JP2003503513A - Ethylene and / or α-olefin / vinyl or vinylidene aromatic interpolymer composition - Google Patents

Abstract

(57) Abstract: The present invention relates to (1) 5-85 mol% of polymer units obtained from at least one vinyl or vinylidene aromatic monomer, and (2) at least one ethylene and / or C _3-20 α. -A polymer obtained from 15 to 95 mol% of a polymer unit obtained from an olefin, and (3) one or more ethylenically unsaturated polymerizable monomers other than the polymer unit obtained from (1) and (2). An interpolymer comprising from 0 to 20 mol% of units and comprising a detectable vinyl or vinylidene aromatic monomer triad.

Description

Detailed Description of the Invention

The present invention relates to vinyl or vinylidene aromatic monomers, ethylene and / or 1
A composition comprising an interpolymer with one or more α-olefin monomers.
The catalysts used to make these interpolymers [(4,5-
Methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyltitanium has a significantly higher reactivity towards vinyl or vinylidene aromatic monomers. The resulting interpolymer contains a continuous insert of vinyl or vinylidene aromatic monomer, so that more than 65 mol% of vinyl or vinylidene aromatic monomer can be introduced.

Until recently, the copolymerization of ethylene with vinyl or vinylidene aromatic monomers was commercially feasible using conventional Ziegler α-olefin polymerization catalysts based on Ti (III) and Ti (IV) halides. It wasn't the right way. The earliest attempts to produce copolymers of vinyl aromatic monomers and α-olefins, especially styrene and ethylene, did not substantially incorporate vinyl aromatic monomers with such catalysts. Alternatively, low molecular weight polymers have been obtained. Polymer Bulletin, 20, 237-241 (1988) discloses a copolymer of styrene and ethylene having 1 mol% of styrene introduced therein. The reported polymer yield was 8.3 × 10 ⁻⁴ g of polymer per micromol of titanium used. However, with the advent of metallocene-based olefin polymerization catalysts, especially constrained geometry type catalysts, ethylene and other α-
It is now possible to copolymerize olefins with styrene and other vinyl or vinylidene aromatic monomers to provide interpolymers.

Copolymers of ethylene and styrene containing materials having a styrene content of more than 50 mol% using ansa metallocene catalyst have been reported, Arai, T; Ohtsu, T.
Macromolecular Rapid Commun. 1998 and Polym. Prepr., 199 by Suzuki, S.
8, 39 (1), 220-221.

Further, US Pat. No. 5,703,187 describes “pseudo-random” ethylene styrene interpolymers, which do not observe continuous head-to-tail styrene monomer incorporation, and SS diad or It features a unique monomer distribution that is not an SSS triad. The term "pseudorandom" is used because the styrene distribution in the interpolymer appears to be well dispersed, except that there is no sequential head-to-tail styrene introduction. A particular distinguishing feature of pseudorandom copolymers is that all phenyl or bulky interfering groups substituted on the polymer backbone are separated by two or more methylene units.
During the addition polymerization reaction, if a vinyl or vinylidene aromatic monomer is introduced into the growing polymer chain, the next monomer introduced is ethylene or the vinyl or vinyl derivative introduced in the opposite manner. It must be a vinylidene aromatic monomer (reverse means 2,1 introduction when the usual manner of introduction is 1,2, but may also be the opposite, for the description of the inventive interpolymers or Those skilled in the art understand that the characteristics are not changed). After the reverse vinyl or vinylidene aromatic monomer insertion, the next monomer must be ethylene. This is because the introduction of another vinyl or vinylidene aromatic monomer results in closer interfering substituents at this point than the minimum separations above. As a result of these polymerization kinetics, the catalyst used did not homopolymerize styrene appreciably, but the mixture of ethylene and styrene polymerized rapidly and had a high styrene content (
It is possible to produce copolymers of up to 50 mol% styrene). As a direct result of this monomer distribution, the practical upper limit for styrene loading was about 50 mol% or 79 wt% styrene.

WO 98/0999 describes “substantially random” ethylene styrene interpolymers, which include the above-described pseudo-random interpolymers, but which are made with certain metallocene polymerization catalysts. Also includes polymers. The use of these particular metallocene polymerization catalysts produces interpolymers featuring a unique monomer distribution. In this distribution most of the polymer chains are pseudo-random in the styrene distribution, but a small sequence involving the introduction of two head-to-tail vinyl aromatic monomers occurred, after which at least one ethylene introduction was observed. It is ethylene / styrene / styrene / ethylene tetrad ESSE, and the styrene monomer incorporation of this tetrad occurs exclusively in the 1,2 fashion. Thus, these particular substantially random ethylene / styrene interpolymers contain similar peaks in the NMR spectrum as pseudorandom ethylene / styrene interpolymers, but at 43.70-44.
． It is also characterized by an additional signal with intensity appearing in the 25 ppm chemical shift range. As a result of this unique monomer distribution, the upper limit of styrene content in the substantially random ethylene / styrene interpolymer is about 65 mol%.
Or raised to 87.5 wt% styrene.

This time, the catalyst [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyltitanium is a vinyl or vinylidene aromatic monomer in the polymerization with ethylene and / or one or more α-olefin monomers. Has a significantly higher reactivity towards S., resulting in the production of new interpolymers containing SSS and higher (eg SSSS, SSSSS, etc.) sequences in the case of ethylene / styrene interpolymers. I found it surprisingly. As a result of this increased reactivity of the catalyst, the resulting interpolymers can also exhibit an upper limit of vinyl or vinylidene aromatic monomer content of more than 65 mol%.

