Source: https://patents.google.com/patent/EP0370736A2/en
Timestamp: 2019-02-21 04:08:56
Document Index: 45011780

Matched Legal Cases: ['application No. 44', 'application No. 53', 'application No. 43', 'application No. 54', 'application No. 57', 'application No. 57', 'application No. 56']

EP0370736A2 - Method for manufacture of modified polypropylene compositions - Google Patents
Method for manufacture of modified polypropylene compositions Download PDF
EP0370736A2
EP0370736A2 EP89312020A EP89312020A EP0370736A2 EP 0370736 A2 EP0370736 A2 EP 0370736A2 EP 89312020 A EP89312020 A EP 89312020A EP 89312020 A EP89312020 A EP 89312020A EP 0370736 A2 EP0370736 A2 EP 0370736A2
EP89312020A
EP0370736A3 (en
EP0370736B1 (en
Eric Charles Kelusky
1988-11-23 Priority to GB8827335A priority Critical patent/GB8827335D0/en
1988-11-23 Priority to GB8827335 priority
1989-11-20 Application filed by DuPont Canada Inc filed Critical DuPont Canada Inc
1990-05-30 Publication of EP0370736A2 publication Critical patent/EP0370736A2/en
1990-08-22 Publication of EP0370736A3 publication Critical patent/EP0370736A3/en
1993-06-23 Publication of EP0370736B1 publication Critical patent/EP0370736B1/en
Polypropylene is used in a wide variety of end-uses. However, it is a non-polar polymer and thus tends to exhibit poor or no adhesion to polar materials. A number of proposals have been made to improve the adhesive properties of polypropylene, including the grafting of alpha,beta unsaturated carboxylic acids and anhydrides onto the polypropylene backbone. For example, Japanese patent application No. 44-15422 of F. Ide et al, Mitsubishi Rayon Co., published (kokoku) on 1969 July 09, discloses the grafting of polypropylene in solution. Japanese patent application No. 53-18144 of K. Sadakata et al, Mitsubishi Rayon Co., published (kokoku) on 1968 August 01, discloses the grafting of polypropylene in a slurry state. Japanese patent application No. 43-27421 of F. Ide et al, Mitsubishi Rayon Co., published (kokoku) on 1968 November 26, discloses the grafting of polypropylene in a molten state.
The use of melt grafting techniques has the advantage of being a simple operation, and thus offers the potential of being the most economical method of grafting polypropylene. The grafting of molten propylene polymers is disclosed in U.K. patent 1 519 500 of BASF, published 1978 July 26. However, Japanese patent applications No. 57-65747 of Y. Wachi et al and No. 57-65746 of M. Fujiyama et al (Tokuyama Soda K.K.), both published 1982 April 21, disclose that the grafted polypropylene obtained from a melt grafting process contains residual unreacted monomer. This residual monomer tends to cause lack of adhesion and the formation of blisters e.g. in moulding or other forming operations.
Methods for the removal of the residual monomer are known, including removal of the unreacted monomer using a solvent-precipitation technique and by agitation with a good solvent e. g. xylene, under conditions that do not dissolve the polymer, the latter being disclosed in Japanese patent application No. 54-99193 of Y. Nakajima et al, published 1979 August 04. European patent application 0 202 921 of T. Inoue et al, published 1986 November 26, which corresponds to U.S Patent 4 698 395, issued 1987 October 06, discloses treatment of grafted polyolefins by adding an aqueous solution of an alkali metal hydroxide to grafted polymer dissolved in organic solvent.
However, processes involving the use of solvent, often large amounts of solvent, add additional steps to the manufacture of grafted polypropylene including steps for the removal of the solvent from the grafted polymer until a commercially-acceptable low level of residual solvent is obtained in the polymer. The aforementioned application of Y. Wachi et al discloses two methods for the reduction in the amount of monomer viz. heating the grafted composition to a temperature of 60°C or higher, and blending the grafted polymer with an ethylene/alpha-olefin copolymer and then heating the resultant mixture to a temperature of 60°C or higher. Compositions of grafted alpha-olefin polymer containing metal carbonates are disclosed in Japanese patent application No. 57 144 731 of Mitsui Polychemicals, published 1982 September 07. Addition of metal compounds e.g. calcium, magnesium or aluminum compounds, to grafted polyolefins is disclosed in Japanese patent application No. 57 080 046 of Toyo Ink Manufacturing KK, published 1982 May 20, and in Canadian Patent No. 1 009 787 of K.Shirayama et al, which issued 1977 May 03. Japanese patent application No. 56 118 411 of Mitsubishi Petrochemical KK, published 1981 September 17, discloses treatment of grafted polyolefin with hot water or hot air at a temperature between the softening point of the grafted polymer and a temperature 25°C lower than the softening point to improve the adhesion of the grafted polymer.
