JP2002544334A - Production of olefin / carbon monoxide polymer - Google Patents

Abstract

  (57) [Summary] An olefin / carbon monoxide copolymer is made by contacting these monomers with a nickel complex of a selected diphosphine ligand. The copolymer is useful as a resin for molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION Olefin / carbon monoxide copolymers are prepared by contacting these monomers with a nickel complex of a selected diphosphine ligand. Also disclosed are novel phosphorus-containing ligands.

TECHNICAL BACKGROUND Olefin / carbon monoxide copolymers are useful products for injection molded parts for various industrial applications. Usually these copolymers are (to a large extent) alternating copolymers. The most common preparation of these polymers is to use various palladium complexes as catalysts for the copolymerization. These complexes are satisfactory from a reaction point of view, but have the major disadvantage of using palladium, which is a very expensive metal economically. Therefore, cheaper catalysts for producing these polymers are being sought.

One way to reduce catalyst cost is to find a cheaper transition metal-based catalyst. WO 97/00127 and WO 97/23492 describe nickel complexes having specific ligands for copolymerizing ethylene and carbon monoxide. None of these references describe the diphosphine ligands discussed herein.

SUMMARY OF THE INVENTION The present invention is a first method for making an olefin / carbon monoxide copolymer, comprising one or more olefins having the formula H ₂ C = CHR ⁵ , carbon,
Bronsted acid and formula

[0005]

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Wherein each Ar ¹ is aryl or substituted aryl; each R ³ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Cy is cyclohexyl; and each R ⁴ is independently an alkyl containing 1 to 20 carbon atoms, R ⁵ contains hydrogen or from 1 to 20 carbon atoms are n- alkyl and each R ⁶ is independently hydrocarbyl Or a substituted hydrocarbyl) with a nickel complex having a ligand of the formula:

[0007] The present invention is also a second method for producing an olefin / carbon monoxide copolymer, comprising one or more olefins having the formula H ₂ C = CHR ⁵ , carbon monoxide, Bronsted acid, nickel [II] compound and formula

[0008]

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Wherein each Ar ¹ is independently aryl or substituted aryl, each R ³ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl, Cy is cyclohexyl, and each R ⁴ Is independently alkyl containing 1 to 20 carbon atoms; R ⁵ is hydrogen or n-alkyl containing 1 to 20 carbon atoms; each R ⁶ is hydrocarbyl or substituted Contacting a ligand having a hydrocarbyl).

[0010] Also, the expression

[0011]

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Wherein R ³ , Cy and R ⁶ are as defined above, are also disclosed herein.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In this specification, a number of terms are used. Some of these are as follows.

“Hydrocarbyl group” is a monovalent group containing only carbon and hydrogen. Unless otherwise specified, it is preferred herein that hydrocarbyl groups contain 1 to about 30 carbon atoms.

[0015] As used herein, "substituted hydrocarbyl group" means a hydrocarbyl group containing one or more substituents that is inert under the process conditions at which the compound containing those groups is subjected. The substituents also do not substantially interfere with the process. Unless otherwise stated, it is preferred herein that substituted hydrocarbyl groups contain 1 to about 30 carbon atoms. The meaning of "substituted" includes heteroaromatic rings. All of the hydrogen atoms in the substituted hydrocarbyl group may be substituted, as in perfluoroalkyl. Other groups may be similarly substituted.

As used herein, “(inactive) functional group” means a group other than a hydrocarbyl group or a substituted hydrocarbyl group that is inert under the process conditions at which the compound containing the group is placed. Functional groups also do not substantially interfere with any of the steps described herein involving the compound in which the group is present. Examples of functional groups include halo (fluoro, chloro, bromo and iodo), - (wherein, R ¹⁸ is hydrocarbyl or substituted hydrocarbyl) OR ¹⁸ include ethers, such as.