The present invention comprises: (1) 5 to 85 mol% of polymer units obtained from at least one vinyl or vinylidene aromatic monomer, (2) at least one ethylene and / or C _3-20 α-olefin 15 to 95 mol% of the polymer unit obtained, and (3) 0 to 20 mol% of a polymer unit obtained from an ethylenically unsaturated polymerizable monomer other than the polymer units obtained from (1) and (2), It relates to interpolymers containing detectable vinyl or vinylidene aromatic triads.

All references herein to elements or metals belonging to the family of properties are CRC
Published by Press, Inc, 1989 and according to the Periodic Table of the Elements, which is copyrighted. Also, the group reference is the group that is reflected in the periodic table of this element using the IUPAC system to quantify the group.

Numerical values quoted herein include all values from lower to higher in increments of 1 unit, provided that at least 2 between the lower and higher values are included.
There is separation of units. For example, if the amount of a component or the value of a process variable, eg temperature, pressure, time is 1-90, preferably 20-80, more preferably 30-.
70 is stated to be 15-85, 22-68, 43-51
, 30-32, etc. are intended to be specified herein. 1
For smaller values, 1 unit is 0.0001, 0.001, 0.01 or 0
． It is considered to be 1 as appropriate. These are examples of what is specifically intended, and all possible combinations of numerical values between the recited upper and lower limits are considered to be expressly specified herein as well.

The term “interpolymer” means at least 2 to make an interpolymer.
As used herein to indicate a polymer in which different monomers are polymerized. This includes copolymers, terpolymers and the like.

The term “detectable vinyl or vinylidene aromatic monomer triad” is used herein to indicate a sequence of introduction of three consecutive vinyl or vinylidene aromatics in an interpolymer. In the case of ethylene / styrene interpolymer, this corresponds to the SSS triad. When the atactic polystyrene impurities are separated from the polymer, these triads have 44.
It is detectable by the presence of a peak in the ¹³ C NMR spectrum resulting from a chemical shift corresponding to the methine carbon atom in the polymer backbone of the ethylene / styrene interpolymer at 6 ppm (ESSSE). Such triads can also be part of longer vinyl or vinylidene aromatic introduction sequences such as SSSS tetraads, SSSSS pentaads. Additional peaks can also be present in the interpolymer corresponding to the following introductions: 46.0 ppm (ESE), 43.
75 (ESSE) and 41.6 ppm (> 3 consecutive S introductions). Those skilled in the art will appreciate that such introductions containing vinyl or vinylidene aromatic monomers other than styrene and α-olefins other than ethylene will result in similar ¹³ C NMR peaks, but with slightly different chemical shifts.

The interpolymer of the present invention is a catalyst [(4,5-methylene-phenanthrenyl)]
(Tert-Butylamido) dimethylsilane] manufactured using dimethyl titanium.

[0013]

[Chemical 4]

We have surprisingly found that this catalyst has a significantly higher reactivity towards vinyl or vinylidene aromatic monomers in the polymerization with ethylene and / or one or more α-olefin monomers. . This produces a new interpolymer, which in the case of ethylene / styrene interpolymers,
Includes SSS and higher sequences (eg, SSSS, SSSSS, etc.).
As a result of the increased reactivity of the catalyst, the resulting interpolymer is 65 mol%
It is possible to indicate an upper limit up to a vinyl or vinylidene aromatic monomer content exceeding 0.

One method of making the interpolymers of the present invention is the preparation of a polymerizable monomer in the presence of [4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyltitanium and a suitable activatable compound. Polymerizing the mixture. Using this catalyst, the interpolymers of the present invention were prepared according to James C. Stevens et al., EP-A-0,416,815 and Francis J. Timmers, US Pat. No. 5,703,187.
Can be made by the methods described in the specification, both of which are incorporated herein by reference in their entirety. Preferable operating conditions for such a polymerization reaction are from atmospheric pressure to 3000.
Pressures up to atmospheric pressure and temperatures of 50-200 ° C. Polymerization of each monomer at temperatures above the autopolymerization temperature and removal of unreacted monomer can result in the production of specific amounts of homopolymer polymerization products resulting from radical polymerization. During the manufacture of the inventive interpolymers, some amounts of atactic vinyl or vinylidene aromatic homopolymers may be produced by homopolymerization of vinyl aromatic monomers at elevated temperatures. The presence of vinyl aromatic homopolymers is generally not deleterious and acceptable for the purposes of the present invention. If desired, the vinyl aromatic homopolymer is separated from the interpolymer by extraction techniques such as liquid chromatography, or by selective precipitation from a solution of the interpolymer or a non-solvent for the vinyl or vinylidene aromatic homopolymer. sell.

The interpolymer of the present invention comprises i) ethylene and / or one or more α-olefin monomers, and ii) one or more vinyl or vinylidene aromatic monomers,
And, optionally, iii) an interpolymer prepared by polymerizing another polymerizable ethylenically unsaturated monomer.

Suitable α-olefins include, for example, α-olefins containing 3 to 20, preferably 3 to 12, more preferably 3 to 8 carbon atoms. Especially suitable is
Ethylene, propylene, butene-1,4-methyl-1-pentene, hexene-1
Or octene-1, or ethylene, and propylene, butene-1,4-methyl-
It is a combination with one or more of 1-pentene, hexene-1 or octene-1. These α-olefins do not contain aromatic moieties.

