AU628803B2 - Composition enabling at least two incompatible thermoplastic polymers to be made compatible, its use for the production of thermoplastic alloys and thermoplastic alloys obtained - Google Patents
Composition enabling at least two incompatible thermoplastic polymers to be made compatible, its use for the production of thermoplastic alloys and thermoplastic alloys obtained Download PDFInfo
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- AU628803B2 AU628803B2 AU30928/89A AU3092889A AU628803B2 AU 628803 B2 AU628803 B2 AU 628803B2 AU 30928/89 A AU30928/89 A AU 30928/89A AU 3092889 A AU3092889 A AU 3092889A AU 628803 B2 AU628803 B2 AU 628803B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08L57/04—Copolymers in which only the monomer in minority is defined
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/353—Five-membered rings
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- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
Composition making it possible to render compatible at least two incompatible thermoplastic polymers at least one of which contains carboxylic functional groups in its molecule and at least one of which does not contain these, characterised in that a bisoxazoline or a hydrogenated bisoxazine is used in combination with a maleinised polymer compatible with the polymers containing no carboxylic functional group. By melt-blending the thermoplastic polymers in the presence of the composition it is possible to obtain new thermoplastic alloys such as, for example, polyolefins-PBT.
Description
L
COMMONWEALTH OF AUSTRA 8 8 Form PATENTS ACT 1952-69 23 I COMPLETE SPECIFICATION
(ORIGINAL)
Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: SPriority Related Art: o Name of Applicant:
ATOCHEM
Address of Applicant: 8 Actual Inventor: 4 8, Cours Michelet, La Defense 10, 92800 Puteaux, France ROLAND PARSY, NADINE RIVAS EDWD. WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.
Address for Service: Complete Specification for the invention entitled: COMPOSITION ENABLING AT LEAST TWO INCOMPATIBLE THERMOPLASTIC POLYMERS TO BE MADE COMPATIBLE, ITS USE FOR THE PRODUCTION OF THERMOPLASTIC ALLOYS AND THERMOPLASTIC ALLOYS OBTAINED The following statement is a full description of this invention, including the best method of performing it known to US COMPOSITION ENASLING Ar LEAST TWO !NCOMPATL9LE THERMOPLASTIC POLYMERS TO BE MADE COMPATIBLE, ITS USE FOR THE PRODUCTION OF THERMOPLASTIC ALLOYS ANi THERMOPLASTIC ALLOYS OBTAINED The present invention relates to a composition which enables at Least two incompatible thermoplastic polymers to be made compatibl;, one of the polymers having carboxyl groups in its molecuLe. This composition is formed from a maLeinated polymer which is compatible with at Least one of the polymers not having carboxyL groups, and from a bisoxazoline, the generic term for hydrogenated oxazoles, or from a hydrogenated bisoxazine.
The general formuCl for hydrogenated oxazole rings is -C C that of hydrogenated bisoxazine is: CN N -C C C OC C C-0 0.-C The invention also relates to the use consisting of combining the composition with at Least two inconpatible thermoplastic polymers at least one of which o #0 O 0 *0 0* 0 o 0 0 *o 0*00 0 r 00~ I 10*0
I
O 0 I t 00 (1 00
I
*000 00 *0 0 0 01 0,0.00 *0 00 0 t 00 II 00 1 1 1 contains carboxyL groups in its molecule and at Least one of which does not contain any carboxyl groups.
Finally, the invention relates to various aLloys of thermoplastic poLymers which are made compatible as a mixture in combination with the composition.
Making two incompatible polymers compatible, in certain types of particular mixtures, by combining them with a third polymer which may be block copoLymerized or grafted, which is partially compatibls with each of the 10 polymers, is known. Initiation of this block copotymerization or this grafting in situ during mixing is also known. This is the case for example with the mixture of polypropyLene and poLyaiuide 6 which are made compatible by mateinated poLypropyLene. The advantage of this technique is that no prior block copoLynierization is necessary. Nevertheless it has the disadvantage of not being effective enough in every case and in particular in the case of mixtures of polypropylene and aromatic polyesters, The composition according to the invention enables the effectiveness of compatibility agents of this kind to be enhanced.
The composition according to the invention is formed by the combination of the two following constitue n ts: 1 a graft copoLymer or a random copoLymer, which is compatible with at Least one of the polymers, having in its molecule the radical of at Least one of the
I
t
I
3 monomers having the foLLowing a) 0 x C I1 0 Y
C\\
formul ae; in which X and Y are either a proton, or a chain having from 1 to 8 carbon atoms, it being understood that one of the two is a proton 00 o
V
0 0 A A0 A 0 o a w f o 10 0 A A 0* u o A 0* 0* «C A A 15 b) W 0 C C C C OH in which W is either I 1 i I II 0 x Y 0 a proton, or an aLkyl chain, which may be straight or branched, containing from I to 10 carbon atoms AI C 0 V C C I -o S- A compound of the 2 -A compound olf the in which W is as defined above and V is a hydrocarbon group, which may be straight chain or branched chain, having from Z to 12 carbon atoms and containing an ethylenic unsaturation formula; Sin which D is either x C D C- x 2 zero, or an alkyL o o
J
0 chain, which may contain at Least one aromatic ring and/or at Least one r 3a atom of oxygen, nitrogen, sulphur, halogen, the said chain being such that the corresponding dibasic acid OH OH has a pka of less than 4.5 and preferably less 1 0 than or equal to
X
1 and X 2 whether the same or different, represent a hydrocarbon chain having from 2 to 3 carbon atoms which may contain chemically reactive groups but does not react with the other components of the composition.
