|Title of Invention||
A PROCESS FOR PRODUCING POLY-PROPYLENE (CO) POLYMER WITH ENHANCED MELT STRENGTH
|Abstract||The present invention relates to a process for producing poly-propylene (co)polymer with enhanced melt strength. The use of initiator dispersion with a particulate initiator dispersed in a polar medium instead of the corresponding non-dispersed initiators or their dilutions or solutions results in a significant enhancement of the melt strength of the modified polymer, and a wide range of initiators turn out to PRICE: THIRTY RUPEES|
|Full Text||The invention pertains to a process for enhancing the melt strength of a poly¬propylene (co)polymer by mixing an initiator with the polypropylene (co)polymer at a temperature below the decomposition temperature and heating the mixture, with most of the initiator decomposing before the polymer has melted and with the formed radicals reacting with the polymer.
Such a process is known from DE-A-4340194, where a polypropylene homo-polymer or copolymer is mixed with bis(2-ethylhexyl) peroxydicarbonate, after which as a result of the initiator decomposing and an after-treatment with heat in an inert atmosphere, a modified polymer with enhanced melt strength is obtained. For greater ease of handling and effective distribution through the polymer, the initiator employed is diluted with an inert solvent.
However, there are several drawbacks to the process disclosed in the German patent application. In particular, the handling of the utilised bis(2-ethylhexyl) peroxydicarbonate is attended with certain risks, among them premature (explosive) decomposition. It is true that this risk is reduced by mixing the initiator with an inert solvent, but this means that a substantial quantity of an undesired additive is introduced into the end product. Besides, the required storage temperature and the temperature at which it is still possible to handle the dissolved initiator continue to be low. The publication also shows that only one specific initiator, the aforesaid bis(2-ethylhexyl) peroxydicarbonate, is suitable for increasing the melt strength of the polymer.
Surprisingly, it has now been found that the effectiveness of the process can be improved significantly, and the range of suitable initiators increased substantially, by making use of specific formulations of initiators.
To this end the invention is characterised in that the polypropylene (co)polymer is contacted with a dispersion of the initiator in a polar medium, with at least 90% by weight of the initiator particles being smaller than 50 jam and at least 99% by weight of the initiator particles being smaller than 65 f^m.
It is recommended to select the smallest possible size for the initiator droplets or particles in the dispersion. Preferably, at least 99% by weight (% w/w) of the initiator particles is smaller than 50 ^m.
It should be noted that EP-A-0384431, like DE-A-4340194, describes a process for modifying a polypropylene (co)polymer with the aid of a reactive initiator. The resulting polymer is characterised by a branching index of less than 1 and having significant strain hardening elongatoinal viscosity. Also mentioned is the use of initiators both in the neat form and in solutions in an inert liquid medium, such as a hydrocarbon. According to this patent publication, suitable initiators in this process are those having a reactivity within certain limits. As suitable compounds are mentioned in particular peroxydicarbonates and peresters of neodecanoic acid and 2,2-dimethyl propanoic acid.
EP-A-0287239 describes a process for the manufacture of non-sticky pellets of slightly degraded polypropylene. To this end the polypropylene (co)polymer is contacted with two initiators, including a reactive initiator. The initiators used in that case may be liquid or solid, dissolved in water or a hydrocarbon, or else associated with an inert solid carrier. The reactivity of the second initiator in
that case will be low enough for it not to decompose until it is in the polymeric melt, usually at temperatures in the range of about 160 to 240°C.
The term "polypropylene (co)polymer" refers to polymers or mixtures of polymers containing at least 50% by weight of polymerised propylene. Use may be made in this connection of block copolymers, tercopolymers, alternating copolymers, and random copolymers. Generally, a polypropylene copolymer in the polymerised form will contain one or more other olefins, such as ethylene, butene, pentene, hexene, heptene, or octene, but it may also comprise other olefinically unsaturated monomers or combinations of these, such as acrylates, styrene and styrene derivatives, acrylonitrile, vinyl acetate, vinylidene chloride, and vinyl chloride. It is preferred here to restrict the content of olefins other than propylene to 30% by weight of the copolymer. Especially suited to be used are copolymers of propylene and ethylene or mixtures of polypropylene and polyethylene containing not more than 10% by weight of polymerised ethylene. The molecular weight of the (co)polymer of which use is made can be selected within wide-ranging limits. Indicative of the molecular weight is the melt-flow index (MFI). Use may be made of (co)polymers having an MFI from 0.1 to 100 g/IOmin (2.16 kg, 230°C). Preferably, use is made of (co)polymers having an MFI from 0.5 to 50 g/IOmin (2.16 kg, 230°C).