“Relative non-coordinating anions” (or “weakly coordinating anions”) are known in the art.
It usually refers to an anion so called, and the coordination ability of such an anion is public.
Knowledge and discussed in the literature. For example, W.S. Beck. , Et al. , Chem. Rev .. , Vol. 88, p. 1405-1421 (1988), and
And S. H. Stares,Chem. Rev. , Vol. 93, p. 927-9
42 (1993). Both documents are incorporated herein by reference.
Shall be. Among such anions are the aluminas in the immediately preceding paragraph.
Compound and X^-And an example of which is R.⁹ _ThreeAl
X^-, R⁹ _TwoAlClX^-, R⁹AlCl_TwoX^-And R⁹AlOX^-(Where R⁹Is archi
). Examples of other useful non-coordinating anions include BAF^-｛B
AF = tetrakis (3,5-bis (trifluoromethyl) phenyl) borate}
, SbF₆ ^-, PF₆ ^-, And BF_Four ^-, Trifluoromethanesulfonate, p-toluene
Ensulfonate, (R_fSO_Two)_Two N^-, And (C₆F_Five)_FourB^-Is mentioned.

[0018] The meaning of adding a particular nickel complex includes the addition of reagents known in the art to form the complex under these process conditions.

In (II), all Ar ¹ are preferably phenyl or substituted phenyl, more preferably phenyl.

In (III), all R ³ are preferably hydrogen.

In (IV), each R ⁴ is preferably independently an alkyl containing 1 to 4 carbon atoms, more preferably each R ⁴ is independently methyl or ethyl, Particularly preferably, all R ⁴ are ethyl.

In (V), each R ⁶ is preferably independently alkyl, more preferably each R ⁶ is independently alkyl containing 1 to 4 carbon atoms,
Particularly preferably, all R ⁶ are methyl.

The amount of compound (I), (II), (III), and / or (IV) supplied to the polymerization step can vary, but may vary from about 0.1 to about 2 per g atom of nickel. It is convenient to choose in the molar range. Preferably, the amount ranges from about 0.5 to about 1.5 moles of compound per mole of nickel compound.

Preferred Bronsted acids are strong acids, ie acids having a pKa value of less than about 6, especially less than about 4, and more particularly less than about 2 when measured in an aqueous solution at 18 ° C. Examples of suitable Bronsted acids are protic acids which can also form nickel salts, for example trifluoroacetic acid. Examples of protonic acids which can be used are sulfonic acids and hydrohalic acids, especially hydrogen fluoride, tetrafluoroboric acid and hexafluoroboric acid (with HBF ₄ and HBF ₆ ).

The activity of the catalyst composition is such that an amount in the range of 10 ^-7 to 10 ^-2 nickel g atoms per mole of olefinically unsaturated compound to be copolymerized is appropriate. Preferably, the amount is 10 ^-6 to 10 ^-3 on the same basis.

In preferred olefins, R ⁵ is hydrogen or alkyl containing 1 to 4 carbon atoms, more preferably R ⁵ is hydrogen (ethylene) or methyl (propylene), particularly preferably R ⁵ is Hydrogen. In preferred polymers, ethylene and other olefins are used, preferably propylene or 1-butene, more preferably propylene.

Generally, the molar ratio of carbon monoxide on one side to olefinically unsaturated compounds on the other side can be selected within a wide range, for example, from about 1:50 to about 20: 1. However, it is preferred to employ a molar ratio ranging from about 1:20 to about 2: 1.

The method of the present invention is conveniently performed in the presence of a diluent. As the diluent, it is preferable to use a solvent in which the copolymer is insoluble or substantially insoluble so that a suspension is formed when the copolymer is formed. Recommended diluents are ketone and air
Polar organic liquids such as ters, esters or amides. Protic liquids,
It is preferred to use mono- and dihydric alcohols, especially lower alcohols having up to 4 carbon atoms per molecule, such as methanol and ethanol. The process of the invention can also be carried out as a gas phase process, in which the catalyst is generally deposited on solid particulate matter or chemically attached thereto.

If a diluent is used in which the resulting copolymer forms a suspension, it is preferred that the solid particulate matter be suspended in the diluent before the monomer contacts the catalyst composition. Suitable solid particulate materials are silica, polyethylene and copolymers of carbon monoxide and olefinically unsaturated compounds, preferably those based on the same monomers as the copolymers produced. The amount of solid particulate matter is about 0.1 to 100 g per 100 g of diluent.
A range of about 20 g is preferred, especially about 0.5 to about 10 g.

Examples of conditions for carrying out the method of the present invention include a temperature of about 0 ° C. to about 200 ° C., preferably between about 30 ° C. and about 130 ° C., and between about 0.1 MPa and about 200 MPa.
In particular, the use of a pressure between about 0.5 MPa and about 10 MPa (sum of ethylene and CO) is mentioned. The pressure of carbon monoxide is generally at least about 0.1 MPa. Preferably, the partial pressure of CO is approximately equal to the pressure of ethylene.