'By hydrocarbon chain which does not react with the other components, is 1 5 meant a chain 4 4
A.L
f V "i e .1 0^* J -3a 8~ 4 84 4 o 80 8 44 0* 88.0 4 @4 @8 8 8464 8 1; 8080 88 ow @8 i 4 8888 8 8 8 86 8 4 88 8 8 8 88 84 88 8 8 8 @8 @8 80 8 0 6 atom of oxygen, nitrogen, sulphur, halogen, the said ch n being such that the corresponding dibasic acid OO H has a pka of Less an 4.5 and preferabLy less than or equal to
X
1 and X2, whether the same different, represent a hydrocarbon chain which oes not react with the other constituents cont ing from 2 or 3 carbon atoms within the imino-et r ring.
10 y hydrocarbon chain which does not react with t (other constituents, is meant a hydrocarbon chain which may possibly contain chemically reactive groups, these not however being able to react with the other components of the composition and of the alloy according to 15 the invention.
In the case where none of the polymers which are to be made compatible contains a hydroxyl group or an amine group, it is recommended to combine with the former two components of the composition, a third compound 3 of the formula; RI T in which: T OH or NH2 and R 1 is an alkyL chain, which may be straight or branched, having from 1 to 20 carbon atoms, and which possibly contains at least one aromatic ring and/or at least 'A1. one atom of oxygen, nitrogen, sulphur or halogen.
U It is known that the compounds 2 which have been '4 5 described can react with carboxyl groups or anhydride groups. Thus, according to the US Patent 4,331,800 bisoxazolines are used to increase the degree of polymerization of aromatic polyesters. This increase results from coupLing of two chains by the carboxyL groups at their ends. Moreover, the reaction between anhydride groups and oxazolines has been used in accordance with US Patent 2,547,495 for preparing bis(phthalimido esters).
r" Thus two types of reaction exist according to 0494 prior art: d) C-D~~jjx ~i 4 W--D~N~lI-O ii d) co c-D-C -C-O-C 2 H 4-N-C-D-C-N-2H 4- C II tII I1 I "0 0 0 HO O H 0 4 4 f 15 M being the polymeric chain N 0 e 0 -D N C 2 C C H4-N
M'
M' again representing the polymeric chain.
These end coupling reactions have no effect on the suitability of making two polymers compatible. Besides, the bisoxazoline has of itself no intrinsic emulsifying power.
Copolymer 1 may be a random copolymer having 300 to 50,000 carbon atoms in its molecule. It results from -6 00 00 0 00 000 0 00 0 00 0090 0 0 00 0 *000 0 t 0000 00 04~ 0 0 0 I 0000 0 00 00 0 0 00 0 0 0 0 00 00 00 0 0 0 0 00 00 0 I the polymerization of a monomer having positions which are reactive with amines or alcohols, with other monomers which can be free-radical polymerized such as oLefins for example: ethylene, propytene, but-i-ene, aLkyL(rneth)acry- Lates for example: methyl, ethyl or butyL acryLates or methacrytates, dienes for example: buta-1,3-dione, isoprene or hexa-1,4-dliene, other common comonomers such as; styrene, methyl vinyl ether, acryLonitrite, vinyl acetate, vinyl chloride.
10 This polymer 1 may also be a graft copoLymer haying from 300 to 50,000 carbon atoms. It results from grafting of a polymer formed from monomers which can be free-radical poLymerized, such as those mentioned above, by a monomer having positions which are reactive with amines or alcohols. This grafting may be carried out by thermal addition at the remaining unsaturation of a dliene as described in the US Patent 3,972,961 or by free radicaL grafting in the molten state. This Latter method which is preferred consists of mixing in an extruder, a polymer to which from 500 ppm to 32 by weight of maLeic anhydride and a free radical initiator, in the order of 250 ppm to 4% by weight, have been added. The thermal decomposition of the initiator and the grafting of maLeic anhydride are carried out in the extruder between 170 and 250 0 C and preferably between 180 and 200 0 C. The remaining maLeic anhydride can be removed by dlegassing of the meLt before it passes through the-die. The average 7 residence time of the material. in the extruder is from seconds to 3 minutes and preferably from 40 to seconds.
The monomers having positions which are reactive with amiines or alcohols correspond to the general formu- Lae described above under b) or Monomers exempLi- K~2* tying the general formula a) are for example maleic anhydride and citraconic anhydride. Monomers exemplifying the general formula b) are for example, maLeic acid, ci- $er,1G traconic acid, funiaric acid, mesaconic acid or the mono esters of these acids in which W is a straight or branched chain having from.1 to 10 carbon atoms and which may have a phenyL ring. Monomers exemplifying the general. formula set) are, for example, aLlcenyL substituted succinic anhy- 15C t rd suha -aLLyL-succinic anhydride or 3-isoproprenyL-succinic anhydride.
The compounds having the general formula 2 are derivatives of bisoxazoLine or of bis(5,6-dlhydro-1,3oxazine). These compounds are formed by a cycLisation reaction carried out on the dibasic acid in accordance with known processes, such as that described for example by H. WANKER, Journal of the American Chemical Society, Vole 60 p. 2152 (1938) or by R.H. WILEY, Chiem. Rev. Vol.