The term initiators comprises all compounds capable of generating free radicals. Examples of such compounds are peroxides, azo initiators, C-C initiators, and N-0 initiators. Optionally, a combination of initiators from one or more of these categories may be employed. During the modification of the polypropylene (co)polymer the initiators preferably should decompose more than 95% at temperatures below the melting point of the polypropylene (co)polymer. If so desired, a combination of initiator and accelerator may be used to attain the required reactivity. However, it is preferred to use initiators
having a half life of one hour at temperatures below lOCC. The quantity of initiator, in the dispersed form, which is actually used according to the invention will be dependent on the desired degree of modification and on the polypropylene (co)polymer employed. Preferably, the initiator concentration in the polar medium is less than 33% by weight. More preferably, use is made of initiator concentrations in the range of 0.05 to 5 mmole/100 g (co)polymer. Depending on the nature of the initiator, the dispersion according to the invention may also con^rise one or more conventional phlegmatisers such as are fi-equently mixed with the initiator to make it safe to handle. When such a mixture is used to make the initiator dispersion, the initiator particles or droplets will also contain this phlegmatiser. Preferably, the initiator used is a peroxydicarbonate. For instance, advantageous use can be made of bis(2-ethylhexyl) peroxydicarbonate, a peroxide which is liquid at room temperature. Depending on the conditions, however, it may be that solid peroxydicarbonates are preferred at room temperature, since they permit higher storage and processing temperatures.
By mixing the initiator dispersion with the (co)polymer below the
decomposition temperature is meant that the (co)poIymer is physically mixed with the
initiator dispersion in a manner known to the skilled person, e.g., in mixers with low
or high shearing forces, with the temperature of the initiator at least being selected
below that at which the half life of the initiator is 0.1 hour. Preferably, the
temperature of the (co)polymer will also meet this criterion. At the temperatures
employed the initiator preferably has a half life of one hour or more. Preferably, both
the (co)polymer and the initiator dispersion are kept at a temperature which is lower
than that at which the half life of the initiator is 10 hours. This makes provision for
the fact that the temperature in the mixer will be raised after mixing to enable the
initiator to decompose and react with the (co)polymer before it has melted. Only after
stringent security measures have been taken can the initiator having a temperature as
defined above be added —
to a (co)polymer with a temperature higher than that at which the half life of the initiator is 0.1 hour.
The medium in which the initiator according to the invention is dispersed should be inert towards the initiator and so polar that the initiator will hardly dissolve in it and the polypropylene (co)polymer will be incompatible with it. The initiator preferably is dispersed in water or an alcohol. Most preferable is a dispersion in water. The use of such a medium makes for comparatively easy removal of any remnant after the modification of the (co)polymer if so desired. Furthermore, the use of water or alcohols is attended with far fewer organoleptic and other drawbacks than the use of organic diluents, such as toluene and xylene, which has been common up to now. Depending on the solubility of the initiator, some initiator will dissolve in the polar medium most of the time, but this is not a problem as regards the present utilisation. For greater ease of handling of the initiator dispersion it may be advisable to obtain the initiator dispersion in the solid form. To this end the dispersion can be incorporated into an appropriate carrier material, preferably an inert porous carrier material. Examples of suitable carrier materials are silica, silicates, alumina, and other inorganic oxides, zeolites and other inorganic minerals, clay, whiting, phosphates, sulphates, cellulose products, diatomaceous earth, and porous polymers.
As is well-known to the skilled person, the use of other adjuvants in initiator dispersions may be advisable or even essential in order to ensure the dispersion's chemical and/or physical stability for a sufficiently long period of time. For instance, if the storage temperature of the initiator dispersion is lower than the freezing point of the medium in which the initiator is dispersed, an appropriate freezing point depression agent can be added to counteract freezing. Also, a wide range of substances can be used for altering the
rheology of the formulation. To this end use is generally made of one or more surface-active materials and one or more thickeners. If so desired, other additives may be incorporated into the formulation. As examples of such additives may be mentioned pH buffers, biocides, chemical stabilisers which counteract premature decomposition of the initiator, and antiagers which counteract the particle size growth in the dispersion.
