CN1187830A - Catalyst composition and method for preparing copolymer of carbon monoxide and ethylenically unsaturated compound - Google Patents

Abstract

A catalyst composition based on (a) a source of nickel cations, and (b) a bidentate ligand having the general formula R ¹ R ² M ¹ -R-M ² R ³ R ⁴ (I), wherein M ¹ and M ² each independently represent phosphorus, nitrogen, arsenic or antimony, R ¹ , R ² , R ³ and R ⁴ each independently represent an optionally substituted hydrocarbon group, provided that R ¹ , R ² , R ³ and R ⁴ At least one of them represents a substituted aryl group, R represents a divalent bridging group, the bridging group is composed of at most two bridging atoms, and a method for preparing a copolymer of carbon monoxide and an ethylenically unsaturated compound, including the presence of the catalyst composition In the case of contacting the monomer.

Description

Catalyst composition and method for preparing copolymer of carbon monoxide and ethylenically unsaturated compound

The present invention relates to catalyst compositions and processes for the preparation of copolymers of carbon monoxide and one or more ethylenically unsaturated compounds.

Linear copolymers of carbon monoxide and one or more ethylenically unsaturated compounds can be prepared by contacting the monomers in the presence of a Group VIII metal-containing catalyst. The copolymers can be processed by conventional techniques into films, sheets, plates, filaments and accessories in the household goods and automotive industries. They are excellent for use in vent holes for many thermoplastics. Units derived from carbon monoxide and units derived from ethylenically unsaturated compounds may be arranged alternately or substantially alternately in the above-mentioned copolymer.

To date, the use of group VIII metal palladium-based catalysts for the preparation of copolymers has been extensively studied because palladium-based catalysts provide high polymerization rates. However, the disadvantage of using palladium-based catalysts is that palladium is expensive, a fact due to the limited availability of this metal from nature. There are also methods for extracting palladium residues from copolymers that allow recovery of palladium, but these methods require the introduction of additional process steps that complicate the overall polymerization process flow. Another disadvantage is that palladium-based catalysts are prone to plate-out, ie transition to the zero-valent metal state. During the gradual formation and further processing of the copolymer, deposition can cause some gray discoloration of the copolymer, especially when the content of catalyst residues is high. Deposition may also occur during the preparation of the catalyst or during storage of the catalyst composition prior to its use in the copolymerization process. The deposition is most likely related to the noble metal properties of palladium. It is therefore desirable to find alternatives to palladium-based catalysts.

Other Group VIII metals that can be used for the copolymerization of carbon monoxide and ethylenically unsaturated compounds are nickel and cobalt. For example, US-A-3984388 discloses the use of nickel cyanide based catalysts. However, these catalysts show low polymerization activity despite the high polymerization temperature applied. In addition, copolymers made with these catalysts contain catalyst residues which are cyanides, from which cyanide-containing compounds, such as hydrogen cyanide, may then be removed during the end use of the copolymers. This is particularly undesirable when the copolymer is used as a packaging material that comes into contact with food.

An improvement in the rate of polymerization was achieved by EP-A-121965, which proposed the use of catalysts containing nickel or cobalt chelated with a bidentate ligand of 1,3-bis(diphenylphosphino) propane or 1,4-bis(diphenylphosphino)butane. In this case, however, the molecular weight of the copolymer was found to be lower than would be expected in many applications. In addition, the resulting polymerization rate still leaves room for further improvement.

EP-A-470759 discloses the use of catalysts based on nickel chelated with mercaptocarboxylic acids. It can be seen from the examples of this application that the polymerization rate achieved is still low.

It can be concluded that to date no satisfactory results have been obtained with nickel or cobalt based catalysts.