Other optionally present polymerizable ethylenically unsaturated monomers include norbornene and norbornenes substituted with C _1-10 alkyl or C _6-10 aryl, exemplary interpolymers being ethylene / Styrene / norbornene and ethylene / styrene / ethylidene norbornene.

Suitable vinyl or vinylidene aromatic monomers that may be used to make the interpolymers include, for example:

[Chemical 5]

Where R ¹ is selected from the group of groups consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms, preferably hydrogen or methyl, each R ² being independently hydrogen or 1
~ Selected from the group of groups consisting of alkyl groups having 4 carbon atoms, preferably
Hydrogen or methyl, Ar is a phenyl group or is a phenyl group substituted with 1 to 5 substituents selected from the group consisting of halo, C _1-4 alkyl and C _1-4 haloalkyl, and n has a value of 0-4, preferably a value of 0-2, most preferably 0). Exemplary vinyl aromatic monomers include styrene, vinyltoluene, α-methylstyrene, t-butylstyrene, chlorostyrene, and all isomers thereof. Particularly suitable such monomers include styrene and its lower alkyl or halogen substituted derivatives. Preferred monomers are styrene, α-methylstyrene, lower alkyl (C ₁ -C ₄ ) -substituted or phenyl ring-substituted derivatives of styrene such as ortho-, meta- and para-methylstyrene, ring-halogenated styrene, para-styrene. -Includes vinyltoluene or mixtures thereof. The more preferred vinyl aromatic monomer is styrene.

The resulting interpolymer may be modified by conventional grafting, hydrogenation, functionalization or other reactions well known to those skilled in the art. Polymer is WO99 / 206
It can be easily sulfonated using the method described in 91, the entire contents of which are incorporated herein by reference. It can also be chlorinated or functionalized as described in co-pending US application Ser. No. 09 / 244,921 filed Feb. 4, 1999 by REDrumright et al. Incorporated herein by reference. The composition of the present invention may be modified by various crosslinking methods. These include, but are not limited to, peroxide-, silane-, sulfur-,
Includes radiation- or azide-based curing systems. A complete description of various cross-linking techniques is provided in US Pat. Nos. 5,869,591 and 5,977,271, the entire contents of both are incorporated herein by reference. A dual cure system using a combination of heat, moisture cure and radiation steps can be used effectively. For example, it may be desirable to use peroxide crosslinkers in combination with silane crosslinkers, peroxide crosslinkers in combination with radiation, sulfur-containing crosslinkers in combination with silane crosslinkers, and the like. Dual cure system is described in US Pat.
No. 1,940, which is disclosed and claimed, the entire contents of which are incorporated herein by reference.

Antioxidants (eg Irganox ™ 101, a registered trademark of Ciba Geigy)
0, such as hindered phenols), phosphites (eg, Irgafos ™ 168, a registered trademark of Ciba Geigy), U.S. V. Stabilizers, cling additives (eg polyisobutylene), slip agents (eg erucamide and / or stearamide), antiblocking agents, colorants, pigments, tackifiers, flame retardants, coupling agents, fillers, plasticizers Additives such as may also be included in the compositions of the present invention.

Possible components of the composition of the invention also include various organic and inorganic fillers.
Representative examples of such fillers are asbestos, boron, graphite, ceramics, glass, metals (eg stainless steel) or polymers (eg aramid fibers), talc, carbon black, carbon fibers, calcium carbonate, alumina. Trihydrate, glass fiber, marble dust, cement dust, clay, feldspar, silica or glass, fumed silica, alumina, magnesium oxide,
Magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, ammonium polyphosphate, calcium silicate, titanium dioxide, titanate,
Includes organic and inorganic fibers such as those made from aluminum nitride, B ₂ O ₃ , nickel powder or chalk.

Other organic or inorganic fibers or mineral fillers include barium carbonate, carbonates such as calcium carbonate or magnesium carbonate, borates such as magnesium borate or zinc borate, fluorides such as calcium or sodium aluminum fluoride, water. Hydroxides such as aluminum oxide, metals such as aluminum, bronze, lead or zinc, aluminum oxide, antimony oxide, magnesium oxide or zinc oxide, or oxides such as silicon dioxide or titanium dioxide, asbestos, mica, clay (kaolin) Or calcined kaolin), calcium silicate, feldspar, glass (ground or flaked glass or hollow glass spheres or microspheres or beads, whiskers or filaments), aragonite, perlite, pyrophyllite, Includes silicates such as talc or wollastonite, sulfates such as barium sulfate or calcium sulfate, metal sulfides, cellulose in the form of wood or shell flour, calcium terephthalate and liquid crystals. Mixtures of more than one such filler can also be used.

The filler may be used in combination with an initiator and / or a coupling agent selected from organic peroxides, silanes, titanates, zirconates, polyfunctional vinyl compounds, organic azides and mixtures thereof.

Other additives include hindered amine stabilizers. Such stabilizers include hindered triazines, such as substituted triazines and reaction products of triazines. Suitable reaction products include reaction products of triazines with alicyclic compounds such as diamines and / or cyclohexane. Particularly suitable hindered amine stabilizers are 1,3-propanediamine, N, N ″ -1,2-ethanediylbiscyclohexane and peroxidized N-butyl-2,2,6,6-tetramethyl-4-.
CG- which contains the reaction product of piperidine amine-2,4,6-trichloro-1,3,5-triazine, which is commercially manufactured by Ciba Geigy and has CAS Registry Number 191680-81-6. It has the name of 116.