If a freezing, point depression agent is employed, preference is given to the use of one or more aliphatic alkanols having 1 to 4 carbon atoms or an aliphatic glycol having 2 to 4 carbon atoms. Alternatively, however, salts, glycerols and/or higher alkanols or combinations of freezing point depression agents may be used if so desired. The following alcohols can be used to advantage: methanol, ethanol, propanol, ethylene glycols, and propane-1,2-diol.
The surface-active material may be either polymeric or non-polymeric in origin. In addition, the surface-active material may be amphoteric, anionic, cationic or non-ionic. Also, a wide range of thickeners, including protective colloids and associative thickeners, either polymeric or non polymeric by nature and either organic or inorganic in origin, may be used in the formulation in order to obtain a product having acceptable rheology and stability.
The quantity of surface-active material and thickener used in the initiator dispersion is dependent on the materials employed. Preferably, the content of surface-active material in the formulation is more than 1% by weight (% w/w) of the weight of the initiator in the formulation. Preferably, more than 2.5% w/w of surface-active material is present, calculated on the weight of the initiator. The desired quantity of thickener and/or freezing point depression agent to be used is dependent on the desired stability and on the nature and concentration
of other substances in the formulation. Preferably, less than 20% w/w of the freezing point depression agent will be present in the total formulation.
Virtually all surface-active materials which are allowable in the products which can be made using the modified polypropylene (co)polymer according to the invention can be utilised in the initiator dispersions. Although this means that certain cationic surface-active materials can be used, preference is given to anionic and non-ionic surface-active materials. Among the preferred anionic and non-ionic surface-active materials, which may be polymeric or not, are alcohols, alkyl phenols, fatty acids and their derivatives, as well as oil derivatives obtained by alkoxylation, sulphonation, sulphating or phosphonating, but also fatty acid esters of sugars, cellulose derivatives, partially saponified polyvinyl acetates, polyacrylates, appropriate (block) copolymers, and mixtures of these substances.
As suitable thickeners may be mentioned water-soluble polymers, such as gelatine, polyacrylates (cross-linked or not), polycarbohydrates such as the well-known gums xanthan gum and guar gum, as well as derivatives of such polycarbohydrates and cellulose derivatives and mixtures of these substances. Optionally, these thickeners may be mixed with mineral or fibrous additives and associative thickeners. Associative thickeners generally are polymers of the A-B-C structure, with A and C representing water-insoluble groups such as alkyl or polyalkoxy (having more than two carbon atoms per alkoxy unit) groups and with B representing polymeric water-soluble groups such as polyglycol ethers or polyglycerol ethers.
In the process according to the invention the polypropylene (co)polymer usually is modified at a temperature in the range of about 50 to 150°C. Optionally, in order to apply the process according to the invention, use may
oe maae or equipment with a processing temperature above the melting temperature of the (co)polymer, e.g., an extruder. Because of its thermal instability, the initiator will decompose for the most part during the heating-up phase and react with the as yet unmolten polymer. If an initiator suspension is used, it is preferred in this case to carry out the modification at a temperature above the melting temperature of the initiator.
The polypropylene (co)polymer can be modified in a range of different equipment. A sealable reactor in which a solid can be kept in motion in an inert atmosphere, at an adjustable temperature, will usually suffice for this purpose. Preferably, the decomposition of the initiator is carried out under oxygen-free conditions. The reactor used may be, say, a powdered bed reactor or a solids mixer with low or high shearing forces. Alternatively, the modification of the (co)polymer may be carried out in a slurry or suspension of the (co)polymer in water or in an inert medium, such as a hydrocarbon, with the initiator preferably having a greater affinity for the (co)polymer than for the medium, or with the initiator being forcibly contacted with the (co)polymer by evaporation of the medium. The modification of the polypropylene (co)polymer according to this process may take place in the polymerisation reactor if so desired. The modification of the (co)polymer is preferably carried out using an extruder.