We have now discovered that the use of nickel chelated with an improved bidentate ligand in the catalyst results in substantial improvements in the performance of nickel-containing catalysts. This modification involves the presence of a chelating atom with a substituted aryl group and the presence of a small bridging group linking the two chelating atoms. The improvement manifests itself in the rate of polymerization, as well as in the molecular weights that can be achieved. The advantage of this discovery is that copolymers can be prepared in a simple and efficient manner using cyanide-free, non-plating metal-containing catalysts. Furthermore, the reactor powders thus produced have a very low content of catalyst residues and they have a good color. The copolymers have a relatively high level of melt stability and they are in principle cyanide-free. It is clear that the use of nickel-based catalysts under the same conditions results in surprisingly higher molecular weight copolymers than palladium-based catalysts. With cobalt the results were unsatisfactory.

Accordingly, the present invention relates to a catalyst composition based on: (a) a source of nickel cations, and (b) a bidentate compound of formula R ¹ R ² M ¹ -RM ² R ³ R ⁴ (I) Ligands, wherein M ¹ and M ² each independently represent phosphorus, nitrogen, arsenic or antimony, R ¹ , R ² , R ³ and R ⁴ each independently represent an optionally substituted hydrocarbon group, provided that R ¹ , R ² , At least one of ^R3 and ^R4 represents a substituted aryl group, and R represents a divalent bridging group consisting of at most two bridging atoms.

The invention also relates to a process for the preparation of copolymers of carbon monoxide and ethylenically unsaturated compounds, comprising contacting the monomers in the presence of the catalyst composition according to the invention.

Further the present invention relates to linear copolymers of carbon monoxide and ethylenically unsaturated compounds comprising up to 500 ppmw by weight of nickel and which are free or substantially free of palladium.

Typically nickel salts are used as the source of nickel cations, such as nickel(II) salts. Suitable salts include those of inorganic acids such as sulfuric, nitric, phosphoric and sulfonic acids, and organic salts such as nickel acetylacetonate. Preference is given to using nickel salts of carboxylic acids, for example carboxylic acids having up to 8 carbon atoms, such as formic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid and citric acid. Other preferred nickel salts are nickel halides, such as nickel(II) bromide and nickel(II) iodide. Nickel (II) acetate is a particularly preferred source of nickel cations. Another very suitable source of nickel cations is nickel in its zero valence state, ie nickel(0), chelated with organic ligands such as dienes or phosphine compounds. Examples of such chelates are nickel(0)tetracarbonyl, nickel(0)bis(triphenylphosphine)dicarbonyl and nickel(0)bicyclooctadiene, the cationic species being defined by their association with e.g. strong acids as defined below formed by the reaction of acids such as trifluoroacetic acid.

In the ligands of formula (I), M ¹ and M ² preferably represent phosphorus atoms. The R ¹ , R ² , R ³ and R ⁴ groups are each independently a hydrocarbon group which may be optionally substituted by polarity. R ¹ , R ² , R ³ and R ⁴ can each independently represent any polar substituted alkyl, aryl, alkaryl, aralkyl or cycloalkyl, which generally contain no more than 20 carbon atoms, preferably Not more than 10 carbon atoms, provided that at least one of R ¹ , R ² , R ³ and R ⁴ represents a substituted aryl group. Such substituted aryl groups preferably contain no more than 20 carbon atoms, more preferably no more than 10 carbon atoms. Generally, at least one of R ¹ and R ² and at least one of R ³ and R ⁴ represent a substituted aryl group, and more typically each of R ¹ , R ² , R ³ and R ⁴ represents a substituted aryl group.

Suitable substituents on substituted aryl groups are alkyl groups such as methyl, ethyl or tert-butyl. However, it is preferred that the substituted aryl group is polar substituted. Suitable polar substituents include halogen atoms such as fluorine and chlorine, alkoxy groups such as methoxy and ethoxy, and alkylamino groups such as methylamino, dimethylamino and diethylamino. The alkyl group in alkoxy and alkylamino especially contains not more than 5 carbon atoms. Preferred polar substituents are alkoxy, especially methoxy.