[0031] The copolymer can be recovered from the polymerization mixture using conventional techniques. If a diluent is used, the copolymer can be recovered by filtration or evaporation of the diluent. The copolymer can be purified to some extent by washing.

In the copolymer, a copolymer in which one polymerized unit formed from carbon monoxide and the other polymerized unit formed from an olefinically unsaturated compound are alternately or substantially alternately arranged is suitable. It is manufactured in. The term “substantially alternating” is generally understood by those skilled in the art as having a molar ratio of polymerized units formed from carbon monoxide to polymerized units formed from olefinically unsaturated compounds of greater than about 35:65, especially about 40:65. : Will be understood to mean over 60. If the polymers are completely alternating, this ratio is equal to 50:50.

It is preferred to produce a copolymer having a melting point above 150 ° C. as measured by a differential scanning calorimeter (DSC). For example, a linear copolymer of carbon monoxide and ethylene, and a linear copolymer of carbon monoxide, ethylene and an α-olefin, which are alternating copolymers or are substantially alternating Belongs to the category. A linear alternating copolymer of carbon monoxide and ethylene, or a linear alternating copolymer of carbon monoxide, ethylene and an α-olefin, wherein other α-olefin to ethylene (R ⁵ is n-alkyl Is generally greater than about 1: 100, preferably in the range of about 1: 100 to about 1: 3, and more preferably in the range of about 1:50 to about 1: 5. It is particularly preferred to produce a state alternating copolymer.

[0034] Preferably, the copolymer produced has a number average molecular weight (Mn) of at least about 10,000, more preferably greater than about 20,000, and more preferably about 30,000.
Is especially preferred. Mn can be measured by gel permeation chromatography using hexafluoroisopropanol as a solvent.

Further, for practical reasons, the nickel content of the copolymer will generally be greater than about 0.01 ppm by weight, based on the weight of the copolymer. It is preferred to produce copolymers having a nickel content in the range of about 0.05 to about 300 ppm, based on the weight of the copolymer, with a range of about 0.1 to about 200 ppm being particularly preferred. It is preferred that the copolymer contains substantially no palladium, especially no palladium. `` Substantially free of palladium '' means to those skilled in the art that the palladium content is lower than would normally be achieved when using a palladium-based catalyst in the copolymerization reaction,
For example, it means less than 1 ppm by weight, especially less than 0.1 ppm based on the weight of the copolymer. Alternatively, if palladium is present, the weight ratio of palladium to nickel is preferably less than about 1:50, particularly less than about 1: 100, or most particularly less than about 1: 200. Preferably, there is even.

The preparation of compound (I) is described in WO 97/00127, the preparation of (III) is described in Example 4 [other compounds (III) can be prepared in a similar manner], and The production of (IV) is described in WO 00/21970. Both of these documents are incorporated herein by reference for all purposes, as if fully set forth. Compound (II)
Is commercially available.

EXAMPLES 1-4 AND COMPARATIVE EXAMPLE A Ethylene / CO 2 Copolymerization This method uses ethylene / carbon monoxide (E / C
This is a common method for the copolymerization of O).

In the reactor, nickel acetate [II] tetrahydrate (0.05 mmol) and diphosphine (
0.06 mmol). Methanol solution of trifluoroacetic acid (0.2m
mol / 5 mL) and the reactor was removed from the drying box. The reactor was evacuated, ethylene (350 kPa; all pressures were gauge pressure) and E / CO
(1: 1, 3.90 MPa) and the reaction was carried out at 90 ° C. for 16 hours.
Under these conditions, the final pressure was 5.17 MPa. The polymer was recovered from shaker vials, washed with methanol and dried overnight under high vacuum.
The sample was subjected to a differential scanning calorimeter (the melting point Tm was measured at a heating rate of 10 ° C./min in the first heating and determined as an endothermic peak). Table 1 shows the results of the polymerization reaction and the structure of diphosphine ("compound"). In Example 3, the molecular weight of the polymer was measured by differential scanning calorimetry in hexafluoroloisopropanol,
A number average molecular weight of 81800 and a weight average molecular weight of 129000 were obtained. Comparative Example A
In, the “compound” used is