These additives are used in functional equivalent amounts known to those skilled in the art. For example, the amount of antioxidant used is that amount which inhibits the polymer or polymer blend from undergoing oxidation at the temperatures and environments used during storage and end use of the polymer. Such amount of antioxidant is generally 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the weight of the polymer or polymer blend.
, And more preferably 0.1 to 2% by mass. Similarly, the amounts of the other listed additives are used in functional equivalent amounts such as those that render the polymer or polymer blend antiblocking and produce the desired result or provide the desired color from the colorant or pigment. To be done. Such additives have a content of 0.0 based on the weight of the interpolymer.
5 to 50 mass%, preferably 0.1 to 35 mass%, more preferably 0.2 to 20 mass%
It can be appropriately used in the range of mass%. The filler can be appropriately used in the range of 1 to 90% by mass.

The polymers of the present invention can be blended with additional polymers, including, but not limited to, other interpolymers of different molecular weight and / or vinyl or vinylidene aromatic monomer content, substantially random. Interpolymers, vinyl and vinylidene halogenated polymers such as, but not limited to, poly (vinyl chloride) and poly (vinylidene chloride), polyethylene and other polyolefins such as, but not limited to LDPE and HDPE, PP, Homogeneous ethylene / α-olefin copolymers produced by metallocene catalysts, including, but not limited to, substantially linear ethylene / α-olefin copolymers and heterogeneous ethylene / α-olefins produced by Ziegler catalysts. Copolymer, Styrenic polymers, including but not limited to polystyrene, SBS copolymers, polyethers, polycarbonates, polyanilines, asphalts or any combination thereof.

The interpolymers or blends thereof of the present invention can be processed into various forms such as, but not limited to, films, fibers, foams, sheets,
It can be processed into injection molded parts, membranes, injection blow molded parts and extruded profiles and emulsions. Applications of the interpolymers or blends thereof of the present invention include, but are not limited to, ignition resistant products, pressure sensitive adhesive film stocks, coating compositions or paints, floor, ceiling and wall coatings, carpet backings, barriers, gaskets. ,
Includes caps and closures, and with the addition of conductive additives such as carbon black, including various conductive applications such as electrical devices, conductor shields, insulation shields, and other wire and cable applications. Other applications include compatibilizers in blends of polystyrene and ethylene and / or alpha-olefin homopolymers and copolymers. Also included are applications of sulfonated derivatives, including use in fuel cell membranes, moisture absorption applications and HVAC devices.

[0030]   The NMR content determines the composition of the ethylene / styrene interpolymer of the present invention.
It may be unclear when the analysis method is used. This ambiguity is due to the styrene triad
And other highly ordered styrene incorporations are present in the interpolymer in small amounts in ubiquitous amorphous
Indistinguishable from the peak of asymmetric atactic polystyrene homopolymer (aPS) ¹ H and¹³This is due to having peaks in both C spectra. However
While the use of liquid chromatography (LC) with gradient solvent polarity
Allows separation of interpolymer from aPS, retention time of interpolymer
Indicates its styrene content.

The interpolymer composition of the present invention comprises 5-85 mol%, preferably 20-85 mol%, more preferably 50-85 mol% of at least one vinyl or vinylidene aromatic monomer, and 15-95. It contains mol%, preferably 15-80 mol%, more preferably 15-50 mol% ethylene and / or at least one aliphatic α-olefin of 3-20 carbon atoms.

The melt index (I ₂ ) of the interpolymer of the present invention is 0.05 g / 10
Min., Preferably 0.5 to 200 g / 10 min, more preferably 0.5 to 200 g / 10 min.
It is 100 g / 10 minutes.

The molecular weight distribution (Mw / Mn) of the interpolymer of the present invention is 1.5 to 20, preferably 1.8 to 10, and more preferably 2 to 5.

The composition of the interpolymers of the present invention comprises a detectable vinyl aromatic monomer triad. In the case of ethylene / styrene interpolymer, this corresponds to the SSS triad. Such triads may be part of a longer vinyl or vinylidene aromatic introduction sequence, eg SSSS tetrad, SSSSS pentad. When the atactic polystyrene impurities are separated from the polymer, these triads have a chemical shift corresponding to the methine carbon in the polymer backbone of the ethylene / styrene interpolymer at 44.6 ppm (ESSSE).
It is detectable by the presence of a peak in the ¹³ C NMR that occurs.

The following examples illustrate the invention but are not to be construed as limiting its scope in any way.

EXAMPLES TEST METHODS The molecular weights of the polymer compositions of the present invention are conveniently indicated using gel permeation chromatography with both UV and refractive index detectors.

To determine the ¹³ C NMR chemical shift of the inventive interpolymers,
The following procedures and conditions are used. A polymer solution of 5 to 10 mass% was added to 1, 1, 2,
Prepared in a mixture consisting of 50% by volume of ₂ -tetrachloroethane-d _{2 and} 50% by volume of 0.10 mol chromium tris (acetylacetonate) in 1,2,4-trichlorobenzene. NMR spectra were obtained at 130 ° C using an inverse gate decoupling sequence, 90 ° -pulse width and a pulse delay of 5 seconds or more.
The spectrum refers to the isolated methylene signal of the polymer assigned at 30.000 ppm.

Material Testing Molded polymer samples into shapes required for physical property determination by compression molding at 150 ° C. with 10 minutes of preheating, 3 minutes of compression with 10000 pounds of force and immediate cooling. did.