Preferred substituted aryl groups R ¹ , R ² , R ³ and R ⁴ are phenyl groups generally bearing substituents in the ortho position to M ¹ or M ² . Other substituents are preferably located in the ortho-position or para-position of ^M1 or ^M2 .

The bridging group R of the ligands of the formula (I) is generally an organic bridging group with up to 10 carbon atoms. The bridging atoms are preferably carbon atoms, but one or both bridging atoms may also be heteroatoms, such as silicon or oxygen atoms. There are preferably two bridging carbon atoms. The bridging group R can be aliphatic, olefinic or aromatic. However, it is preferably 1,2-alkylene, for example 1,2-propene, 2,3-butenyl or 1,2-cyclohexenyl. R most preferably represents vinyl ( _-CH2 - _CH2- ).

Preferred bidentate ligands are 1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane, 1,2-bis[bis(2,4-dimethoxyphenyl)phosphino ]ethane, 1,2-bis[bis(2,4,6-trimethoxyphenyl)phosphino]ethane, and most preferably 1,2-bis[bis(2-methoxyphenyl)phosphine base] ethane.

The amount of bidentate ligand added to the catalyst composition can vary, but is generally selected within the range of 0.1-2 moles of bidentate ligand per gram atom of nickel. Preferably, the amount is in the range of 0.5 to 1.5 moles of ligand per gram atom of nickel.

Catalyst compositions containing nickel may be based on a source of anions for another catalyst component. Those skilled in the art will understand that suitable anions are those that do not coordinate or only weakly coordinate to nickel under the conditions of the copolymerization. Examples of suitable anions are anions of protic acids, including those obtainable by combining Lewis acids with protic acids, and those obtained by addition of boric acid with 1,2-diol, catechol or salicylic acid acid. Preferred acids are strong acids, ie those with a pKa of less than 6, especially less than 4, more especially less than 2, measured in aqueous solution at 18°C. Examples of suitable protic acids are the acids mentioned above which can also be doped in the nickel salt, eg trifluoroacetic acid. Examples of Lewis acids which can be combined with the protophilic acid are the Lewis acids defined and exemplified below, in particular boron trifluoride, boron pentafluoride, tin dichloride, tin difluoride, bis(methylsulfonic acid ) tin, aluminum trifluoride and arsenic pentafluoride, triphenylborane, tris(perfluorophenyl)borane and tris[3,5-bis(trifluoromethyl)phenyl]borane . Examples of protic acids which can be combined with Lewis acids are sulfonic acids and hydrohalic acids, especially hydrofluoric acid. Particularly suitable combinations of Lewis acids with protic acids are tetrafluoroboric acid and hexafluoroboric acid (HBF ₄ and HBF ₆ ). Other suitable anions are anions which obviously do not have a stable conjugate acid, such as tetrahydrocarbylborate anions or carbonate anions. The borate anion may contain the same or different hydrocarbyl groups such as alkyl, aryl, aralkyl and cycloalkyl groups attached to the boron. Preference is given to tetraarylborates such as tetraphenylborate, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and tetrakis(perfluorophenyl)borate, and carbonate (B ₁₁ CH ₁₂ ^- ).

The source of anions can be an acid or a salt thereof from which anions can be derived. Further sources of anions are suitable Lewis acids such as halides, especially fluorides, of boron, tin, antimony, aluminum or arsenic. Boron trifluoride and boron pentafluoride are particularly suitable. Other suitable Lewis acids are hydrocarbylboranes. The hydrocarbyl borane may contain one hydrocarbyl group or two or three hydrocarbyl groups which are the same or different, such as alkyl, aryl, aralkyl and cycloalkyl groups, preferably aryl groups, attached to boron. They may also contain hydrocarbyloxy or hydroxyl groups or halogen atoms attached to boron. Examples of particularly suitable hydrocarbylboranes are triphenylborane, tris(perfluorophenyl)borane and tris[3,5-bis(trifluoromethyl)phenyl]borane. Other suitable compounds which can serve as sources of anions are aluminoxanes, especially methylaluminoxane and tert-butylaluminoxane.