[0039]

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Was

[0041]

[Table 1]

Example 5 In a dry box, 1.20 g of R-(+)-1,1′-bi-2-naphthol (Al
drich Chemical Co. , Milwaukee, WI, U.S.A. S.
A. ), 2.00 g of dicyclohexylline chloride (Strem Chemica)
l) and 1.70 g of triethylamine were dissolved in 25 mL of THF. The mixture was allowed to stir at room temperature for 35 hours. The mixture was filtered through Celite® and then washed three times with 10 mL of tetrahydrofuran. The collected filtrate was evaporated under reduced pressure. The product was vacuum dried overnight. A white solid was obtained. The conversion was quantitative. ¹ H-NMR (CD ₂ Cl ₂ , δ): 0.25 to 1.85 (44H), 7.
10-8.10 (12H, Ar-H), ³¹ P-NMR (CD ₂ Cl ₂ , δ): 11
4.33 (s).

Example 6 1,3-bis (dichlorophosphino) benzene (1.0 g, 3 g
. 57 mmol). Diethyl ether (20 mL) was added and the solution was cooled to -30C. Slowly add trimethylsilylmethylmagnesium chloride (1.0 M in diethyl ether, 17.9 mL, 17.9 mmol),
The reaction was then slowly warmed to room temperature. The next day, water (2.0 mL) was added and the reaction was stirred for 30 minutes. The solvent was removed in vacuo. Toluene (35 mL) was added and the reaction was stirred for another 30 minutes. The reaction mixture was filtered and the product was washed with toluene (2 × 5 mL) and dried under vacuum. Pale yellow oil (0.52 g,
30%) was recovered _{(Me 3 SiCH 2) 2 P} (C 2 H- 4) P (CH 2 SiMe 3) 2. ³¹ P NMR (121.5 MHz, 20 ° C., C6D6) δ-44.8.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country 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, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS , JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZWF terms (reference) 4H050 AA01 AA03 AB40 4J005 AB01 BB02

Claims (10)

[Claims] 1. One or more olefins having the formula H ₂ C ＝ CHR ⁵ ,
A process for preparing an olefin / carbon monoxide copolymer comprising contacting a nickel complex of a ligand containing carbon monoxide, a Bronsted acid and phosphorus, wherein the ligand has the formula: Formula 1 Wherein each Ar ¹ is aryl or substituted aryl; each R ³ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Cy is cyclohexyl; and each R ⁴ is independently R ⁵ is hydrogen or n-alkyl containing 1 to 20 carbon atoms, and each R ⁶ is independently hydrocarbyl or substituted hydrocarbyl. ). 2. One or more olefins having the formula H ₂ C ＝ CHR ⁵ ,
A method for producing an olefin / carbon monoxide copolymer, comprising the step of contacting a ligand containing carbon monoxide, a Bronsted acid, a nickel [II] compound and phosphorus. , The formula Wherein each Ar ¹ is independently aryl or substituted aryl; each R ³ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Cy is cyclohexyl; and each R ⁴ is independently Wherein R ⁵ is hydrogen or n-alkyl containing 1 to 20 carbon atoms, and each R ⁶ is hydrocarbyl or substituted hydrocarbyl ). 3. The method according to claim 1, wherein the contacting is performed at a temperature of about 30 ° C. to about 130 ° C. 4. All Ar ¹ are phenyl or substituted phenyl; all R ³ are hydrogen; each R ⁴ is independently alkyl containing 1-4 carbon atoms; and each R ⁶ is, independently, the method according to claim 1 or 2, characterized in that alkyl. 5. The method according to claim 4, wherein all Ar ¹ are phenyl, and all R ⁴ are methyl or ethyl, and all R ⁶ are methyl. . 6. The method according to claim 1, wherein R ⁵ is hydrogen, or R ⁵ is both hydrogen and methyl. 7. The method according to claim 1, wherein an alternating copolymer is produced. 8. The method according to claim 1, wherein the Bronsted acid has a pKa of about 2 or less. 9. A compound of the formula Wherein each R ³ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl, Cy is cyclohexyl, and each R ⁶ is hydrocarbyl or substituted hydrocarbyl. 10. The compound according to claim 9, wherein all R ³ are hydrogen and all R ⁶ are methyl.