(a) contacting molten grafted polypropylene in melt processing apparatus with a minor amount of an aqueous solution of an alkaline material, said melt-grafted polypropylene having been formed in melt processing apparatus by the grafting of polypropylene with 0.01 to 5% by weight of at least one of alpha,beta unsaturated carboxylic acids and alpha,beta-­unsaturated carboxylic anhydrides and 0.01 to 2% by weight of an organic peroxide at a temperature above the melting point of the polypropylene;
The melt processing apparatus used in the method of the present invention preferably has a feed section, a section in which the grafted polymer may be contacted with a minor amount of the aqueous solution of alkaline material and a die or other device through which the grafted and treated polymer is discharged from the melt processing apparatus; if melt-grafted polypropylene is fed to the extruder, it is not necessary to have a section in the melt processing apparatus in which a grafting reaction may occur. The section in which the polymer is contacted with the aqueous solution would have an inlet port and an outlet port; the outlet port may be located upstream or downstream of the inlet port, or both. Melt processing apparatus having such ports is known, examples of which are extruders obtainable from Welding Engineers Inc. of Blue Bell, Pennsylvania, U.S.A., an embodiment of which is described in U.S. Patent No. 3 742 093 of R.H. Skidmore, which issued 1973 June 26. Techniques for obtaining flow of solutions counter current to the extrusion of polymer in extruders is described in that patent. In preferred embodiments of the present invention, the melt processing apparatus is a twin screw extruder that is equipped with non-intermeshing screws. The use of such apparatus in the grafting of monomers onto polypropylene is described in greater detail in the copending patent application of E.C Kelusky (Case DC-0238) filed on the same day as this application.
The organic peroxide, which as used herein includes hydroperoxides, may for example be a bis(tert. alkyl peroxy alkyl) benzene, dicumyl peroxide or acetylenic diperoxy compound. Other organic peroxides are known to those skilled in the art, including t-butyl hydroperoxide and di-t-butyl peroxide. The peroxides used in the method of the present invention preferably have a half-life at 150°C of from about one minute to about 120 minutes. A preferred organic peroxide is 2,5-dimethyl-2,5-bis-­(tert. butyl peroxyisopropyl) benzene which is available under the trademark Vulcup from Hercules Inc. Other preferred organic peroxides are 2,5-dimethyl-2,5-di-(tert. butyl peroxy) hexane and 2,5-dimethyl-2,5-di-(tert. butyl peroxy) hexyne-3, which are available under the trademarks Lupersol 101 and Lupersol 130, respectively, from Lucidol Division of Pennwalt Corporation.
In embodiments of the method of the invention, additional polymers and/or stabilizing agents, pigments or the like are added to the grafted polymer subsequent to the treatment with alkaline material but prior to extrusion of the grafted polymer from the melt processing apparatus. For example, additional polypropylene may be added, especially to decrease the melt index of the grafted polymer composition. Toughening agents, for example, elastomers may be added e.g. in amounts of up to about 25% by weight of the composition, but any such toughening agents should be highly dispersed in the resultant composition. Furthermore, metal oxides or hydroxides e.g. calcium oxide, may be added, for example in amounts of up to 10% by weight, to further improve the adhesive characteristics of the resultant compositions.
The extruder used in this example was a 2.0 cm non-intermeshing, counter-rotating twin screw extruder. The extruder had a barrel with a ratio of length:diameter (L/D) of 60:1, and was equipped with vents ports at L/D positions (as measured from the inlet) of 33:1 and 45:1 and a liquid (solvent) injection port between the vents, at an L/D of 40:1. The extruder was operated at 350 rpm and a barrel temperature of 170°C; the final melt temperature of the polymer was 210°C. The polymer was extruded from the extruder in the form of a strand, which was fed to a water bath and pelletized.
A film (0.1 mm) of the grafted polymer, formed by pressing pellets between sheets of Teflon® fluoropolymer, was placed between sheets of aluminum (0.2 mm) that had been pre-cleaned with carbon tetrachloride. The resultant sandwich was heated at 220°C for 10 minutes and then pressed (70 kg/cm²) for one minute at 220°C. The laminate obtained was cut into a number of strips measuring 200 x 25 mm, which were subjected to a 180° peel test, at 23°C and 50% relative humidity, using an Instron* testing apparatus.