The amount of the anion source is preferably such that it provides 0.5-50 equivalents of anions/gram-atom nickel, especially 0.1-25 equivalents of anions/gram-atom nickel. However, the amount of aluminoxane can be: the molar ratio of aluminum to nickel is 4000:1-10:1, preferably 2000:1-100:1, most preferably 500:1-200:1.

Suitable catalyst compositions have an activity of from 10 ^-7 to 10 ^-2 gram atoms of nickel per mole of ethylenically unsaturated compound to be copolymerized. Preferably, the amount is 10 ^-6 -10 ^-3 on the same basis.

Ethylenically unsaturated compounds useful as monomers in the copolymerization process of the present invention include compounds consisting only of carbon and hydrogen atoms as well as compounds also containing heteroatoms, such as unsaturated esters. Unsaturated hydrocarbons are preferred. Examples of suitable monomers are lower olefins, i.e. olefins containing 2 to 6 carbon atoms such as ethylene, propylene and butene-1, cycloalkenes such as cyclopentene, aromatic compounds such as styrene and α-methylstyrene, and vinyl esters such as vinyl acetate and vinyl propionate. Preference is given to ethylene and mixtures of ethylene with another alpha-olefin such as propylene or butene-1.

In general, the molar ratio of carbon monoxide to ethylenically unsaturated compound can be chosen within a wide range, for example from 1:50 to 20:1. Preferably, however, a molar ratio of 1:20 to 2:1 is used.

The process of the present invention is generally carried out under diluent conditions. Preference is given to using diluents in which the copolymers are insoluble or practically insoluble, so that they form a suspension. Recommended diluents are polar organic liquids such as acetone, ether, esters or amides. Preference is given to prophilic liquids such as monohydroxyethanol and dihydroxyethanol, 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 case the catalyst is typically applied by depositing on solid particulate matter or chemical bonds.

When using a diluent in which the formed copolymer forms a suspension, it is preferred that a solid particulate material has been suspended in the diluent prior to contacting the monomer with the catalyst composition. Suitable solid particulate materials are copolymers of silicon, polyethylene and carbon monoxide with ethylenically unsaturated compounds, preferably copolymers based on the same monomers as the copolymers to be prepared. The amount of solid particulate matter used is preferably 0.1-20 g, especially 0.5-10 g per 100 g of diluent.

Conditions for carrying out the process of the invention include the use of elevated temperature and pressure, such as at 20-100°C, especially 30-130°C, between 1-200 bar, especially 5-100 bar. Typically the carbon monoxide pressure is at least 1 bar.

The copolymer can be isolated from the polymerization mixture using conventional techniques. When a diluent is used, the copolymer can be isolated by filtration or by evaporation of the diluent. The copolymer can be refined to some extent by washing.

Suitable copolymers are produced in which the units derived from carbon monoxide and the units derived from the ethylenically unsaturated compound are arranged alternately or substantially alternately. Generally those skilled in the art will understand the term "substantially alternating" to mean that the molar ratio of units derived from carbon monoxide to units derived from ethylenically unsaturated compounds is higher than 35:65, especially higher than 40:60. This ratio is equal to 50:50 when the copolymers are arranged alternately.

In the high intrinsic viscosity number (LVN) or intrinsic viscosity of a copolymer, the LVN is indicative of high molecular weight. The LVN is calculated from the viscosity values measured at 60°C in m-cresol at different copolymer concentrations. Copolymers are preferably produced with an LVN in the range of 0.2-10 dl/g, especially 0.4-8 dl/g, more especially 0.6-6 dl/g. It is also preferred that the resulting copolymer has a melting point above 150°C as determined by differential scanning calorimetry (DSC). For example, alternating or substantially alternating linear copolymers of carbon monoxide and ethylene and linear copolymers of carbon monoxide, ethylene and another alpha-olefin fall into this category. It is particularly preferred to prepare linear alternating copolymers of carbon monoxide and ethylene or linear alternating copolymers of carbon monoxide, ethylene and another α-olefin, wherein the molar ratio of another α-olefin to ethylene is generally higher than 1:100, preferably 1:100-1:3, more preferably 1:50-1:5.

