WO2010017553A1 - Triallyl phosphate enabled grafting of compatible monomers to chain scissionable polyolefins - Google Patents
Triallyl phosphate enabled grafting of compatible monomers to chain scissionable polyolefins Download PDFInfo
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- WO2010017553A1 WO2010017553A1 PCT/US2009/053294 US2009053294W WO2010017553A1 WO 2010017553 A1 WO2010017553 A1 WO 2010017553A1 US 2009053294 W US2009053294 W US 2009053294W WO 2010017553 A1 WO2010017553 A1 WO 2010017553A1
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- free
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- weight percent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
Definitions
- Free-radical initiated grafting of maleic anhydride to polyolefins is practiced commercially, typically with peroxides. When propylene polymers are used, chain scission and grafting are competitive reactions. Unfortunately, chain scission is dominant and decreases the molecular weight and viscosity of the grafted resin.
- Co-grafting reagents containing two or more terminal carbon-carbon double bonds or triple bonds can be combined with free -radical generation to mitigate the loss in melt viscosity of polypropylene by coupling of polymer chains.
- An example of such a co-grafting reagent is triallyl trimesate.
- the present invention provides a free-radical reactive polymer composition
- a free-radical reactive polymer composition comprising (a) a free-radical, chain scissionable polyolefin, (b) a graftable, compatible monomer, and (c) a triallyl phosphate coagent.
- the components of the invented composition can be present in a variety of combinations.
- the composition can further comprise a free-radical inducing species used to make a crosslinked copolymer from the composition. Additionally, the composition can further comprise antioxidants and other polymers.
- Polypropylene (PP) is an example of a free-radical, chain scissionable polyolefin suitable for use in the present invention.
- propylene polymers include propylene homopolymers and copolymers of propylene with ethylene or another unsaturated comonomer. Copolymers also include terpolymers, tetrapolymers, etc.
- the polypropylene copolymers comprise units derived from propylene in an amount of at least about 60 weight percent.
- the propylene monomer is at least about 70 weight percent of the copolymer, more preferably at least about 80 weight percent.
- the resulting grafting level is preferably greater than about 0.5 weight percent monomer. More preferably, the grafting level is greater than about 1.0 weight percent monomer. Most preferably, the grafting level is greater than about 1.5 weight percent monomer.
- the triallyl phosphate coagent is present in an amount between about 0.05 weight percent to about 20 weight percent; more preferably, between about 0.1 weight percent to about 10 weight percent; even more preferably, between about 0.2 weight percent to about 10 weight percent; and most preferably, between about 0.3 to about 5 weight percent.
- Free-radicals can be produced for use in the present invention in a variety of ways known to persons skilled in the art.
- Useful free-radical inducing species include organic peroxides, Azo free-radical initiators, and bicumene.
- the free- radical inducing species is an organic peroxide.
- oxygen-rich environments can initiate useful free-radicals.
- Preferable organic peroxides include dicumyl peroxide and Vulcup R. The organic peroxide can be added via direct injection.
- the peroxide is present in the reactive composition in an amount of about 0.005 weight percent to about 20 weight percent, preferably about 0.01 weight percent to about 10 weight percent, more preferably about 0.02 weight percent to about 10 weight percent, and most preferably about 0.03 weight percent to about 5 weight percent.
- the crosslinked copolymer has a gel content, as measured by extraction in trichlorobenzene or decalin, of less than about 30 weight percent; more preferably, less than about 15 weight percent, and even more preferably, less than about 10 weight percent.
- FIG. 1 is a set of three graphs, illustrating dynamic rheology data for unmodified polypropylene and its maleic anhydride/triallyl trimesate co-grafted derivatives with the maleic anhydride at 2 weight percent and the temperature at 180 degrees Celsius.
- FIG. 2 is a set of three graphs, illustrating dynamic rheology data for unmodified polypropylene and its maleic anhydride/triallyl phosphate co-grafted derivatives with the maleic anhydride at 2 weight percent, dicumyl peroxide at 0.2 weight percent, and the temperature at 180 degrees Celsius.
- FIG. 3 is a graph of creep compliance data for unmodified polypropylene and its maleic anhydride/triallyl phosphate co-grafted derivative with the maleic anhydride at 2 weight percent, the triallyl phosphate at 3 weight percent, dicumyl peroxide at 0.2 weight percent, and the temperature at 180 degrees Celsius.