The adhesion results obtained are reported in Table I. TABLE I
Run No. Vacuum (mm) Solvent Grafted Monomer (%)* Residual Monomer (%)** Adhesion (g/cm)
1 0 - 0.36 735 0
2 100 - 0.31 166 500
3 100 water 0.26 147 485
4 100 0.1% NaOH 0.29 263 555
5 100 1.0% NaOH 0.27 163 735
6 100 acetone 0.25 65 520
* obtained by infrared analysis
** obtained by liquid chromatography
The results show that the application of a vacuum and contacting with a solution improves the adhesive characteristics of the resultant polymer. The runs of the invention, Runs 4 and 5 in which the grafted polymer was washed with sodium hydroxide, gave the best results, especially Run 5 which used the higher concentration of sodium hydroxide.
The extruder used in this example was a counter rotating, non-intermeshing twin screw extruder having a 2.0 cm screw and an L/D of 72:1. Vents were located in the extruder at L/D's of 51:1 and 63:1, and an injection port was located at 58:1. The temperature of the polymer was 170°C and the extruder was operated at 400 rpm.
(b) 1 part of dicumyl peroxide (40% on clay); and
(c) 1 part of crystalline maleic anhydride.
The results obtained are given in Table II. TABLE II
Run No. Vacuum (mm) Solvent Grafted Monomer (%) Residual Monomer (%) Adhesion (g/cm)
7 50 - 0.37 658 <180
8 50 0.5% NaOH 0.27 88 355
9 50 2.5% NaOH 0.27 44 625
In another peel test, a 0.073 mm thick sample of grafted polymer was pressed to a pre-cleaned aluminum sheet using a heat sealer, at 210°C and a pressure of 3.6 kg/cm² for 5 seconds. The peel strengths obtained were as follows: for the grafted polymer of Run 7, 0 g/cm; for the grafted polymer of Run 8, 445 g/cm; and for the grafted polymer of Run 9, >895 g/cm which was the yield strength of the sample of polymer. This test also illustrates the improvement obtained with the present invention.
Further details and the results obtained are given in Table III. TABLE III
Run No. Vacuum (mm) Solvent Adhesion (g/cm)
10 - - 0*
11 50 2.5% NaOH 2680
12 50 5.0% NaOH 1910
13 50 7.5% NaOH 2070
14 50 10.0% NaOH 2790
* without treatment with sodium hydroxide solution
1. A method for the treatment of melt-grafted polypropylene formed by the grafting of alpha,beta-unsaturated acids and anhydrides onto polypropylene, said method comprising the steps of:
(a) contacting molten grafted polypropylene in melt processing apparatus with a minor amount of an aqueous solution of an alkaline material, said melt-grafted polypropylene having been formed in melt processing apparatus by the grafting of polypropylene with 0.01 to 5% by weight of at least one of alpha,beta unsaturated carboxylic acids and alpha, beta-­unsaturated carboxylic anhydrides and 0.01 to 2% by weight of an organic peroxide at a temperature above the melting point of the polypropylene;
2. A method for the grafting of alpha,beta-unsaturated acids and anhydrides onto polypropylene comprising the steps of:
(b) contacting the resultant molten grafted polypropylene in melt processing apparatus with a minor amount of an aqueous solution of an alkaline material;
3. The method of Claim 1 or Claim 2 in which the polypropylene is grafted with at least one of maleic acid and maleic anhydride.
4. The method of any one of Claims 1-3 in which the grafted polypropylene is treated with an aqueous solution of at least one of a hydroxide, carbonate and bicarbonate of an alkali metal.
5. The method of Claim 4 in which the grafted polypropylene is treated with an aqueous solution of sodium hydroxide.
6. The method of any one of Claims 1-5 in which the amount of organic peroxide is in the range of 0.05 to 0.5% by weight.
7. The method of any one of Claims 1-6 in which the polypropylene is grafted with maleic anhydride and the amount of maleic anhydride is in the range of 0.1 to 0.4% by weight.
8. The method of any one of Claims 1-7 in which the grafted polypropylene is treated with an aqueous solution of 0.05-15% by weight of sodium hydroxide.
9. The method of Claim 8 in which the grafted polypropylene is treated with an aqueous solution of 0.1-10% by weight of sodium hydroxide.
10. The method of any one of Claims 1-9 in which the rate at which the aqueous solution is contacted with the grafted polypropylene is 1-15%, by weight, of the rate of extrusion of the grafted polymer.
11. The method of Claim 10 in which the rate at which the aqueous solution is contacted with the grafted polypropylene is 3-7%, by weight, of the rate of extrusion of the grafted polymer.
12. The method of any one of Claims 1-11 in which the melt processing apparatus is a twin screw extruder with non-intermeshing counter rotating screws.