Furthermore, for practical reasons, the nickel content in the copolymer is generally higher than 0.01 ppmw relative to the weight of the copolymer. Preferably, the content of nickel relative to the weight of the copolymer in the prepared copolymer is 0.05-300 ppmw, especially 0.1-200 ppmw. The copolymer is substantially free, preferably free, of palladium. For those skilled in the art, "substantially free of palladium" means that the palladium content is lower than the value usually achieved when palladium-based catalysts are used in the copolymerization, for example, it is lower than 1 ppmw relative to the weight of the copolymer , especially below 0.1ppmw. On the other hand, if palladium is present, it is preferred that the weight ratio of palladium to nickel is less than 1:50, especially less than 1:100, most preferably even less than 1:200.

Preferably the copolymer is free or substantially free of inorganic cyanides. Substantially free of organic cyanide is understood to mean that the inorganic cyanide content of the copolymer, measured as weight of CN, is less than 10 ppm, especially less than 1 ppm, more particularly less than 0.1 ppm relative to the weight of the copolymer. The cyanide content of the copolymer can be determined by introducing cyanide into an aqueous solution, for example by dissolving the copolymer in a suitable polar solvent such as hexafluoroisopropanol and adding water, which can then be determined using standard methods cyanide content in the.

The invention will be illustrated by the following examples of the preparation of linear alternating carbon monoxide/olefin copolymers. Example 1

Carbon monoxide/ethylene copolymers were prepared as follows.

A catalyst solution consisting of 100 ml of methanol, 0.25 mmol of nickel(II) acetate, 1 mmol of trifluoroacetic acid, and 0.3 mmol of 1,2-bis(2-methoxyphenyl) was added to a stirred 200 ml autoclave. ) phosphino] ethane.

The air in the autoclave was evacuated, then it was pressurized to 20 bar with ethylene and 30 bar of carbon monoxide was added, ie a total of 50 bar of ethylene and carbon monoxide. The autoclave was then heated to 90°C. After 5 hours the polymerization was terminated by cooling to room temperature and the pressure was reduced. The copolymerized reactant powder was isolated by filtration, washed with methanol and dried under reduced pressure at 60°C under a nitrogen atmosphere.

13.5 g of a water-white copolymer were obtained with an LVN of 1.67 dl/g, corresponding to a number average molecular weight of about 25,000. Embodiment 2 (comparison)

A carbon monoxide/ethylene copolymer was prepared as described in Example 1 except that 0.3 mmol of 1,3-bis[bis(2-methoxyphenyl)phosphino]propane was used instead of 1,2-bis[bis(2-methoxy Phenyl) phosphino] ethane, the polymerization time was changed from 5 hours to 10 hours.

0.7 g of a yellow-white copolymer is obtained. Embodiment 3 (comparison)

A carbon monoxide/ethylene copolymer was prepared as described in Example 1 except that 1,2-bis[bis(2-methoxyphenyl)phosphino] was replaced by 0.3 mmol of 1,2-bis(diphenylphosphino)ethane Ethane, the polymerization time was changed from 5 hours to 10 hours.

0.6 g of a yellow-white copolymer is obtained. Embodiment 4 (contrast)

A carbon monoxide/ethylene copolymer was prepared as described in Example 1, except that 1,2-bis[bis(2-methoxyphenyl)phosphino]ethane was replaced by 0.3 mmol of 1,3-bis(diphenylphosphino)propane. alkane, the polymerization time was changed from 5 hours to 3 hours.