44 p. 447, (1949). The preferred compounds are 2,2ibls (2-oxazoLine), 2,2'bis(4.4 dimethyL-2-oxazoLine), 2,21 bis(S.6-dihydro 4H1-1,3 oxazine), phenyL 2,2'bis(Z-oxazolin N,N'-ethylene bis(2-carbamoyL-2-oxazoLime) and -8 N,N'-ethylene bis(2-carbamoyl-5,6-dihydro-4H-1,3 oxazine).
In the case in which no incompatible polymer contains a hydroxyl group or an amine group, a third component may be added to the composition, this being preferably a fatty alcohol or fatty amine such as Lauryl alcohol, oleyl alcohol or stearyl alcohol or Laurylamine,
S*
oleylamine or stearylamine.
Although the components of the composition may be mixed prior to being added to the mixture of incompat- 10 ible thermoplastic polymers at least one of which contains carboxyl groups and at Least one other of which is compatible with copolymer 1, it is preferable to introduce the components of the composition separately in order to combine the two thermoplastic polymers in a homogeneous way. The addition of the composition to the thermoplastic polymers is normally carried out by homo- *t tr genisation in a mixer of the different components in the molten state. In order to obtain optimal effectiveness from the composition, adding the components of the composition to the mixture of thermoplastic polymers in the .i molten state is recommended, the compound described in 2 above being added after the other constituent or other constituents of the composition so that the anhydride groups are present in acid ester or acid amide form. In an initial stage the polymers are kneaded with copolymer 1 and possibly compound R 1 .The compound 2 is added to the mixture obtained, which has preferably been well i k9 1 9 14 homogenised.
The quantity of copoLymer as described above in 1, which is added to the mixture of incompatible thermot plastic polymers is about 0.1 to 10% and preferably 1 to i 5 5% by weight based on the weight of the mixture of tharmo- V plastic polymers. The quantity of compound 2 combined with the composition is such that the molar ratio of oxazoline groups or 4,5-dihydro-1,3-oxazine groups to active groups of copolymer I or these active groups after reaction with compound 3 such as anhydrides, acid-esters, I acids, or acid-amides, is between 0.1 and 10 and preferi ably between 1 and 3.
I In the case in which the compound 3 is added, I the quantity combined is such that the molar ratio of alcohol groups or amine groups to the active groups of I copoLymer 1 is between 0.1 and 10 and preferably between 1 I and 3.
The compatibility brought about by the composition according to the invention is revealed by electron SZO microscopy of the product resulting from the mixture of incompatible thermoplastic polymers.
The morphology of a mixture of incompatible thermoplastic polymers in the absence of a compatibility agent appears under the electron microscope in the form of large nodules of one of the polymers contained within the matrix formed by the other polymer. No adhesion exists between the nodules and the matrix. Addition of the composition according to the invention to the polymers produces a significant diminution in the size of the nodules. Moreover, an enhancement of the adhesion between the phases is observed, this being apparent from a coating of the nodules by the matrix. What may be called an alloy is formed under these conditions, by analogy a.# with metallurgical structures, as distinct from mix- It is known that increasing the dispersion and I~ 10 particularLy increasing nodule-matrix adhesion improves mechanicaL properties: G. MAGLIO R. PALUMBO, "PoLymer BLiendst CoL. 2 p. 41 Ed. PLENUM 1984. Moreover, incor- Ja :1' V porating the composition produces an improved stretching of the polymers when extruded, a riduction of die swell 15 and a reduction of delamination of the, oxtrudate which is observed during granulation.
Without Limiting the scope of the invention, thermopLastic polymers containing carboxyL groups may be selected from poLyesters such as potybutytene ttrephthaLate or potyethylene terephthatailte, potyamides such as polyamide 6, potyamide 11 or polyarnide 12, random copoLymers of acrylic acid or niethacryLilc acid such as ethyleneacrytic acid copoLymers.
The thermoplastic polymers which become part of the aLloy composition but do not contain carboxyL groups can be formod from ethytenicaLLy unsaturated monomers such as styrene, propylene, ethytene, which may be -11 copolym,.rized with other monomers such as an aipha-otefin such as octene, hexene, butane, or such as vinyl acetate, ethyl acrytate or methyl acrylate.
Due to the composition according to the invention which has been incorporated, in quantities previousLy given, in mixtures of incompatible thermoplastic poLymers, it is possible to produce novel alloys of thermoplastic t poLymers such as aLLoys of at Least one of the folowing ~resins: polypropylene, polystyrene, acrylonitrile- *etc 10 butedlene-styrene copolymer, styrene-acryLonitrie copolymer, polyphenylene oxide, polyethylene, ethylene-vinyl acetate copolymer, poLyvinytidene fluoride, polymethylmethacryLate, EPM copotymer, EPDM copolymer, polymethytpentene, polyphenytene suiphide (PPS), with at Least one of the following incompatible resins: potyamide or copolyamlde 6,11,12,6-106-6 or 6-9, poLyethereteramide, polybutylene terephthalate, polyethyLene terehthaLate, ethylene-acrylic acid copoLymer, semi-aromatic amorphous potyamides such as those described for exampte in the French Patents 1,588,130 and 2,324,672, European Patent 53,876 and Japanese Patent 60,217237, aromatic polyesters based on hydroxybenzoic acid, based on dibasic aromatic acids and based on diphenols such as those described in the US Patent 4,067,852 and 8elgian Patent 4,184,996, potyarytates, potycarbonate.