The polypropylene (co)polymer obtained using the process according to the invention may be processed into an end product without any further adaptations if so desired. It was found that in that case the modified (co)polymer obtained by the process according to the invention has a substantially better melt strength than the (co)polymer types of increased melt strength known so far, which were obtained, say, by making use of non-dispersed initiators or irradiation sources. Optionally, the modified polypropylene (co)polymer may be purified, modified or moulded, in one or
more process steps, prior to its final processing. Thus there may be further modification using another polymer or monomer in order to enhance the end product's compatibility with other materials. Alternatively, the modified polypropylene (co)polymer may be degraded or, on the contrary, cross-linked slightly, optionally again with the aid of initiators, to increase its processability and/or applicability.
Generally, to achieve the desired end product conventional adjuvants such as antioxidants, UV-stabilisers, lubricants, antiozonants, foaming agents, nucleating agents, fillers and/or antistatic agents are added to the (co)polymer. These adjuvants can be added to the (co)polymer before as well as during or after the modifying step according to the invention. The modified (co)polymer can be processed into the desired end product in all kinds of ways known to the skilled person, with the processing conditions generally being dependent on the material and equipment employed. Preferably, a stabiliser, e.g., one or more antioxidants, is added to the obtained modified polypropylene, in order to render harmless any free radicals still present as well as any radicals which may be formed later from as yet unreacted initiator.
The modified polypropylene (co)polymer obtained by this invention is pre¬eminently suited to be used in the manufacture of foamed products, such as described, int. al., in British Plastics & Rubber, January 1996, pp. 4-5. When the foam to be manufactured is used for packaging purposes, generally use is made of a non-cross-linked polypropylene (co)polymer. However, cross-linked polypropylene (co)polymer may be employed as well, e.g., in applications where dimensional stability, optionally at high temperatures, is of the essence. Especially when polyolefin foams are used in automobiles, e.g., as sound insulating and/or coating material, cross-linked polymers are frequently employed. Also, in these types of applications it is often advisable to increase
the melt strength of the polymer. The process according to the invention can be of use here. In that case the modification of the polypropylene (co)polymer is preferably carried out in the apparatus which is also used for shaping the foamed products.
In addition to the aforementioned advantages, the use of water as dispersion medium is advantageous in that very safe initiator formulations are obtained, incorporated into a carrier material or not, making the initiator easier to handle and use. Furthermore, the use of water as dispersion medium for the initiator may have the additional advantage that any phosphite employed to passify residual catalyst (from the (co)polymerisation process) will be hydrolysed during the modification, which has a beneficial effect on colour stability, as is described in G. Scott, ed.. Developments in Polymer Stabilisation-2, (London: Applied Science Publishers Ltd., 1986), pp. 168-169.
Accordingly, the present invention provides a process for producing poly¬propylene (co)polymer with enhanced melt strength by mixing the initiator with the polypropylene (co)polymer at a temperature below the decomposition temperature and heating the mixture, with most of the initiator decomposing before the polymer has melted and with the fomied radicals reacting with the polymer, wherein the polypropylene (co)polymer is contacted with a dispersion of the initiator in a polar medium, with at least 90% by weight of the initiator particles being smaller than 50 \im and at least 99% by weight of the initiator particles being smaller than 65 jjm.
The invention will be further illustrated with reference to the following, unlimitative, examples.
- Moplen® FLS20 homo-polypropylene ex Himont.
- Fortilene® 9500 K21 polypropylene copolymer ex Solvay.
- HC00A1-B1 homo-polypropylene ex Borealis.
- Profax® PF8i4 high melt strength polypropylene ex Himont.
Initiators, all ex Akzo Nobel:
- Liladox® dicetyl peroxydicarbonate.
- Liladox 33W suspension of Liladox in water (33% w/w).
- Perkadox® 16 bis(4-tert-butylcyclohexyl) peroxydicarbonate.
- Perkadox 16-W40 suspension of 40 wt% Perkadox 16 in water.
- Perkadox 26 dimyristyl peroxydicarbonate.
- Laurox® dilauroyl peroxide.
- Laurox-V\/40-GD4 suspension of 40% w/w Laurox in water.
- Lucidol®-W75 dibenzoyi peroxide containing water (solid).
- Lucidol-W40 suspension of 40 wt% dibenzoyi peroxide in water.
- Trigonox®99 ct-cumyl peroxyneodecanoate. -Trigonox 151 2,4,4-trimethylpentyl-2-peroxyneodecanoate.
- Trigonox 23 tert-butyl peroxyneodecanoate.
- Trigonox 23-W50 emulsion of 50% w/w Trigonox 23 in water.