0.1 g of a yellow-white copolymer is obtained. Example 5

Carbon monoxide/ethylene copolymers were prepared as described in Example 1, with the following changes: (1) the catalyst solution consisted of 100 ml methanol,

     0.1 mmol nickel(II) acetate,

    0.2 mmol tetrafluoroboric acid, and

Composed of 0.12mmol 1,2-bis[bis(2-methoxyphenyl)phosphino]ethane, (2) the temperature was changed from 90°C to 100°C, and (3) the polymerization time was changed from 5 hours to 3 hours.

8 g of water-white copolymer were obtained with an LVN of 1.64 dl/g. Example 6

Carbon monoxide/ethylene copolymers were prepared as described in Example 1, with the following changes: (1) the catalyst solution consisted of 100 ml methanol,

     0.1 mmol nickel(II) acetate,

    0.2 mmol trifluoroacetic acid, and

0.12mmol 1,2-bis[bis(2-methoxyphenyl)phosphino]ethane, (2) temperature changed from 90°C to 100°C, (3) ethylene and The carbon monoxide was changed to 30 bar and 20 bar respectively, and (4) the polymerization time was changed from 5 hours to 1 hour.

4.5 g of a water-white copolymer were obtained with an LVN of 2.10 dl/g. Embodiment 7 (comparison)

A carbon monoxide/ethylene copolymer was prepared as described in Example 6, except that 0.1 mmol of cobalt(II) acetate was used instead of nickel(II) acetate in the catalyst solution, and the polymerization time was changed from 1 hour to 3 hours.

0.3 g of a yellow-white copolymer is obtained. Example 8

Carbon monoxide/ethylene copolymers were prepared as described in Example 1, with the following changes: (1) the catalyst solution consisted of 100 ml methanol,

     0.02mmol nickel(II) acetate,

  0.04 mmol trifluoroacetic acid, and

0.024 mmol 1,2-bis[bis(2-methoxyphenyl)phosphino]ethane, (2) temperature changed from 90°C to 100°C, (3) ethylene and The carbon monoxide was changed to 40 bar and 20 bar respectively, and (4) the polymerization time was changed from 5 hours to 1.5 hours.

6.0 g of a water-white copolymer were obtained with an LVN of 2.35 dl/g. Example 9

Carbon monoxide/ethylene copolymers were prepared as described in Example 1, with the following changes: (1) the catalyst solution consisted of 100 ml methanol,

     0.02mmol nickel(II) acetate,

  0.04 mmol trifluoroacetic acid, and

0.024 mmol 1,2-bis[bis(2-methoxyphenyl)phosphino]ethane, (2) temperature changed from 90°C to 50°C, (3) ethylene and The carbon monoxide was changed to 30 bar and 10 bar respectively, and (4) the polymerization time was changed from 5 hours to 0.12 hours.

3.5 g of a water-white copolymer were obtained with an LVN of 5.95 dl/g. Example 10

Carbon monoxide/ethylene copolymers were prepared as described in Example 1, with the following changes: (1) the catalyst solution consisted of 100 ml methanol,

    0.1 mmol nickel(II) acetate, and

0.12 mmol 1,2-bis[bis(2-methoxyphenyl)phosphino]ethane composition, (2) ethylene and carbon monoxide added at pressures of 20 bar and 30 bar were changed to 40 bar and 10 bar respectively, (3) Carbon monoxide at a pressure of 10 bar was added at three time points after the start of the polymerization, namely 0.5, 1.0 and 1.5 hours, and (4) the polymerization time was changed from 5 hours to 2.5 hours.

11 g of a water-white copolymer were obtained with an LVN of 4.1 dl/g.

Claims (14)

1. catalyst composition, its based on (a) a kind of Ni positive ion source and (b) general formula be R ¹R ²M ¹-R-M ²R ³R ⁴(I) bidentate ligand, wherein M ¹And M ²Represent phosphorus, nitrogen, arsenic or antimony independently of one another, R ¹, R ², R ³And R ⁴The alkyl that representative independently of one another replaces arbitrarily, condition is R ¹, R ², R ³And R ⁴In have at least one to represent substituted aryl, R represents divalent abutment, this abutment is made up of two bridge atoms at most.