13. The method of any one of Claims 1-12 in which the polypropylene is a homopolymer of propylene.
14. The method of any one of Claims 1-12 in which the polypropylene is selected from the group consisting of block copolymers of ethylene and propylene containing less than 25% by weight of eithylene and random copolymers of ethylene and propylene containing less than 8% by weight of ethylene.
EP89312020A 1988-11-23 1989-11-20 Method for manufacture of modified polypropylene compositions Expired - Lifetime EP0370736B1 (en)
GB8827335A GB8827335D0 (en) 1988-11-23 1988-11-23 Method for manufacture of modified polypropylene compositions
GB8827335 1988-11-23
EP0370736A2 true EP0370736A2 (en) 1990-05-30
EP0370736A3 EP0370736A3 (en) 1990-08-22
EP0370736B1 EP0370736B1 (en) 1993-06-23
ID=10647303
EP89312020A Expired - Lifetime EP0370736B1 (en) 1988-11-23 1989-11-20 Method for manufacture of modified polypropylene compositions
US (1) US5137975A (en)
EP (1) EP0370736B1 (en)
CA (1) CA2003614C (en)
DE (2) DE68907320D1 (en)
GB (1) GB8827335D0 (en)
WO1996039448A1 (en) * 1995-06-06 1996-12-12 Alliedsignal Inc. Process for producing ionomers of low molecular weight acid copolymers
WO2000066641A1 (en) * 1999-04-29 2000-11-09 Solvay (Societe Anonyme) Polyolefins and method for the production thereof
US6265455B1 (en) 1998-02-10 2001-07-24 Montell North America Inc. Foamed crystalline ionomer polyolefins
WO2008044121A1 (en) 2006-10-11 2008-04-17 Universidad De Chile Compatibilizers for producing nanocomposites, microcomposites and polymer blends and process for obtaining them.
US5344886A (en) * 1993-05-14 1994-09-06 Quantum Chemical Corporation Process for making graft propylene polymers
US6187870B1 (en) * 1993-12-16 2001-02-13 Eastman Chemical Company Apparatus and process for the production of low molecular weight grafted polyolefins
AT415444T (en) * 2002-02-22 2008-12-15 Dow Global Technologies Inc Small particle aggregates containing thermoplastic foams
US6855771B2 (en) * 2002-10-31 2005-02-15 Grant Doney Process for making block polymers or copolymers from isotactic polypropylene
KR100816411B1 (en) * 2003-02-14 2008-03-26 미쯔비시 가가꾸 가부시끼가이샤 Polymer composite material and process for producing the same
GB1519500A (en) * 1974-11-23 1978-07-26 Basf Ag Manufacture of graft polymers
JPS5836014B2 (en) * 1980-10-09 1983-08-06 Tokuyama Soda Kk
JPS5856579B2 (en) * 1980-10-09 1983-12-15 Tokuyama Soda Kk
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1988-11-23 GB GB8827335A patent/GB8827335D0/en active Pending
1989-11-17 US US07/437,801 patent/US5137975A/en not_active Expired - Fee Related
1989-11-20 DE DE8989312020A patent/DE68907320D1/en not_active Expired - Fee Related
1989-11-20 EP EP89312020A patent/EP0370736B1/en not_active Expired - Lifetime
1989-11-20 DE DE89312020T patent/DE68907320T2/en not_active Expired - Lifetime
1989-11-22 CA CA002003614A patent/CA2003614C/en not_active Expired - Fee Related
EP0659784A3 (en) * 1993-12-27 1995-08-16 Solvay Continuous process of grafting a polyolefin, and the graft polyolefins obtained by this process.
AU779727B2 (en) * 1999-04-29 2005-02-10 Solvay (Societe Anonyme) Polyolefins and method for the production thereof
CN101583639B (en) 2006-10-11 2013-02-20 智利大学 Compatibilizers for producing nanocomposites, microcomposites and polymer blends and process for obtaining them.
US8664308B2 (en) 2006-10-11 2014-03-04 Universidad De Chile Compatibilizers for producing nanocomposites, microcomposites and polymer blends and process for obtaining them
EP0370736A3 (en) 1990-08-22
EP0370736B1 (en) 1993-06-23
US5137975A (en) 1992-08-11
GB8827335D0 (en) 1988-12-29
CA2003614A1 (en) 1990-05-23
DE68907320T2 (en) 1993-12-23
CA2003614C (en) 1999-07-13
DE68907320D1 (en) 1993-07-29
Ref document number: 68907320
1993-08-12 ITF It: translation for a ep patent filed
Owner name: DATA SOLLECITO LETT. INC.:13/02/96;ING. C. GREGORJ