- the filled triangle and diamond indicate when the stress of 10 Pa is applied to the composition.
- the unfilled triangle and diamond indicate when the composition is under recovery and the stress is no longer being applied to the composition.
- DCP Dicumyl peroxide
- MAn Maleic anhydride
- MAn 99%, Sigma- Aldrich
- TAM Triallyl trimesate
- TCI America, Portland, Oregon, USA triallyl phosphate
- PP powder 40 g was coated with an acetone solution containing the desired amount of DCP, coagent and MAn. Acetone was removed by evaporation. The mixture was charged to a Haake Polylab R600 internal batch mixer and processed at a set temperature of 190 degrees Celsius for 10 minutes at 60 rpm.
- Oscillatory elastic (G') and loss (G") moduli were measured under a nitrogen atmosphere using a Reologica ViscoTech controlled stress rheometer equipped with 20 mm diameter parallel plates. The instrument was operated at 180 degrees Celsius with a gap of 1.5 mm over frequencies 0.007-30 Hz. Stress sweeps ensured that all data were acquired within the linear viscoelastic regime. Creep experiments were also conducted using the aforementioned rheometer at 180 degrees Celsius with a stress of 10 Pa for 1000 seconds. The data were analyzed to calculate zero-shear viscosity and recoverable compliance (but only for cases where steady-state had been attained).
- compatibility assessments are based on average graft yields.
- the data presented in Table 1 show that the presence of TAM or TAP had no significant effect on the amount of MAn grafted to PP and that substantial TAM conversions can be achieved in the presence of MAn.
- TAM Triallyl trimesate
- TAP Triallyl phosphate
- Example 7 0.1 2.0 0.7 0.9 N/A 0 700
- Example 8 0.2 2.0 0.7 1.3 N/A 0 730
- FIG. 1 also shows that maleating PP in the absence of coagent produced a reduction in melt viscosity, and altered shear-thinning characteristics in a manner that is generally associated with a narrowing of the molecular weight distribution.
- the addition of about 1 weight percent to about 2 weight percent of TAM to the maleation process reduced viscosity losses, but this coagent could not maintain the starting material properties.
- a closer examination of the dynamic storage modulus (G') at low frequencies reveals a shift away from terminal flow behavior where G' generally scales with ⁇ .
Abstract
The present invention is a free-radical reactive polymer composition made from or containing (a) a free-radical, chain scissionable polyolefin, (b) a graftable, compatible monomer, and (c) a triallyl phosphate coagent. By teaching the use of triallyl phosphate coagent as the selected coagent, this invention mitigates the loss in melt viscosity of chain scissionable polyolefins during free-radical-initiated grafting of a comonomer onto the polyolefin.
Description
TRIALLYL PHOSPHATE ENABLED GRAFTING OF COMPATIBLE MONOMERS TO CHAIN SCISSIONABLE POLYOLEFINS
Free-radical initiated grafting of maleic anhydride to polyolefins is practiced commercially, typically with peroxides. When propylene polymers are used, chain scission and grafting are competitive reactions. Unfortunately, chain scission is dominant and decreases the molecular weight and viscosity of the grafted resin.
Co-grafting reagents containing two or more terminal carbon-carbon double bonds or triple bonds can be combined with free -radical generation to mitigate the loss in melt viscosity of polypropylene by coupling of polymer chains. An example of such a co-grafting reagent is triallyl trimesate.
It is desirable to identify other coagents that are more effective than the previously known coagents.
The present invention provides a free-radical reactive polymer composition comprising (a) a free-radical, chain scissionable polyolefin, (b) a graftable, compatible monomer, and (c) a triallyl phosphate coagent. It is contemplated that the components of the invented composition can be present in a variety of combinations. The composition can further comprise a free-radical inducing species used to make a crosslinked copolymer from the composition. Additionally, the composition can further comprise antioxidants and other polymers.