- Trigonox 25-C75 75% w/w tert-butyl peroxypivalate in isododecane.
- Trigonox 25-W33 44% w/w Trigonox 25-C75 in water
- Sucroester® SE15 non-ionic fatty acid ester of sucrose ex Gattefosse
- Lubrol® N13 non-ionic ethoxylated nonyl phenol ex ICI
- Serdet® DMK 50 anionic sodium lauryl benzene sulphonate ex Servo
- Gohsenol® KP08 non-ionic partially hydrolysed polyvinyl acetate (PVA)
ex Nippon Gohsei
- Unitika® UMR 10m PVA ex Unitika
- Methocel® F50 non-ionic cellulose ether derivative ex Dow Chemical
- Dapral® GE202 copolymer ex Akzo Nobel.
- Dispex® N40 anionic sodium polyacrylate ex Allied Colloids -Arquad® 2.10-50 cationic didecyl dimethyl ammonium chloride ex Akzo
- Amphoteric 16® amphoteric cetyl dimethyl betaine ex Akzo Nobel
- Irganox® 1010 antioxidant ex Ciba Geigy.
- Perkalink® 300 triallyl cyanurate ex Akzo Nobel.
- Silica Ketjensil® SM500 ex Akzo-PQ Silica -Water demineralised.
- All other chemicals were of standard laboratory quality.
Initiator dispersions were prepared by adding the initiator to a polar medium which, optionally, included additives in a concentration of 1.3% w/w. Next, the initiator was dispersed with an UltraTurrax® type S25N-25GM for 30 seconds and with an UltraTurrax type S25N-25F for 2 minutes, both at full power, with the temperature of the solution/dispersion being kept below the decomposition temperature of the initiator. The initiator suspensions were then subjected to an ultrasonic treatment in a Retch ultrasonic bath type UR-275 for 2.5 hours and, optionally, sieved in a 100 f.im sieve.
Unless stated otherwise, the modification of the polypropylene (co)polymer took place at atmospheric pressure, by mixing it with the desired quantity of initiator in a 500-ml or a 1000-ml flask of a rotating "Rotavapor" ex Buchi in a nitrogen atmosphere. After 2 hours of reacting at 70°C and a cooling down period of 30 minutes, with N2 being passed over the reaction mixture, 0.1% w/w of Irganox 1010 was added to the modified (co)polymer.
Unless othenA/ise stated, the melt strength of the polypropylene (co)polymer was determined at 180°C, using a Gottfert Rheotens® and a Gbttfert Rheograph® 2001 (speed 0.5 mm/s, acceleration 24 mm/s^, sample length 70 mm).
The "MFI" or "melt flow index" of the modified or unmodified polymers was determined in a standard manner using a Gottfert Melt Indexer® model MP-D, in accordance with DIN 53735 and ASTM 1238 (230°C, 21.6 N).
The "die-swell," i.e., the degree to which the extrudate swells after it has left the nozzle, was measured on samples made during the MFI measurements by subtracting the nozzle diameter from the average thickness of 10 extruded samples. In the evaluation of the modified polymer the die-swell was usually found to be proportional to the melt strength.
The particle size distribution of initiator dispersions was measured with the aid of light diffraction in a known manner using a Malvern® Particle Sizer.
Comparative Example A
100 g of Moplen FLS20 were modified as specified above, without an initiator being added. The melt strength of the obtained polypropylene was 0.25 N, the MFI was 3.5 g/10min, and the die-swell was 2.7 mm.
Comparative Example B
The experiment of Example A was repeated, without the addition of antioxidant. The melt strength of the obtained polypropylene was 0.26 N, the MFI was 3.5 g/10min, and the die-swell was 2.6 mm.
Comparative Example C
The experiment of Example A was repeated at a temperature of 140°C. The melt strength, the MFI, and the die-swell of the obtained polypropylene corresponded to those obtained in Example A.
Comparative Examples D-F
In an experiment according to Example A an initiator was added to the reactor as well as the polypropylene. In Examples D and E 25% w/w solutions of Trigonox EHP in isododecane and Trigonox 25-C75 in isododecane, respectively, were employed. In Example Fa 10% w/w solution of Perkadox 16 in acetone was used. Use was made of 2 mmoles of initiator per 100 g of polypropylene. The melt strengths of the resulting polymers are listed in Table
Comparative Examples K-P
Experiment G was repeated, except that tlnis time instead of tlie pure Liladox coarse dispersions of it were employed. In the dispersions various surface-active materials were evaluated. Listed in the table below are d90 and d99 characteristic of the particle size distribution (the average particle size of 90 and 99% by weight of initiator particles, respectively), as well as the surface-active material employed and the results.