Differential operating calorimetry (DSC) analysis of this polymer was performed using a DuPont Instruments 910 Differential Scanning Calorimeter under nitrogen atmosphere at a heating rate of 5 ° C./min. All samples are subjected to two heating cycles (to eliminate the effects of previous heating history) and data are reported for the second scan in all cases.

Microtensile testing was performed according to ASTM D638 test protocol using compression molded Microten Silver. Instron 4507 S at room temperature with 0.1 inch / min crosshead speed and 224.8 lbf load cell.
Pulled using an eries instrument.

Samples of plane-strain fracture toughness compact tension single-edge notch geometry were compression molded into 1 ″ × 1 ″ × 1/8 ″ squares. These squares were machined and side for mounting to the test rig. Provided notches and holes, cooled with liquid nitrogen,
Then, a preliminary crack was formed in each sample by making a crack with a laser blade and a hammer. 224 at 0.02 inch / min crosshead speed
． A fracture toughness test was performed using an Instron 8501 instrument with an 8 lbf load cell.

Dynamic mechanical spectroscopy analysis was performed on rectangular bars compression molded at 100 ° C.
Temperature rise in the range of -100 ° C to 150 ° C at a set frequency of 1 rad / sec.
This was done using the auto-distortion function set by the MS instrument.

The density was measured using a helium pycnometer. Rockwell hardness is ASTM
It was evaluated using D785-93.

L. C. Analysis 0.100-0.102 g of polymer was weighed into a 30 ml vial.
10 ml of THF was added. The vial was capped and placed on a heated shaker to dissolve the sample. The temperature of the heating shaker was 65 ° C. After lysis, approximately 1 ml of solution was transferred to a HP1090LC autoinjector vial.
All chromatographic data was collected using a Hewlett Packard 1090LC (serial number 2541A00700) with a diode array detector. Signals were collected at 254 nm and 400 nm. Chromatographic data was processed using Gram 386 and Excel software.

The styrene content of the resin was determined by liquid chromatography using two columns. The first column was used to determine the atactic polystyrene content (its peak was clearly distinct). This value was subtracted from the total styrene content of the sample as determined by ¹³ C NMR to provide the weight percent copolymerized styrene. Copolymerized styrene v retention time (50 of chromatogram peak)
A calibration curve (at percentile) was then generated and the fit obtained was applied to all new samples. This analysis was performed using two types of columns.

These first columns are C18 columns from Alltech: Spherisorb ODS II 5
The size was micron, 250 × 4.60 mm. There was a guard column above the C18 column. It was RP 8.5 microns. The following are the instrument conditions used on the HP1090 with a C18 column.

[0047]

[Table 1]

The second best of the two columns was a nitro column from Phenomenex: Nucleosil 5 NO2 250 x 4.60 mm, 5 micron, serial number 243745. There was a guard column above the nitro column. It ’s Nucleo from Phenomenex
sil 5 NO2 30 × 4.6 mm, 5 micron, 100 Å, serial number 243747G. The following are the instrument conditions used for HP1090 using Nitro2 (nitro column).

[0049]

[Table 2]

Preparation of the inventive interpolymers of Examples 1-6 1) Preparation of the catalyst General Synthesis and operation were carried out in an inert atmosphere (argon) glove box. Solvents were purchased from Aldrich. Pangborn, AB; Giardello, MA; Gru
bbs, RH; Rosen, RK; Timmers, FJ, Organometallics, 1996, 15, 1518-15
As disclosed in 20, liquid reagents and solvents were first saturated with nitrogen and then dried over activated alumina before use. The deuterium-substituted benzene was dried over sodium / potassium alloy and filtered before use. Methylenephenanthrene was purchased from Lancaster. The NMR spectra of the ligand and metal complex were recorded on a Varian 300 MHz NMR spectrometer at ambient conditions. The ¹³ C NMR spectrum of the copolymer was recorded on a Bruker 600 MHz spectrometer.

Synthesis of lithium methylenephenanlenide 4,5-methylenephenanthrene (0.485 g, 2 in 50 ml hexane)
． 55 mmol), 1.6 M n-BuLi in hexane (1.75 mL, 2.
80 mmol) was added. After stirring for 1 day at ambient conditions, the solution became dark orange and a small amount of orange precipitate formed. A larger amount of precipitate formed after 14 days. This was isolated by decanting the upper layer liquid from the solids that adhered to the inner wall of the flask. After drying under reduced pressure 0.430 g was isolated (8
6% yield). Volatile material was removed from the overlying liquid to provide an orange solid. Proton NMR of this material showed it to be the starting material, methylenephenanthrene.

Synthesis of (4,5-methylenephenanthrenyl) (tert-butylamino) dimethylsilane (tert-butylamino) dimethylsilyl chloride (0.
To 436 g, 2.63 mmol) was added a cherry red solution of lithium methylenephenanthrenide (0.430 g, 2.19 mmol) in 20 mL of THF. The solution was allowed to stir overnight at ambient temperature. Volatile material was removed under reduced pressure. The solid residue was slurried in 10 mL hexane and volatile material was removed under reduced pressure. The solid residue was extracted twice with a total of 30 mL hexane. The extracts were filtered and volatile material was removed from the combined filtrate under reduced pressure to give 0.690 g (
It provided an orange oil (99% yield). ¹ H NMR spectrum was consistent with the desired product.