The following exampLes describe the invention 12 without Limiting it however.
2,21-bis(2-oxazoLine), 1,4-bis(5',6'-dihydro-4'H- 1',31-oxazine-2'yt)benzene, maLeinated propylene are prepared beforehand under the conditions below.
-Preparation of 2,21-bi3(2-oxazoLine) 146 g of ethyl oxalate and 200 cm 3 of dichioromethane are added to a two Litre flask with stirring and while swept with nitrogen. 122 g of ethanoLamine are added at ambient temperature and the reaction is allowed to proceed for 1 hour. The diethanotoxamide obtained is isoLated by filtration and dried. 160 g of this product are dissoLved in 900 cm 3of toluent, to which 205 cm 3 of
SOCL
2 are added, and heated to 70 0 C for 9 hours. The mixture obtained is filtered, washed with ethanol and then with boiling water and recrystaLLised in ethoxy-2ethanol. 127 g of the preceding product and 78.5 g of an 85% potassium hydroxide solution are dissolved in 1.2 t. of methanol and then refLuxed for 2 hours. After fiLtration, the organic phase is evaporated to dryness and the product is recrystaLLised in toluene.. The product obtained is 2,2'-bis(2-oxazoLlne). The pka of the dlibasic acid corresponding to this bisoxatoLine: oxatic acid is 1.2.
-Preparation of 1,4-bis(5',6'-dihydro-4'ft-1 ,1-xzie Z'yL)benzene The synthesis of this product is carried out in accordance with the process described in the German Patent 13 2,153,513 from dimethyL terephthaLate and 3-aminopropanoi. After reaction a white crysttLised product is obtained the melting point of which is 221 0 C. The microsnaLytical figures for carbon, hydrogen and nitrogen are given respectiveLy as 66.77%,' 6.59%, 11.05%. The pka of the dibasic acid corresponding to this hydrogenated bisoxazine; terephthaLic acid is -Grafting of poLypropylene by inaLeic anhydride in solution (A) 5 Litres of chtorobenzene, 1200 g of polypropy- Lens (3020 GN3 supplied by the APPRYL company) and 200 g of mateic anhydride are added to a 25 Litre vesseL. The whole is brought to 125 0 C then 216 g of peroxide (Luc idoL CHi 50) are added over 2 hours.
After this has been added, the whole is kept at 125 0 C for 30 minutes, then cooledl to 90 0 C and 10 Litres of acetone are injected over thirty minutes. The precipitated product is washed with acetone in order to extract free uuaLeic anhydride, then dried under vacuum at 80 0 C for 6 hours. A polypropylene grafted with 6.6% by weight of maLeic anhydride is obtained.
-Grafting of poLypropylene with maleic anhydridle, in the moLten state (B) A mixture of 100 parts of polypropylene (3050 MN4 suppLied by the APPRYL company), 1.5 part of maLeic anhydride and 1.7 part of 2,5-dimsthyL-2,5-diterbutyLPeroxide hexane dlissolved in one part of chLorobenzene are r 14 t f t T, i:I C t C; C C C 1I 1 C Vt continuously combined in a ZSK30 extruder (supplied by the WERNER company).
The temperature of the components is 20 0 0C and the rotational speed of the screw is 100 rpm. DevoLatilisation is carried out upstream of the die, in order to extract the chLorobenzene and unreacted maleic anhydride.
A polypropyLene grafted with 1% by weight of maleic anhydride is obtained.
EXAMPLE 1 PoLypropyLene-poLybutylene terephthaLate (PBT) 10 alloy a) reference mixture parts of polypropylene (3050 MN1 supplied by the APPRYL company) and 50 parts of PDT (ORGATER TMNO supplied by the ATOCHEM company) are kneaded at 250 0
C
for 30 minutes in the chamber of a HAAKE plastograph (SAMPLE 1).
Morphological examination by scanning electron microscopy of a cryogenic fracture shows the existence of nodules of PBT of 14 microns and a poor adhesion between these nodules and the polypropyLene matrix.
b) mixture compatibilised with maleinated polypropylene 0.4; 0.6; 1; 2 and 3 parts (SAMPLES 2, 3, 4, 6 respectively) of grafted polypropylene in the case of sample 4 and in the case of the other samples are added to the previous reference mixture and kneaded under the previous conditions. The morphoLogy of these mixtures is formed from nodules of PBT of 4 to 6 microns.
J
7* c) mixture kneaded in the presence of bisoxazoline 0.6 part of 2,2'-bis(2-oxazoline) is added to the previous reference mixture and kneaded under the previous conditions (SAMPLE The product obtained is formed from nodules of PBT of 17 to 18 microns. Comparison of this sample with samples 1 and 4 shows that 2,2'bis(2-oxazoline)-has no intrinsic power of compatibility.
d) alloy obtained according to the invention 1 part of maleinated polypropylene is added to the previous reference mixture and kneaded at 250 0 c.
After kneading for 15 minutes, 0.6 part of 2,2'-bis(2-oxazoline) is added and kneading is carried on for a further minutes (SAMPLE The morphology of this alloy is formed from nodules of PBT of 2.5 microns whose adhesion 15 to the matrix is excellent. The quality of the adhesion between the nodules and the matrix can be evaluated by t calculating the percentage of nodules which are excavated during the cryogenic fracture prior to the morphological examination. This percentage is 48 in the case of sample 4 and 38 in the case of sample S.
