between 20 and 75, and advantageously between 30 and 70, and an intrinsic viscosity, measured in metacresol at 25° C., of between 0.8 and 2.5.
Whether the polyether blocks derive from polyethylene glycol, polyoxypropylene glycol or polyoxytetramethylene glycol, they are either used as they are and copolycondensed with polyamide blocks having carboxylic ends, or they are aminated in order to be converted into polyether diamines and condensed with polyamide blocks having carboxylic ends. They may also be blended with polyamide precursors and a chain stopper in order to make polymers containing polyamide blocks and polyether blocks and having randomly distributed units.
Polymers having polyamide blocks and polyether, blocks are disclosed in Patents U.S. Pat. No. 4,331,786, U.S. Pat. No. 4,115,475, U.S. Pat. No. 4,195,015, U.S. Pat. No. 4,839,441, U.S. Pat. No. 4,864,014, U.S. Pat. No. 4,230,838 and U.S. Pat. No. 4,332,920.
The polyether may be, for example, a polyethylene glycol (PEG), a polypropylene glycol (PPG) or a polytetramethylene glycol (PTMG). The latter is also called polytetrahydrofuran (PTHF).
Whether the polyether blocks are introduced into the chain of the polymer containing polyamide blocks and polyether blocks in the form of diols or diamines, they are called, for simplification, PEG blocks or PPG blocks or PTMG blocks.
It would not be outside the scope of the invention if the polyether blocks were to contain units different from units derived from ethylene glycol, propylene glycol or tetramethylene glycol.
Advantageously, the polymer containing polyamide blocks and polyether blocks is such that the polyamide is the predominant constituent by weight, that is to say the amount of polyamide which is in block form and that which is possibly distributed randomly in the chain represents 50% by weight or more of the polymer containing polyamide blocks and polyether blocks. Advantageously, the amount of polyamide and the amount of polyether are in the ratio (polyamide/polyether) of 50/50 to 80/20.
Preferably, the polyamide blocks and the polyether blocks of the same polymer (B) have {overscore (M)}
n
masses of 1000/1000, 1300/650, 2000/1000, 2600/650 and 4000/1000, res
Bouilloux Alain
Lacroix Christophe
Le Blevec Jean-Marc
Montanari Thibaut
Atofina
Smith , Gambrell & Russell, LLP
Woodward Ana
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