Synthesis of [(4,5-methylenephenanthrenyl) (tert-butylamido) dimethylsilane] titanium bis (dimethylamide) Titanium tetrakisamide (0.484 g, 2.16 mmol) and (4,5-
Methylenephenanthrenyl) (tert-butylamido) dimethylsilane (0.69
A solution of 0 g, 2.16 mmol) in 50 mL n-octane was heated to reflux and stirred. The reaction progress was monitored by ¹ H NMR by removing a small aliquot of the solution, removing the volatile materials under reduced pressure, and analyzing the residue in C6D6.
Monitored by spectroscopic analysis. Proton NMR analysis showed clean conversion to the desired product (eg, 55% conversion after reflux for about 48 hours). A few drops of titanium tetrakisamide were added periodically. After 7 days under reflux, over 82% conversion,
The reaction did not seem to proceed. Volatile material was removed from the cooled mixture under reduced pressure. The residue was dissolved in 20 mL hexane and the resulting mixture was filtered. Volatile material was removed from the filtrate under reduced pressure to give a dark powder (0
． 95 g) was provided. Proton NMR analysis of the product showed that it was a 82/18 mol% mixture of the desired product and starting ligand, respectively (87% by weight of the desired product).

Synthesis of [(4,5-methylenephenanthrenyl) (tert-butylamido) dimethylsilane] titanium dichloride Dissolved in 40 mL of hexane, the above isolated bis (amide) / ligand mixture (0 To 0.83 g, 1.83 mmol of bis (amide)) was added trimethylsilyl chloride (1.33 mL, 10.5 mmol). The solution was stirred under reflux for 6 hours. A small aliquot of the cooled solution was removed and volatile material was removed under reduced pressure. The residue was dissolved in C ₆ D ₆ and analyzed by ¹ H NMR spectroscopy. The spectrum showed a very clean conversion to the monochloride-monoamide intermediate. An additional 1.3 mL of trimethylsilyl chloride was added and the sealed vessel was stirred at ambient temperature for 8 days. The solution was then heated to reflux for 6 hours. The cooled solution was placed in a glove box freezer (-25 ° C). The solid formed was collected on a glass frit by vacuum filtration. The solid residue was washed once with cold hexane (ca 10 mL), and then the solid was dried under reduced pressure to provide 0.516 g (65% yield). Proton NMR analysis was consistent with the desired product with very clean material.

Synthesis of [(4,5-methylenephenanthrenyl) (tert-butylamido) -dimethylsilane] dimethyltitanium To this dichloride (0.516 g, 1.18 mmol) in 30 mL THF, 3.0 M was added. Methylmagnesium chloride (0.87 mL, 2.6 mmol) was added resulting in an immediate color change. After standing overnight, the volatile material was removed under reduced pressure. The solid residue was slurried in hexane and the volatile material was removed under reduced pressure. The residue was extracted several times with hexane. The extracts were filtered and volatile material was removed from the combined filtrate under reduced pressure to give a bright orange powder 0.39
Provided 2 g. Proton and ¹³ C NMR analysis in C ₆ D ₆ shows that the desired product was isolated as a 1: 1 adduct with THF. The isolated yield was 71%, with a molecular weight of 467.6 g / mol. The THF adduct (0.345 g) was dissolved in 50 mL of toluene and heated to reflux for 6 hours. A color change from orange to tan was observed. Volatile material was removed under reduced pressure. Proton NMR analysis of the residue showed clean conversion to the new compound.

2) Polymerization All transfers of solvents and solutions below were carried out using a dry, pure nitrogen or argon gas pad. The gas feed to the reactor was passed through a column of A-204 alumina and Q5 reactants for purification. Alumina was preactivated with nitrogen at 375 ° C and the Q5 reactant was activated with 200% 5% hydrogen in nitrogen. The operation of the catalyst and the auxiliary catalyst (trispentafluorophenylborane) was carried out in an inert atmosphere glove box.

Polymerization in a semi-batch reactor was carried out in a 2 liter Par reactor equipped with an electric heating jacket, an internal serpentine coil for cooling and a bottom drain valve. Pressure, temperature and block valves were computer monitored and controlled. Isopar
E and styrene were measured in a balanced solvent shot tank.
The resulting solution was then added to the reactor from the solvent shot tank. The contents of the reactor were stirred at 1200 rpm. Hydrogen was first added by differential expansion (about 50 psi) from a 300 mL 75 mL shot tank. The reactor contents were then heated to the desired operating temperature (90 ° C) under the desired ethylene pressure.

The catalyst [(4,5-methylenephenanthrenyl) (tert-butylamide)
[Dimethylsilane] dimethyltitanium and co-catalyst tris (pentafluorophenyl) borane are combined in a glove box (0.0050 M solution in toluene), and toluene is used to aid the catalyst from the glove box. Transferred to shot tank through 1/16 inch (0.16 cm) tube. The catalyst tank was then pressurized with nitrogen. After stabilizing the reactor contents at the desired operating temperature, the catalyst solution was injected into the reactor via a dip tube. The temperature was maintained by passing cold glycol through an internal cooling tube. The reaction was allowed to proceed for the desired time, providing ethylene on demand. During the run, further catalyst injections were likewise prepared and added.

The contents of the reactor were then placed in a 4 liter nitrogen-purged container, quenched with isopropyl alcohol, and 100 mg Irganox 1010 in toluene.
Was added as an antioxidant. The polymer was stripped of volatile materials at 140 ° C. in a vacuum oven overnight and cooled to 50 ° C. before being removed from the oven. The reactor conditions and polymerization data are shown in Table I.