In an experiment according to Example A there was added to the reactor, in addition to the polypropylene, an aqueous emulsion of 40% w/w of bis(2-ethylhexyl) peroxydicarbonate (Trigonox EHP-W40). The quantity of initiator used per 100 g of polypropylene and the characteristics of the resulting polymer are listed in Table IV. At least 99% w/w of the peroxide droplets in the emulsions was smaller than 50 ^im (d99
In an experiment according to Examples 1-3 a Liladox 33W suspension was used instead of the bis(2-ethylhexyl) peroxydicarbonate emulsion. Again the initiator concentration was varied. The quantity of initiator used and the results are listed in Table V. The d99 of the initiator suspension is smaller than 50 |.im.
Example 6 was repeated, except that this time the 2 meq. of initiator per 100 g of polypropylene were added in various dilutions. The d99 of the suspensions is smaller than 50 jam. The concentration of the dilution used and the results are listed in Table VI.
Surface-active materials were evaluated in experiments 10-16. To this end the process according to experiment 6 was employed, with a number of products representative of the different classes of surface-active materials being incorporated into the Liladox suspension having an initiator concentration in the range of 5 to 33% w/w. The dispersions have a particle size distribution characterised by d90
Experiment 6 was repeated, except that instead of a Liladox suspension various other aqueous initiator formulations were evaluated, all of which had a particle size distribution with d99 Table VIII
Exp initiator Temp. MFI die-swell melt strength
(°C) (g/10min) (mm) (N)
16 Perkadox 16-W40 70 8.7 2.5 0.66
17 Laurox-W40-GD4 95 5.5 2.4 0.41
18 Lucidol-W40 105 5.7 3.5 0.67
19 Laurox-W40-GD1 95 5.5 2.4 0.41
20 Trigonox 23-W50 80 3.5 2.6 0.42
21 Trigonox 99-W40 70 4.1 2.6 0.36
22 Trigonox 151-W50 70 6.6 2.7 0.36
23 Trigonox EHP-W40 70 8.8 3.6 1.02
24 Trigonox 25-W33 70 3.1 2.7 0.43
Comparative example Q and Examples 25-28
In a process according to Example A a polar medium was added to the flask in addition to 100 g of polypropylene (Moplen FLS20) in Example Q to obtain a slurry or suspension of the polymer. After the reaction at 70°C antioxidant was added and the modified polymer was dried in a vacuum oven at 50°C for 18 hours. This experiment was repeated with initiator dispersions with d90 Table IX
Exp Initiator Noot MFI die-swell melt strength
(g/IOmin) (mm) (N)
25 Perkadox 16-W40 1 9.9 3.5 0.60
26 Liladox33W 1 6.2 2.8 0.38
27 Liladox33W 2 3.6 3.8 0.43
28 Liladox33W 3 10.2 2.7 0.46
Q Geen 4 4.3 2.5 0.27
'^otes: 1= medium is 100 g of water
2= medium is 200 g of water and 5 g of CaCl2 3= medium is 100 g of water and 100 g of acetone 4= medium is 200 g of water
Example 29 and Comparative example R
Two parts by weight of Liladox-33W suspension, with d99 smaller than 50 f.im, were incorporated into one part by weight of silica by briefly mixing the components in a mixing drum at room temperature.
The solid peroxide formulation thus obtained was mixed in the same way with the polymer to be modified (HC00A1-B1), in a quantity of 1 mmole of peroxide per 100 g of polymer and 0.1% w/w of Irganox 1010. This mixture was stored for further use in sealed drums for at least 16 hours.
In a Haake® Rheocord System equipped with Rheomex® TW100 screws, which provide intensive mixing, the latter mixture was mixed and heated under the following conditions:
- temperature profile 170/180/180/190C
- screw speed 80 rotations/minute.
During the experiment nitrogen was passed through the mixture in the feed funnel. The resulting modified polymer was cooled in a water bath and then granulated. The same procedure was adopted in comparative example R, except that no peroxide was used. The results are listed in the table below. The melt strength was determined at 200°C.