Polypropylene (PP) is an example of a free-radical, chain scissionable polyolefin suitable for use in the present invention. Examples of propylene polymers include propylene homopolymers and copolymers of propylene with ethylene or another unsaturated comonomer. Copolymers also include terpolymers, tetrapolymers, etc. Typically, the polypropylene copolymers comprise units derived from propylene in an amount of at least about 60 weight percent. Preferably, the propylene monomer is at least about 70 weight percent of the copolymer, more preferably at least about 80 weight percent.
An example of useful, graftable, compatible monomers is maleic anhydride. The resulting grafting level is preferably greater than about 0.5 weight percent monomer. More preferably, the grafting level is greater than about 1.0 weight percent monomer. Most preferably, the grafting level is greater than about 1.5 weight percent monomer.
Preferably, the triallyl phosphate coagent is present in an amount between about 0.05 weight percent to about 20 weight percent; more preferably, between about 0.1 weight percent to about 10 weight percent; even more preferably, between about 0.2 weight percent to about 10 weight percent; and most preferably, between about 0.3 to about 5 weight percent.
Free-radicals can be produced for use in the present invention in a variety of ways known to persons skilled in the art. Useful free-radical inducing species include organic peroxides, Azo free-radical initiators, and bicumene. Preferably, the free- radical inducing species is an organic peroxide. Also, oxygen-rich environments can initiate useful free-radicals. Preferable organic peroxides include dicumyl peroxide and Vulcup R. The organic peroxide can be added via direct injection. When a peroxide is used to generate free-radicals, the peroxide is present in the reactive composition in an amount of about 0.005 weight percent to about 20 weight percent, preferably about 0.01 weight percent to about 10 weight percent, more preferably about 0.02 weight percent to about 10 weight percent, and most preferably about 0.03 weight percent to about 5 weight percent.
Other methods of generating free-radicals include electron-beam and gamma radiation.
The crosslinked copolymer has a gel content, as measured by extraction in trichlorobenzene or decalin, of less than about 30 weight percent; more preferably, less than about 15 weight percent, and even more preferably, less than about 10 weight percent.
FIG. 1 is a set of three graphs, illustrating dynamic rheology data for unmodified polypropylene and its maleic anhydride/triallyl trimesate co-grafted derivatives with the maleic anhydride at 2 weight percent and the temperature at 180 degrees Celsius.
FIG. 2 is a set of three graphs, illustrating dynamic rheology data for unmodified polypropylene and its maleic anhydride/triallyl phosphate co-grafted derivatives with the maleic anhydride at 2 weight percent, dicumyl peroxide at 0.2 weight percent, and the temperature at 180 degrees Celsius.
FIG. 3 is a graph of creep compliance data for unmodified polypropylene and its maleic anhydride/triallyl phosphate co-grafted derivative with the maleic anhydride at 2 weight percent, the triallyl phosphate at 3 weight percent, dicumyl peroxide at 0.2 weight percent, and the temperature at 180 degrees Celsius. The filled
triangle and diamond indicate when the stress of 10 Pa is applied to the composition. The unfilled triangle and diamond indicate when the composition is under recovery and the stress is no longer being applied to the composition.
EXAMPLE
The following non-limiting examples illustrate the invention.
Dicumyl peroxide (DCP, 98%, Sigma Aldrich, Oakville, Ontario, Canada), maleic anhydride (MAn, 99%, Sigma- Aldrich), triallyl trimesate (TAM, Monomer Polymer Inc., Feasterville, Pennsylvania, USA), and triallyl phosphate (TAP, 98%, TCI America, Portland, Oregon, USA) were used as received. An additive-free (unstabilized), powder grade of isotactic polypropylene homopolymer (i-PP, Mn= 70,000, polydispersity = 4.9) was used as supplied by The Dow Chemical Company, Midland, Michigan, USA.
For i-PP graft modification, PP powder (40 g) was coated with an acetone solution containing the desired amount of DCP, coagent and MAn. Acetone was removed by evaporation. The mixture was charged to a Haake Polylab R600 internal batch mixer and processed at a set temperature of 190 degrees Celsius for 10 minutes at 60 rpm.
Material for FT-IR and DSC analysis was purified by dissolving 1 g in boiling xylenes (20 ml), precipitating from acetone (100 ml), and then drying under vacuum. Bound maleic anhydride, triallyl trimesate contents were determined from the area derived from the 1818-1755 cm"1 and 1670-1751 cm"1 resonances, respectively, relative to a 422-496 cm"1 internal standard region originating from the resin. Comparison of the ratio of these areas to calibration mixtures provided an estimate of the concentrations of the grafted moieties.