The diminution in the size of the nodules and the enhancement of nodule-matrix adhesion reflect the improved effectiveness of the composition in making propy- Lane and PST compatible.
The graph below shows the diameter of nodules of PBT, measured by morphological examination of the samples, as a function of the number of parts of grafted 1 6 polypropylene kets refer to added to the mixture. The figures in bracthe numbers of the samples.
Nodule diameter in microns (2) (3) l's 1.
4 g (6) 2 1 S 15 t 0,4 0,6 1 2 3 Parts of grafted polypropylene St r t t t r l iI' EXAMPLE 2 The following mixtures are kneaded at 250°C for minutes in the chamber of a Haake plastograph, using a blade rotation speed of 50 rpm; a) 50 parts of polypropylene (3050 MN1 supplied by the APPRYL company) and 50 par"s of polyamide 6 (orgamide supplied by the ATOCHEM company); SAMPLE 9 b) the previous constituents to which 1 part of grafted polypropylene is added: SAMPLE c) the constituents of mixture a) to which 1 part 6f it i _I I- -17 grafted polypropylene and after 15 minutes of kneading, 0.6 part of 2,2'-bis(2-oxazoline) are added: SAMPLE 11 These three alloys are examined by scanning eLectron microscopy. The morphologies show nodules of polypropylene dispersed in a polyamide matrix, characterized by their diameter and their adhesion to the matrix. The observations are summarised in the table below 10 Diameter of Adhesion between nodules in nodules and matrix microns S tr
S*
S. ts SAMPLE 9 14 nL SAMPLE 10 3.3 nit SAMPLE 11 1.6 good EXAMPLE 3 The following mixtures are kneaded at 260 0 C for minutes in the chamber of a Haake pLastograph, the speed of blade rotation being 50 rpm: a) 50 parts of polystyrene (Lacqr ne 1160c suppLied by the ATOCHEM company) and 50 parts of polybutylene terephthalate (ORGATER TMNO supplied by the ATOCHEM company): SAMPLE 12 b) the previous constituents to which is added 1 part of a styrene-maleic anhydride copolymer comprising 8% by weight of maleic anhydride (DyLark 700 supplied by the ARCO company): SAMPLE 13 d-:i :k r d 18 c) the constituents of the previous mixture b) to which, after 15 minutes of kneading, 0.5 part of 2,2'bis(2-oxazoline) have been added: SAMPLE 14 The morphologies of these three aLLoys are characterized by nodules of polypropyLene dispersed in a matrix of polybutylene torephthalate. The diameters of these nodules and the quality of their adhesion to the matrix are presented in the following table et 1 ttet Stt ePII S* p 4 Diameter of nodules in m icrons Adhesion between nodules and matrix SAMPLE 12 37 nil SAMPLE 13 6.4 good 15 SAMPLE 14 3.9 good EXAMPLE 4 The following mixtures are kneaded at 250 0 C for minutes in the chamber of a Heake plastograph, the rotational speed of the blades being 50 rpm: 20 a) 50 parts of a high density polyethylene having a melt index of 7 (PEHD 2070 MN60 supplied by the ATOCHEM company) and 50 parts of polybutylene terephthalate (ORGATER TMNO supplied by the ATOCHEM company): SAMPLE b) the previous constituents a) to which 5 parts of an ethylene-vinylacetate-maleic anhydride terpolymer are added the contents of vinylacetate and maLeic anhydride in the terpolymer being 14% and 0.385% (OREVAC 9307 supplied .s
I
19 by the ATOCHEM company): SAMPLE 16 c) the previous constituents (mixture b) to which, after 15 minutes of kneading, 0.5 part of 2,2'-bis(2-axazoline) are added: SAMPLE 17.
These three samples were observed by scanning electron microscopy. The size of the noduLes of PBT and their adhesion to the PE matrix are presented in the foLLowing table: c ec Vt Vr
V
t Vt t t erer VI t
IVV
t
V
1C
VL
*r 1 Ii q 15 EXAMPLE The following mixtures are kneaded at 270 0 C for minutes in the chamber of a Haake plastograph the rotational speed of the blades being 50 rpm a) 50 parts of polypropylene (PP 3050 MN1 supplied by the ATOCHEM company) and 50 parts of poLyethyene terephthaLate (PET): SAMPLE 18 b) the previous components (mixture a) to which I part of grafted poLypropyLent is added: SAMPLE 19 c) the previous components (mixture b) to which, after 15 minutes of kneading, 0.5 part of 2,2'bis(2-oxazoLine) is added: SAMPLE The morphology of these alloys is formed from nodules of PET dispersed in a PP matrix. The diameters of the nodules and the quality of the nodule/matrix adhesion are presented in the following table: Diameter of Adhesion between nodules in nodules and matrix microns re ,r t
C
I
I t- SAMPLE 18 20 nil SAMPLE 19 3 very good SAMPLE 20 2.2 very good EXAMPLE 6 The following mixtures are kneaded at 220 0 C for 30 minutes in the chamber of a Haake plastograph having a speed of blade rotation of 50 rpm; a) 60 parts of polypropylene (PP 3050 MN1 supplied by 15 the ATOCHEM company) and 40 parts of ethylene-acrylic acid copolymer (EAC) whose content of acrylic acid is 8% by weight and whose melt index is 5.5 at 1900C, under 2.16 kg (DOW 499): SAMPLE 21 b) the previous components (mixture a) to which 1 part of grafted polypropylene is added: SAMPLE 22 c) the components of mixture b) to which 0.5 part of 2,2'bis(Z-oxazollne) is added after 15 minutes of kneading; SAMPLE 23 d) the components of mixture a) to which 0.889 part of grafted polypropylene 0.111 part of dodecanol are added, then after 15 minutes of kneading, 0.5 part of 2,2'bis(2-oxazoLine) is added: SAMPLE 24 .2 21 The morphologies of these samples show nodules of EAC dispersed in a poLypropylene matrix.