2. catalyst composition as claimed in claim 1 is characterized in that Ni positive ion source comprises the compound of nickel salt or nickel (0) and organic ligand chelating.

3. catalyst composition as claimed in claim 1 or 2 is characterized in that: the M of general formula (I) bidentate ligand ¹And M ²Phosphor atom, R ¹And R ²In have one at least, R ³And R ⁴In also have at least one to represent the polar substitution aryl, be typically R ¹, R ², R ³And R ⁴Each all represents the polar substitution aryl.

4. catalyst composition as claimed in claim 3 is characterized in that: the polar substitution aryl is at M ¹Or M ²The phenyl that replaces of ortho position alkoxy, particularly methoxyl group.

5. as each described catalyst composition among the claim 1-4, it is characterized in that: divalent abutment R is 1,2-alkylidene group, preferred ethylidene (CH ₂-CH ₂-).

6. as each described catalyst composition among the claim 1-5, it is characterized in that: the amount of general formula (I) bidentate ligand is selected from 0.5-1.5 moles per gram atom nickel.

7. as each described method among the claim 1-6, it is characterized in that: this catalyst composition is based on as the negative ion source of added ingredients, it is selected from negatively charged ion, tetraalkyl borate anion and the anion, carbonate source of protophilia acid, or be selected from Lewis acid and aikyiaiurnirsoxan beta, the preferred add-on of this negatively charged ion is 1-25 equivalent/grammeatom nickel, condition is that preferably to make the mol ratio of aluminium and nickel be 2000 to the consumption of aikyiaiurnirsoxan beta: 1-100: 1, particularly 500: 1-200: 1.

8. the preparation method of the multipolymer of carbon monoxide and alefinically unsaturated compounds is included in as making the monomer contact under the situation that each described catalyst composition exists among the claim 1-7.

9. method as claimed in claim 8 is characterized in that: alefinically unsaturated compounds is the mixture of unsaturated hydrocarbons such as ethene or ethene and another kind of alpha-olefin.

10. method as claimed in claim 8 or 9, it is characterized in that: contact is carried out in the insoluble therein or in fact insoluble thinner of multipolymer, as methyl alcohol or ethanol, so that they form suspension, the amount of the catalyst composition that uses is: with respect to every mole with the polymeric alefinically unsaturated compounds, the amount of the nickel of existence is 10 ^-7-10 ^-2Grammeatom, preferred 10 ^-6-10 ^-3Grammeatom, and the carbon monoxide of using is 1 with the mol ratio of alefinically unsaturated compounds: 50-20: 1, preferred 1: 20-2: 1, and temperature is between 20-200 ℃, and particularly between 30-130 ℃, pressure is between the 1-200 crust, particularly between 5-100 clings to.

11. the straight copolymer of carbon monoxide and alefinically unsaturated compounds, this multipolymer comprise with respect to the maximum 500ppmw nickel of this multipolymer weight, and this multipolymer does not contain or do not contain palladium in fact.

12. multipolymer as claimed in claim 11 is characterized in that: the nickel content of this multipolymer is 0.05-300ppmw, particularly 0.1-200ppmw with respect to the weight of multipolymer.

13. as claim 11 or 12 described multipolymers, it is characterized in that: if having palladium and/or inorganic cyanide to exist, then palladium content calculates as the weight of CN with inorganic cyanide content less than 1ppm, it is less than 10ppm, and the two all is for the weight of polymkeric substance.

14. as each described multipolymer among the claim 11-13, it is characterized in that: this multipolymer is the straight chain alternating copolymer of carbon monoxide and ethene or the straight chain alternating copolymer of carbon monoxide, ethene and another kind of alpha-olefin.