Oscillatory elastic (G') and loss (G") moduli were measured under a nitrogen atmosphere using a Reologica ViscoTech controlled stress rheometer equipped with 20 mm diameter parallel plates. The instrument was operated at 180 degrees Celsius with a gap of 1.5 mm over frequencies 0.007-30 Hz. Stress sweeps ensured that all data were acquired within the linear viscoelastic regime. Creep experiments were also conducted using the aforementioned rheometer at 180 degrees Celsius with a stress of 10 Pa for 1000 seconds. The data were analyzed to calculate zero-shear viscosity and recoverable compliance (but only for cases where steady-state had been attained).
The functionalization of PP by radical-mediated addition of the polyolefin to MAn has been studied extensively, and the accompanying losses of melt viscosity that arise from macroradical fragmentation are well known. Table 1 summarizes baseline information, in which dicumyl peroxide (DCP) is used to initiate MAn grafting in the absence of coagent. The required peroxide loadings are much greater than those demanded by ethylene -rich polymer modifications, despite the fact that the exemplified PP homopolymer contained no stabilizing agents. Nevertheless, MAn conversions ranging from 55 to 75% were readily achieved.
In their simplest form, compatibility assessments are based on average graft yields. The data presented in Table 1 show that the presence of TAM or TAP had no significant effect on the amount of MAn grafted to PP and that substantial TAM conversions can be achieved in the presence of MAn.
Microstructure differences arising from radical-mediated polyolefin modifications are reflected by melt-state rheological properties. As also reported in Table 1, zero-shear viscosities (η0) derived from creep measurements and oscillatory dynamic properties (η*, G', tanδ) permitted assessment of changes in chain length distributions and branching architectures. FIG. 1 shows that the starting homopolymer (Mn = 70,000, polydispersity = 4.9) demonstrated rheological properties that were consistent with its linear structure. When extrapolated to zero frequency, the complex viscosity (η*) agreed with the zero-shear viscosity (ηo), and the storage modulus (G') showed none of the low-frequency complexity commonly reported for materials containing long-chain branching.
Table 1: PP Co-grafting Yields3
Ex. No. Reagent Loadings Graft-modified Product
[DCP] [MAn] [Coagent] Bound Bound Gel ηo
(wt%) (wt%) (wt%) MAn Coagent Content (Pa-s)b
(wt%) (wt%) (wt%)
Comparative Examples: no coagent
Comp. Ex. 1 ... ... ... ... ... 0 11,130
Comp. Ex. 2 0.1 2.0 0.0 1.1 ... 0 350
Comp. Ex. 3 0.2 2.0 0.0 1.5 ... 0 170
Comparative Examples: Triallyl trimesate (TAM)
Comp. Ex. 4 0.1 2.0 1.0 1.2 0.4 0 540
Comp. Ex. 5 0.2 2.0 1.0 1.4 0.5 0 290
Comp. Ex. 6 0.2 2.0 2.0 1.6 0.7 0 298
Examples: Triallyl phosphate (TAP)
Example 7 0.1 2.0 0.7 0.9 N/A 0 700
Example 8 0.2 2.0 0.7 1.3 N/A 0 730
Example 9 0.2 2.0 1.4 1.4 N/A 0 1486
Example 10 0.2 2.0 3.0 1.5 N/A 6 N/A a. T=190 degrees Celsius; 10 minutes; b. From creep analysis at T=180 degrees Celsius, σ=10 Pa.
FIG. 1 also shows that maleating PP in the absence of coagent produced a reduction in melt viscosity, and altered shear-thinning characteristics in a manner that is generally associated with a narrowing of the molecular weight distribution. The addition of about 1 weight percent to about 2 weight percent of TAM to the maleation process reduced viscosity losses, but this coagent could not maintain the starting material properties. A closer examination of the dynamic storage modulus (G') at low frequencies reveals a shift away from terminal flow behavior where G' generally scales with ω .
When used under equivalent reaction conditions, TAP provides a higher crosslink density than does its aromatic ester analogue, TAM. The data illustrated in FIG. 2 demonstrate the use of this higher reactivity to control product viscosities. The co-grafting of 3 weight percent TAP produced a maleated derivative whose η* versus ω profile resembled, at least superficially, that of the starting material. However, a closer examination reveals important differences, particularly at low oscillation frequencies where the branching effects are most acute. The co-grafted material lacks a Newtonian plateau as a result of a storage modulus which shows no signs of diminishing toward a standard terminal flow condition. Indeed, the phase angle declined continuously in this frequency region.
As FIG. 3 illustrates, a creep compliance test did not reach steady-state within 1000 seconds and recovered a substantial fraction of the final compliance after releasing the applied stress. Although ηo could not be determined from the creep compliance test for the derivative co-grafted with TAP at a concentration of 3 weight percent, the data in Figure 2 indicate that ηo would have been substantially greater than that of the unmodified PP. Without being bound to any theory, it is believed that the very high degree of shear-thinning observed with this composition is likely to reflect comparatively higher melt strength of the TAP co-grafted derivative as well as good processability during extrusion or other high-shear mixing processes.
Claims
1. A free-radical reactive polymer composition comprising:
(a) a free-radical, chain scissionable polyolefin,
(b) a graftable, compatible monomer, and
(c) a triallyl phosphate coagent.
2. The crosslinked copolymer of Claim 1 further comprising a free-radical inducing species.
3. The crosslinked copolymer of Claim 1 wherein the free-radical, chain scissionable polyolefin is a polypropylene.
4. The crosslinked copolymer of Claim 1 wherein
(a) the free-radical, chain scissionable polyolefin is a polypropylene,
(b) the graftable, compatible monomer is maleic anhydride, and
(c) the triallyl phosphate coagent is present between about 0.3 to about 5 weight percent.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2018160403A1 (en) | 2017-02-28 | 2018-09-07 | Dow Global Technologies Llc | Ethylene-alpha-olefin copolymer-triallyl phosphate composition |
WO2018160402A1 (en) | 2017-02-28 | 2018-09-07 | Dow Global Technologies Llc | Ethylene-alpha-olefin copolymer-triallyl phosphate composition |
CN109575190A (en) * | 2018-10-22 | 2019-04-05 | 佳易容相容剂江苏有限公司 | A kind of phosphorous polyethylene maleic anhydride graft copolymer and preparation method thereof with cooperative flame retardant effect |
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US20050147824A1 (en) * | 2003-12-30 | 2005-07-07 | Kimberly-Clark Worldwide, Inc. | Surface initiated graft polymerization |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018160403A1 (en) | 2017-02-28 | 2018-09-07 | Dow Global Technologies Llc | Ethylene-alpha-olefin copolymer-triallyl phosphate composition |
WO2018160402A1 (en) | 2017-02-28 | 2018-09-07 | Dow Global Technologies Llc | Ethylene-alpha-olefin copolymer-triallyl phosphate composition |
CN110248994A (en) * | 2017-02-28 | 2019-09-17 | 陶氏环球技术有限责任公司 | Ethene-alpha-olefin copolymer-triallyl phosphate composition |
CN110312757A (en) * | 2017-02-28 | 2019-10-08 | 陶氏环球技术有限责任公司 | Ethene-alpha-olefin copolymer-triallyl phosphate composition |
US10913872B2 (en) | 2017-02-28 | 2021-02-09 | Dow Global Technologies Llc | Ethylene-alpha-olefin copolymer-triallyl phosphate composition |
US11299613B2 (en) | 2017-02-28 | 2022-04-12 | Dow Global Technologies Llc | Ethylene-alpha-olefin copolymer-triallyl phosphate composition |
CN110248994B (en) * | 2017-02-28 | 2022-09-27 | 陶氏环球技术有限责任公司 | Ethylene-alpha-olefin copolymer-triallyl phosphate composition |
CN110312757B (en) * | 2017-02-28 | 2023-11-28 | 陶氏环球技术有限责任公司 | Ethylene-alpha-olefin copolymer-triallyl phosphate composition |
CN109575190A (en) * | 2018-10-22 | 2019-04-05 | 佳易容相容剂江苏有限公司 | A kind of phosphorous polyethylene maleic anhydride graft copolymer and preparation method thereof with cooperative flame retardant effect |
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