The diameters of these nodules and their adhesion to the matrix are presented in the following table: Diam*ter of nodules in microns Adhesion between nodules and matrix nil average very gOOd very good
C-
'C gampto 21 10 Ssmple 22 Sampte 23 Sample 24 11 2.4 1.3 b0 C 16- Ct
I
:"i~z EXAMPLE 7 15 A reference mixture is prepared under the conditiuns of ExampLe lot SAMPLE 1 part of grafted polypropylene is added to the previous mixture and kneaded at 250*C for 30 minutes in the chamber of the HAAKE plastographi SAMPLE 26.
1 part of maLeinated polypropylene is added to the Previous reference mixture and kneaded at 250 0 C in the chamber of the HAAKI plastographo After kneading for minutes, 0.6 part of 1,4-bic(5',6'-dihydro-4'H-'3'osxazine-2'-yLbenzeno is added and kneading is carried on for 15 minutest SAMPLE 27, The morphotlogies of these aLLoys are examined under
I--
22 a sanning eLectron microscope, SAMPLE 25 has nodules of PST whose diameter is 14 ruicrons and whose adnesion with tne polypropylene matrix is nil.
In the-case of SAMPLE 26, the diameter of the nodules is 5 microns and the noduLes-matrix adhesion ii good, In the case if SAMPLE 27, the diameter of the nodules ie 3.2 mlcrons end the nodules-matrix adhesion is good.
Incorporation of hydrogenated bisoxazine Causes a reduction in the diameter of nodules.
r rr I l I 1 t It *1S*1 12D 4, 4 It 1 1t *4 fit I 4 *1 t
I
:r% "i;
Claims (7)
- 2. Composition according to Claim 1 characterized in that a combination is formed from: St at a copolymer 1, containing in its molecule the radical of at Least one of the monomers having the foL- Lowing formulae; a t 15 a) o in which X and Y are either 11 t: t: a proton, or a chain having -I 0 from 1 to 8 carbon atoms, it Y C being understood that one of II the two is a proton 0 b) W 0 C C C C OH in which W is either a 0 X Y 0 proton, or an alkyl chain, which may be straight or branched, containing from 1 to carbon atoms 24 H w- I-c in which W is as defined above and V is a hydrocarbon group, which may be straight chain or branched chain, having from 2 to 12 carbon atoms and con- taining an ethylenic unsaturation a compound 2 of the formula; in which D is ei thcr N .Ns or an alkyl chain which X, C D c X i 2 may contain at least one aromatic ring and/or at Least one atom of oxygen, nitrogen, sulphur, haLogen, the said chain being such that the corresponding dibasic acid 00 OH OH f I t L t has a pka of less than XI and X2, which may be the same or different, repre- sent a hydrocarbon chain which does not react with the other components containing from 2 or 3 carbon ms within the imino-ether ring.
- 3. Composition according t no of Claims I or 2 characterized in that i e case in which none of the polymers which to be made compatible contains a hydr- oxyl gro or an amine group, a compound 3 is combined h the composition, having the formula R 1 T in which: t3.,. -1 1 i *1 I I wjl~ hr -24a sent a hydrocarbon chain which may contain chemically reactive groups but does not react with the other components of the composition. 3. Composition according to one of Claims 1 or 2 characterized in that in the case in which none of the polymers which are to be made compatible contains a hydroxyl group or an amine group, a compound 3 is combined with the composition, having the formula R 1 T in which: Clr a I I 25 T OH or NH2 and R 1 is an alkyL chain which may be straight or branched, having 1 to 20 carbon atoms, and which may contain at least one aromatic ring and/or at least one atom of oxygen, nitrogen, sulphur, halogen.
- 4. Composition according to Claim 3 characterized in that the compound R 1 T is selected from fatty amines or fatty alcohols. Composition according to one of Claims 1 to 4 characterized in that the quantity of the compound 2 com- bined with the composition is such that the molar ratio of oxazoline groups or 4,5-dihydro-1,3-oxazine groups to the active groups of the copolymer 1 or to these active groups after reaction with the compound 3 is between 0.1 15 and Composition according to one of Claims 1 to characterized in that the quantity of compound 3 RI T added is such that the molar ratio of the alcohol groups or amine groups to the active groups of copolymer 1 is between 0.1 and
- 7. Process enabling at least two incompatible thermo- plastic polymers at least one of which contains carboxyL groups in its molecule and at least one of which does not contain carboxyl groups, to be made compatible by mixing in the molten state characterized in that a composition according to one of Claims 1 to 6 is incorporated in the mixture. '"-la *1 A 26
- 8. Process according to Claim 7 characterized in that the copolymer 1, and possibly the compound of formula R 1 T are previously incorporated in the mixture of polymers in the molten state, before adding the compound 2 to the mixture.