[0060]

[Table 3]

Polymer Characterization The LC method with gradient solvent polarity was used to separate the interpolymer from aPS, and the retention time of the interpolymer peak indicated its styrene content.
Shown in Table II is the composition of the polymer reported here, the apparent molecular weight (
Polystyrene standards) and density data.

[0062]

[Table 4]

The information that these copolymers contained aPS showed the SSS triad peak of its ¹³ C NMR spectrum. The very small EEE triad peak indicated that the interpolymer had very little and had a short ethylene sequence.

All of these materials exhibited low levels of crystallinity or were amorphous. As a result, the densities of these polymers increase with increasing styrene content, approaching the density of aPS of 1.06 g / cc.

The molecular weight data show that the catalyst is capable of producing high molecular weight polymers. GPC
Due to the dual detector used in the analysis, the refractive index /
It was possible to examine the ratio of UV responses. It was found that this ratio did not change significantly, indicating a relatively uniform composition over the entire molecular weight range, with some increase in styrene content at very low molecular weights being seen in all samples. This is consistent with the presence of aPS in these materials.

[0066] Material property   The thermal transition data determined by DSC is shown in Table III.

[0067]

[Table 5]

As expected, the Tg of these materials was found to increase with increasing styrene content. The last two that greatly exceed the composition range of pseudo-random materials
The two input values show that the Tg rapidly approaches the Tg of aPS (about 100 ° C.) as the styrene content approaches 100%. It should also be noted that none of the materials showed a significant Tg due to the aPS homopolymer. However, the LC data show aPS in the isolated material. The polymer with the highest crystallinity (lowest styrene content, 55 wt% S) exhibited a melting temperature peak near 120 ° C and a Tg near 32 ° C.

Microtensile tests and fracture toughness tests were performed and Table IV evaluated the mechanical properties of these materials. Short-term tensile analysis shows a relatively glassy response with high modulus at low tensile stress and a relatively linear stress / strain relationship for all materials below about 2% strain. The Young's modulus of all of these materials is 350,000-
It was in the range of 430,000 psi (2.4-3 GPa). All materials experience ductile yield at relatively low strains, with yield strain steadily migrating to lower elongations with increasing styrene content. All polymers showed some elongation above the yield point to ultimate failure.

[0070]

[Table 6]

Fracture toughness was measured using compact tension geometry samples. These experiments were designed to quantify the polymer's resistance to crack initiation and growth to applied loads. The tests were performed on compression molded notched square polymers and a razor blade was used to crack at the V of the notch. A tensile load was then applied to the sample with plane stress, and the prepared sample was of ideal thickness sufficient to prevent twisting from the plane of the applied load. The relationship obtained between load and displacement can determine the instantaneous stress required to grow a crack, known as the stress intensity factor Klc.
It is also useful to identify the energy required to spread the crack over a given unit area, this quantity is expressed as Glc (Fracture Energy or Critical Strain-Energy Release Rate), which is equal to Klc There is a relationship of 1.

[0072]

[Equation 1]

Where E is Young's modulus and Poisson's ratio. Higher values of Klc and Glc mean that fracture toughness is enhanced.

Fracture toughness measurements showed no significant differences among the samples of material tested. Table V shows the critical stress intensity factor (Klc) for the four samples with the highest styrene content, and the data was obtained under the same test conditions as the high molecular weight radically polymerized polystyrene homopolymer. The copolymers show significantly higher Klc and Glc values, and the load to cause yielding and failure is much higher for the copolymer than the polystyrene homopolymer.

The improved toughness of these materials to polystyrene results from the ability of the introduced ethylene units to produce a more ductile response in response to applied stress on the time scale of the fracture test. Can be

[0076]

[Table 7]

DMS analysis of the amorphous interpolymers was performed to determine the location of the glass transition point and to identify other transitions associated with these materials. The glass transition temperature and the room sub-Tg storage modulus at room temperature below Tg increase with increasing styrene content in the copolymer.

The glass transition temperatures of these materials were clearly observed in the shear loss modulus (G ″) response of amorphous ES copolymers, and a broad transition was observed between about −50 ° C. and room temperature. In polystyrene, this transition was due to relaxation of the main chain accompanied by displacement of the phenyl ring.

The physical properties of the high styrene content interpolymers of the present invention show improved resistance to fracture. This suggests that these interpolymers offer unique utility for particular applications. Amorphous interpolymers with the highest styrene content are transparent, so these polymers can have utility in film applications, and have advantages over aPS due to their increased toughness. In addition, these novel polymeric foam sheets can exhibit better resilience than aPS sheets and can perform better in applications where improved durability is required. These polymers can also be used to enhance aPS, while maintaining good transparency if compatible compositions can be discovered.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 69/00 C08L 69/00 71/00 71/00 Z 79/00 79/00 A 95/00 95 / 00 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, C , CN, CR, CZ, DE, DK, DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, K R, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, YU, ZA, ZW (72) Inventor Shanker, Rabbi. Congress Drive 4300, Midland 48642, Michigan, USA 4300 (72) Inventor Timers, Francis Jay. United States, Michigan 48642, mission Dorando, land drive 4605 F-term (reference) 4J002 AG00X BB03X BB15X BC03X BC04W BC05X BD03X BD10X CG00X CH00X CM01X GQ01 GQ02 4J028 AA01A AB01A AC08A BA00A BA01B BB00A BB00B BC12B EB02 EB21 GA01 GA06 GA08 GA19 GB01 4J100 AA02Q AB02P CA04 DA04 DA05 DA11 DA24 DA25 DA48 DA49 DA51 FA10 FA19 JA01 JA03 JA28 JA45