Exp Initiator quantity MFI die-swell melt strength
(meq./100g) (g/IOmin) (mm) (N)
29 1 1.8 4.8 0.22
R 0 2.6 2.6 0.12
Comparative example S
Also analysed was Profax PF814, a commercially available polypropylene with
improved melt strength probably obtained by subjecting polypropylene to electron
irradiation treatment (see Modern Plastics Int., July 1995, p. 18), to give the
MFI 4.1 g/IOmin.
Die swell 5.4 mm
Melt strength 0.18 N (measured at 180°C)
0.11 N (measured at200°C).
1. A process for producing poly-propylene (co)polymer with enhanced melt strength by mixing the initiator with the polypropylene (co)polymer at a temperature below the decomposition temperature and heating the mixture, with most of the initiator decomposing before the polymer has melted and with the formed radicals reacting with the polymer, wherein the polypropylene (co)polymer is contacted with a dispersion of the initiator in a polar medium, with at least 90% by weight of the initiator particles being smaller than 50 \tm and at least 99% by weight of the initiator particles being smaller than 65 jun.
2. The process as claimed in claim 1, wherein at least 99% by weight of the initiator particles is smaller than 50 pm.
3. The process as claimed in claim 1 or 2, wherein the initiator is dispersed in water.
4. The process as claimed in any one of the preceding claims, wherein polypropylene (co)polymer is mixed with an initiator that has a half life of one hour or less, at a temperature of 1 OO^C.
5. The process as claimed in claim 4, wherein the initiator is a peroxydicarbonate.
6. The process as claimed in claim 5, wherein the peroxydicarbonate is a solid compound at room temperature.
7. The process as claimed in claim 5, wherein the peroxydicarbonate is bis(2-ethylhexyl)peroxydicarbonate.
8. The process as claimed in any one of the preceding claims, wherein the polar medium comprises a freezing point depression agent.
9. The process as claimed in claim 8, wherein the freezing point depression agent is made up of methanol, ethanol, propanol, ethylene glycol, propane-1,2-diol, or a mixture of two or more of these compounds.
10. The process as claimed in any one of the preceding claims, wherein the polar medium in which the initiator is dispersed comprises at least one surface-active material.
11. The process as claimed in claim 10, wherein one or more of the surface-active materials are anionic or non-ionic.
12. The process as claimed in any one of the preceding claims, wherein the polar medium in which the initiator is dispersed contains at least one thickener.
13. The process as claimed in any one of the preceding claims, wherein the initiator concentration in the polar medium is less than 33% by weight.
14. The process as claimed in one or more of the preceding claims, wherein the initiator dispersion is incorporated into a carrier material.
15. The process as claimed in any one of the preceding claims, wherein the polypropylene (co)polymer has a melt flow index (MFI) in the range of 0.5 to 50 g/lOmin (2.16 kg, 230°C).
16.' The process as claimed in any one of the preceding claims, wherein use is made of 0.05 to 5 mmoles of initiator per 100 g of polypropylene (co)polymer.
17. The process as claimed in any one of the preceding claims, wherein during the
decomposition of the initiator oxygen-free conditions are maintained.
18. The process as claimed in any one of the preceding claims, wherein the
modification of the polypropylene (co)polymer is carried out in an extruder.
19. The process as claimed in claimed in any one of the preceding claims, wherein
a stabilizer is added to the obtained modified polypropylene in order to render
harmless any free radicals still present as well as any radicals which may be
formed later from as yet unreacted initiator.
20. The process as claimed in any one of the preceding claims, wherein the
modification of the propylene (co)polymer is carried out in an apparatus which
is also used to make foamed materials.
21. A process for producing a foamed material which includes the step of
enhancing the melt strength of polypropylene according to any one of the
22. A process for producing poly-propylene (co)polymer with enhanced melt
strength substantially as herein described and exemplified.
|Indian Patent Application Number||1921/MAS/1996|
|PG Journal Number||20/2006|
|Date of Filing||31-Oct-1996|
|Name of Patentee||AKZO NOBEL N V|
|Applicant Address||VELPERWEG 76, 6824 BM ARNHEM|
|PCT International Classification Number||C08K8/50|
|PCT International Application Number||N/A|
|PCT International Filing date|