- 9. Process according to one of Claims 7 or 8 characterized in that the quantity of copolymer 1 added to the mixture of incompatible thermoplastic polymers is about 0.1 to 10% by weight based on the weight of the mixture of the said polymers. Compositions of thermoplastic polymers, one of which has carboxyl 1 0 groups in its molecule, containing the composition according to one of Claims 1 to 6.
- 11. Compositions of at least one of the following resins: polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polyphenylene oxide, polyethylene, ethylene-vinyl acetate copolymer, polyvinylidene fluoride, polymethyl methacrylate, EPM copolymer, EPDM copolymer, 1 5 polymethylpentene, polyphenylene sulphide (PPS), with at least one of the following incompatible resins: polyamide or copolyamide 6,11,12,6-10,6-6 or 6,9, polyether-esteramide, polybutylene terephthalate, polyethylene terephthalate, ethylene-acrylic acid copolymer, amorphous semi-aromatic polyamides, aromatic polyesters based on 20 hydroxybenzoic acid, based on dibasic aromatic acids and based on diphenols, polyarylates, polycarbonate. DATED this 30th day of June 1992 25 ATOCHEM I~ 4 o *i *I 4 C CC I Cr Ct C C> WATERMARK PATENT TRADEMARK ATTORNEYS 2ND FLOOR, "THE ATRIUM" 290 BURWOOD ROAD HAWTHORN VICTORIA 3122
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8802809 | 1988-03-04 | ||
FR8802809A FR2628115B1 (en) | 1988-03-04 | 1988-03-04 | COMPOSITION FOR MAKING COMPATIBLE WITH AT LEAST TWO INCOMPATIBLE THERMOPLASTIC POLYMERS, ITS APPLICATION TO THE MANUFACTURE OF THERMOPLASTIC ALLOYS, THERMOPLASTIC ALLOYS OBTAINED |
Publications (2)
Publication Number | Publication Date |
---|---|
AU3092889A AU3092889A (en) | 1989-09-07 |
AU628803B2 true AU628803B2 (en) | 1992-09-24 |
Family
ID=9363935
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU30928/89A Ceased AU628803B2 (en) | 1988-03-04 | 1989-03-03 | Composition enabling at least two incompatible thermoplastic polymers to be made compatible, its use for the production of thermoplastic alloys and thermoplastic alloys obtained |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0331554B1 (en) |
JP (1) | JPH01275662A (en) |
KR (1) | KR890014669A (en) |
CN (2) | CN1036143C (en) |
AT (1) | ATE92088T1 (en) |
AU (1) | AU628803B2 (en) |
CA (1) | CA1336030C (en) |
DE (1) | DE68907751T2 (en) |
DK (1) | DK103589A (en) |
FI (1) | FI98528C (en) |
FR (1) | FR2628115B1 (en) |
IE (1) | IE61465B1 (en) |
NO (1) | NO172246C (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02209953A (en) * | 1989-02-09 | 1990-08-21 | Mitsubishi Rayon Co Ltd | Polyarylene sulfide resin composition |
JP2556376B2 (en) * | 1989-03-31 | 1996-11-20 | 日本ジーイープラスチックス株式会社 | Polycarbonate and polystyrene composition |
GB8922557D0 (en) * | 1989-10-06 | 1989-11-22 | Exxon Chemical Patents Inc | Polyolefin/thermoplastic blend |
US5419861A (en) * | 1990-02-15 | 1995-05-30 | Elf Aquitaine Production | Method for improving the paintability of objects fashioned from polyamide and polyolefin blends |
EP0523258A1 (en) * | 1991-06-19 | 1993-01-20 | General Electric Company | Polymer mixture which comprises a polyphenylene ether and a styrene-containing polymer or copolymer, as well as products formed therefrom |
NL9200603A (en) * | 1992-03-31 | 1993-10-18 | Dsm Nv | A POLYMER COMPOSITION CONTAINING A MIXTURE OF A POLYOLEFINE AND A POLYMER BASED ON VINYLAROMATIC AND DICARBONIC ACID ANHYDRIDE MONOMERS. |
JP3643621B2 (en) * | 1995-05-09 | 2005-04-27 | 株式会社Kri | Compatibilizer and method for producing the same |
CN101434744B (en) * | 2007-11-14 | 2013-12-18 | 财团法人工业技术研究院 | Mixture and encapsulating material |
DE102008043863A1 (en) | 2007-11-19 | 2009-05-20 | Basf Se | Use of branched homo- or copolymer obtained by polymerization of a monomer of e.g. 2-phenyl-4,5-dihydro-oxazole compound, to increase the glass transition temperature of thermoplastic partially aromatic polyamides |
WO2014175364A1 (en) * | 2013-04-25 | 2014-10-30 | 住友精化株式会社 | Polyolefin-type resin composition |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0148743A2 (en) * | 1984-01-06 | 1985-07-17 | Mitsui Petrochemical Industries, Ltd. | Thermoplastic resin composition |
EP0295103A2 (en) * | 1987-06-10 | 1988-12-14 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition |
AU3170889A (en) * | 1988-03-24 | 1989-09-28 | Atochem | New alpha-mono-olefin based graft copolymer |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
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DE2245957A1 (en) * | 1972-09-19 | 1974-03-28 | Basf Ag | THERMOPLASTIC MOLDING COMPOUNDS AND LAMINATES |
JPS5645953A (en) * | 1979-09-25 | 1981-04-25 | Teijin Ltd | Modifier for molding compound |
JPS55151008A (en) * | 1979-05-15 | 1980-11-25 | Takeda Chem Ind Ltd | Preparation of high molecular polymer having crosslinked structure |
JPS5622366A (en) * | 1979-07-30 | 1981-03-02 | Takeda Chem Ind Ltd | Composition for powder coating material |
JPS57164A (en) * | 1980-06-04 | 1982-01-05 | Teijin Ltd | Method of molding aromatic polyamide resin |
DE3168127D1 (en) * | 1980-07-17 | 1985-02-21 | Ici Plc | Films from compositions of polyesters and olefine polymers |
JPS58122950A (en) * | 1982-01-19 | 1983-07-21 | Idemitsu Kosan Co Ltd | Polypropylene composition having improved rigidity |
WO1985002858A1 (en) * | 1983-12-27 | 1985-07-04 | The Dow Chemical Company | Polymer blends containing a polymer having pendant oxazoline groups |
US4615941A (en) * | 1984-12-27 | 1986-10-07 | Mobil Oil Corporation | Opaque pearlescent films containing dispersed incompatible polymer and polymeric interfacial agent |
NL8500427A (en) * | 1985-02-15 | 1986-09-01 | Stamicarbon | IMPACT RESISTANT POLYAMIDE COMPOSITION. |
WO1987005304A1 (en) * | 1986-03-07 | 1987-09-11 | The General Electric Company | Polyphenylene ether/polyamide blends having improved physical properties |
JPS63146928A (en) * | 1986-08-28 | 1988-06-18 | Sumitomo Chem Co Ltd | Thermoplastic resin composition |
JPH0623293B2 (en) * | 1987-02-09 | 1994-03-30 | 住友ダウ株式会社 | Thermoplastic resin composition |
JP2555610B2 (en) * | 1987-06-29 | 1996-11-20 | 三菱瓦斯化学株式会社 | Resin composition |
-
1988
- 1988-03-04 FR FR8802809A patent/FR2628115B1/en not_active Expired - Lifetime
-
1989
- 1989-01-17 NO NO890199A patent/NO172246C/en unknown
- 1989-02-15 IE IE48989A patent/IE61465B1/en not_active IP Right Cessation
- 1989-02-20 AT AT89400466T patent/ATE92088T1/en active
- 1989-02-20 EP EP89400466A patent/EP0331554B1/en not_active Expired - Lifetime
- 1989-02-20 DE DE89400466T patent/DE68907751T2/en not_active Expired - Fee Related
- 1989-03-03 FI FI891037A patent/FI98528C/en not_active IP Right Cessation
- 1989-03-03 AU AU30928/89A patent/AU628803B2/en not_active Ceased
- 1989-03-03 KR KR1019890002661A patent/KR890014669A/en not_active Application Discontinuation
- 1989-03-03 DK DK103589A patent/DK103589A/en not_active Application Discontinuation
- 1989-03-03 CA CA000592659A patent/CA1336030C/en not_active Expired - Fee Related
- 1989-03-04 JP JP1052752A patent/JPH01275662A/en active Pending
- 1989-03-04 CN CN89101049A patent/CN1036143C/en not_active Expired - Fee Related
-
1994
- 1994-11-03 CN CN94117804A patent/CN1111259A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0148743A2 (en) * | 1984-01-06 | 1985-07-17 | Mitsui Petrochemical Industries, Ltd. | Thermoplastic resin composition |
EP0295103A2 (en) * | 1987-06-10 | 1988-12-14 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition |
AU3170889A (en) * | 1988-03-24 | 1989-09-28 | Atochem | New alpha-mono-olefin based graft copolymer |
Also Published As
Publication number | Publication date |
---|---|
KR890014669A (en) | 1989-10-25 |
JPH01275662A (en) | 1989-11-06 |
NO172246B (en) | 1993-03-15 |
DK103589A (en) | 1989-09-04 |
EP0331554B1 (en) | 1993-07-28 |
CN1037352A (en) | 1989-11-22 |
NO890199L (en) | 1989-09-05 |
CN1111259A (en) | 1995-11-08 |
AU3092889A (en) | 1989-09-07 |
FI98528C (en) | 1997-07-10 |
CA1336030C (en) | 1995-06-20 |
DK103589D0 (en) | 1989-03-03 |
FR2628115A1 (en) | 1989-09-08 |
DE68907751T2 (en) | 1994-01-27 |
ATE92088T1 (en) | 1993-08-15 |
FI891037A (en) | 1989-09-05 |
FI98528B (en) | 1997-03-27 |
DE68907751D1 (en) | 1993-09-02 |
NO890199D0 (en) | 1989-01-17 |
NO172246C (en) | 1993-06-23 |
EP0331554A1 (en) | 1989-09-06 |
IE61465B1 (en) | 1994-11-02 |
CN1036143C (en) | 1997-10-15 |
FI891037A0 (en) | 1989-03-03 |
FR2628115B1 (en) | 1990-07-13 |
IE890489L (en) | 1989-09-04 |
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