Claims (17)

[Claims] 1. From 1 to 5 to 85 mol% of polymer units obtained from at least one vinyl or vinylidene aromatic monomer, (2) from at least one ethylene and / or C _3-20 α-olefin. 15 to 95 mol% of the polymer units obtained, and (3) polymer units 0 to 20 obtained from at least one ethylenically unsaturated polymerizable monomer other than the polymer units obtained from (1) and (2). %, And containing a detectable vinyl or vinylidene aromatic monomer triad. 2. The component (1) is represented by the following formula: (In the formula, R ¹ is selected from the group of groups consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms, and each R ² is independently hydrogen and an alkyl group having 1 to 4 carbon atoms. Ar is a phenyl group or is a phenyl group substituted with 1 to 5 substituents selected from the group consisting of halo, C _1-4 alkyl and C _1-4 haloalkyl. , And n is a value of 0 to 4) with 20 to 85 polymer units obtained from said vinyl or vinylidene aromatic monomer.
Or at least one of (2) ethylene and / or propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1.
The polymer contains 15 to 80 mol% of a polymer unit obtained from an olefin, and (3) the ethylenically unsaturated polymerizable monomer other than the polymer unit obtained from (1) or (2) is norbornene or C. The interpolymer of claim 1, comprising norbornene substituted with _1-10 alkyl or C _6-10 aryl. 3. (1) Component (1) is a polymer obtained from the vinyl aromatic monomer containing styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene and ring-halogenated styrene. 50 to 85 mol% of the unit, or (2) contains ethylene, or at least one of ethylene and propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1. Ethylene, or 15 to 50 mol% of a polymer unit obtained from ethylene and the α-olefin, and (3) a polymer unit other than the polymer units obtained from (1) and (2). The interpolymer according to claim 1, wherein the ethylenically unsaturated polymerizable monomer is norbornene. 4. The interpolymer of claim 3, wherein component (1) (a) is styrene and component (2) is ethylene. 5. The component (1) (a) is styrene, and the component (2) is one of ethylene and propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1. The interpolymer of claim 3, wherein the interpolymer is at least one. 6. (a) at least one vinyl or vinylidene aromatic monomer, (b) at least one ethylene and / or C _3-20 α-olefin, and (c) optionally (1) and Polymerizing one or more ethylenically unsaturated polymerizable monomers other than those obtained from (2) in the presence of a catalyst containing [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyltitanium. An interpolymer produced by: 7. (a) The vinyl or vinylidene aromatic monomer has the following formula: (In the formula, R ¹ is selected from the group of groups consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms, and each R ² is independently hydrogen and an alkyl group having 1 to 4 carbon atoms. Ar is a phenyl group or is a phenyl group substituted with 1 to 5 substituents selected from the group consisting of halo, C _1-4 alkyl and C _1-4 haloalkyl. , And n is a value from 0 to 4), or (b) the α-olefin is one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1. The ethylenically unsaturated polymerizable monomer other than those obtained from (1) and (2) contains at least one norbornene or norbornene substituted with C _1-10 alkyl or C _6-10 aryl. , Claim 6 Terpolymers. 8. The interpolymer of claim 7, wherein component (a) is styrene and component (c) is ethylene. 9. Component (a) is styrene, and component (c) is ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1. The interpolymer according to claim 7, which is Tsuto. 10. (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one ethylene and / or C _3-20 α-olefin, and
(C) optionally one or more ethylenically unsaturated polymerizable monomers other than those obtained from (1) and (2), [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] A method for producing an interpolymer by polymerizing in the presence of a catalyst containing dimethyl titanium. 11. The (a) vinyl or vinylidene aromatic monomer is
Ceremony     [Chemical 3] (In the formula, R¹Is a group of groups consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms
Selected from each R²Are independently hydrogen and an alkyl group having 1 to 4 carbon atoms.
Selected from the group of groups consisting of Ar is a phenyl group or halo, C_1-4Archi
Le and C_1-4Substituted with 1 to 5 substituents selected from the group consisting of haloalkyl
Is a phenyl group, and n has a value of 0 to 4), or   (B) The α-olefin is propylene, 4-methyl-1-pentene, butene
-1, at least one of hexene-1 or octene-1,   (C) Ethylenically unsaturated polymerizability other than those obtained from (1) and (2)
The monomer, if present, is norbornene or C_1-10Alkyl or C _6-10 The method of claim 10, comprising norbornene substituted with aryl. 12. The method of claim 11 wherein component (a) is styrene and component (c) is ethylene. 13. Component (a) is styrene, and component (c) is ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1. The method according to claim 11, which is Tsutoto. 14. A) the interpolymer of claim 1, and   B) one or more additional polymer components, Blend containing. 15. The additional polymer component B) is a substantially random interpolymer, vinyl and vinylidene halide, ethylene homopolymer, α.
A blend according to claim 15 selected from the group consisting of: olefin homopolymers, ethylene / α-olefin copolymers, styrenic polymers, polyethers, polycarbonates, polyanilines, asphalts, or combinations thereof. 16. A transition metal complex of [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyltitanium. 17. A catalyst composition comprising [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyltitanium.