A water-soluble polyketone catalyst ligand and its synthesis method

Abstract

The present invention provides a water-soluble polyketone catalyst ligand and a synthesis method thereof; the synthesis method comprises the following steps: 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane is subjected to a hydrolysis reaction and a sulfonation reaction in sequence to obtain a water-soluble polyketone catalyst ligand; or 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane is subjected to a hydrolysis reaction, a sulfonation reaction and a neutralization reaction in sequence to obtain a water-soluble polyketone catalyst ligand. Compared with the prior art, the present invention selects specific raw materials and synthesizes water-soluble polyketone catalyst ligands according to specific process steps to achieve overall good interaction. The synthesis method has a simple and efficient synthesis route, a high yield, few by-products, a novel synthesized ligand structure, and a catalyzed polyketone polymerization process that is economical, safe, green and environmentally friendly, with little reactor fouling, a high apparent density of the obtained polyketone product, and a catalytic activity of up to 18 to 25 kg (g h). ‑1 .

Description

Technical Field

[0001] The present invention relates to the technical field of fine chemical industry, and more particularly to a water-soluble polyketone catalyst ligand and a synthesis method thereof. Background Art

[0002] Polyketones (POKs) are novel green polymer materials synthesized from carbon monoxide and olefins (ethylene, propylene, and styrene). They exhibit photodegradation and biodegradability and are amenable to further chemical modification. Their excellent and broad performance profile makes them a "natural" thermoplastic engineering plastic. The synthesis of polyketones has evolved through the development of three primary catalytic systems: free radical initiation, γ-ray induced initiation, and Group VIII transition metal initiation. Group VIII transition metal catalysis, comprising a transition metal compound, a bidentate ligand, a strong acid and its anion, an oxidant, a cocatalyst, and a solvent, has been predominant to date. Initially, the palladium acetate / 1,3-bis[bis(2-methoxyphenyl)phosphino]propane / trifluoroacetic acid catalytic system developed by Shell demonstrated high catalytic activity for the polymerization of ethylene and carbon monoxide polyketones. The development of novel bidentate ligands within these polymerization catalytic systems has played a crucial role in enhancing the catalytic activity of polyketone polymerization. Since then, ST Pharmaceuticals has developed bidentate ligands such as 2,2-dimethyl-1,3-bis[bis(2-methoxyphenyl)phosphino]propane, 3,3-bis[bis-(2-methoxyphenyl)phosphinomethyl]-1,5-dioxa-spiro[5,5]undecane, and ((2,2-dimethyl-1,3-dioxane-5,5-diyl))bis(bis(2-methoxyphenyl)phosphine). These ligands have shown higher catalytic activity than 1,3-bis[bis(2-methoxyphenyl)phosphino]propane in the synthesis of polyketones. However, the catalysts synthesized with these ligands are suitable for polymerization reaction processes using mostly alcohol solvents, with methanol being the most effective. However, alcohol solvents are flammable and explosive, which poses a significant safety risk in industrialized polymerization processes. In addition, a large amount of methanol will be adsorbed during the polyketone polymerization process, causing the polyketone particles to be wrapped with a large number of methanol molecules during their growth, resulting in a large number of cavities inside the polyketone powder particles and a low apparent density, which in turn causes reactor fouling. Water has great advantages as an economical, safe, green and environmentally friendly solvent to replace alcohol solvents in polymerization processes. In recent years, there have been many reports on water-soluble polyketone catalyst ligands, such as 1,3-bis[di(2-methoxy-5-sulfonic acid phenyl) phosphino] propane and 1,3-bis[di(2-methoxy-3-sulfonic acid phenyl) phosphino] propane. However, the catalytic activity of the currently reported water-soluble ligands in polyketone polymerization applications is difficult to match the several types of non-water-soluble ligands mentioned above. Therefore, the development of a water-soluble ligand with high catalytic activity has become an urgent problem to be solved. Summary of the Invention

[0003] In view of this, the object of the present invention is to provide a water-soluble polyketone catalyst ligand and a synthesis method thereof. The synthesis method has a simple and efficient synthesis route, high yield, few by-products, and a novel structure of the synthesized ligand. The catalyzed polyketone polymerization process is economical, safe, green and environmentally friendly, with little reactor fouling. The obtained polyketone product has a high apparent density and a catalytic activity of up to 18 to 25 kg·(g·h) -1 .

[0004] The present invention provides a water-soluble polyketone catalyst ligand having a structure shown in formula (I):

[0005] Formula (I);

[0006] In formula (I), X and Y are independently selected from H, Na, K or other alkali metal ions.

[0007] Preferably, X is H, Na or K, and at most ¾ of X are H.

[0008] Preferably, Y is H, Na or K, and at most 1 / 2 of Y is H.

[0009] The present invention also provides a method for synthesizing the water-soluble polyketone catalyst ligand described in the above technical solution, comprising the following steps:

[0010] 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane is subjected to a hydrolysis reaction and a sulfonation reaction in sequence to obtain a water-soluble polyketone catalyst ligand;

[0011] or,

[0012] 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl1,3-dioxane is subjected to hydrolysis reaction, sulfonation reaction and neutralization reaction in sequence to obtain a water-soluble polyketone catalyst ligand.

[0013] Preferably, the hydrolysis reaction process undergoes a ketal hydrolysis reaction under the action of acid and water; the acid is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, formic acid, acetic acid, and oxalic acid.

[0014] Preferably, the process of the hydrolysis reaction is specifically as follows:

[0015] 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl1,3-dioxane is dispersed in an ethanol and water system to obtain a suspension of 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl1,3-dioxane; acid is then added to hydrolyze the mixture to obtain 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol.

[0016] Preferably, the hydrolysis reaction temperature is 25° C. to 80° C., and the time is 1 h to 6 h.

[0017] Preferably, the sulfonation reaction is carried out in the presence of a sulfonating agent; the sulfonating agent includes concentrated sulfuric acid, fuming sulfuric acid or a mixed acid system of other acids and concentrated sulfuric acid.

[0018] Preferably, the sulfonation reaction temperature is 25° C. to 70° C., and the time is 12 h to 48 h.

[0019] Preferably, the neutralization reaction is carried out in the presence of a neutralizing agent; the neutralizing agent is an alkali metal base or an alkaline alkali metal carbonate.

[0020] The present invention provides a water-soluble polyketone catalyst ligand and a synthesis method thereof. The synthesis method comprises the following steps: subjecting 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane to a hydrolysis reaction and a sulfonation reaction in sequence to obtain a water-soluble polyketone catalyst ligand; or, subjecting 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane to a hydrolysis reaction, a sulfonation reaction, and a neutralization reaction in sequence to obtain a water-soluble polyketone catalyst ligand. Compared with the prior art, the present invention selects specific raw materials and synthesizes the water-soluble polyketone catalyst ligand according to specific process steps, achieving better overall interaction. The synthesis method has a simple and efficient synthesis route, high yield, few by-products, and a novel structure of the synthesized ligand. The catalyzed polyketone polymerization reaction process is economical, safe, green, and environmentally friendly, with little reactor fouling. The resulting polyketone product has a high apparent density and a catalytic activity of up to 18 to 25 kg·(g·h). -1 . DETAILED DESCRIPTION

[0021] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0022] The present invention provides a water-soluble polyketone catalyst ligand having a structure shown in formula (I):

[0023] Formula (I);

[0024] In formula (I), X and Y are independently selected from H, Na, K or other alkali metal ions.

[0025] In the present invention, the water-soluble polyketone catalyst ligand contains multiple sulfonic acid groups to increase its water solubility. At the same time, its catalytic activity is not reduced and is comparable to that of water-insoluble ligands (see comparative experimental examples), and is higher than other water-soluble ligands in the prior art.

[0026] In the present invention, in formula (I), X is selected from H, Na, K or other alkali metal ions, preferably H, Na or K, and at most ¾ of X is H.

[0027] In the present invention, in formula (I), Y is selected from H, Na, K or other alkali metal ions, preferably H, Na or K, and at most 1 / 2 of Y is H.

[0028] In a preferred embodiment of the present invention, when all X are Na, K or other alkali metal ions, Y is H, Na or K, and at most 1 / 2 of Y is H.

[0029] In summary, the water-soluble polyketone catalyst ligand includes 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate and 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate Y, preferably: 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate; 1 / 4 of X is Na, 3 / 4 of X is H 2,2-bis[bis-(2-methoxy- 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate; 2 / 4 of X is Na, 2 / 4 of X is H; 3 / 4 of X is Na, 1 / 4 of X is H, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate; 4 / 4 of X is Na, 4 / 4 of Y is Na, 1 / 2 of Y is Na, 1 / 2 of Y is H, 2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl) phosphinomethyl]-propylene glycol sulfate Y; 4 / 4 of X is Na, 2 / 2 of Y is Na, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl) phosphinomethyl]-propylene glycol sulfate Y; 1 / 4 of X is K, 3 / 4 of X is H, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl) phosphinomethyl]-propylene glycol sulfate; 2 / 4 of X is K, 2 / 4 of X is H, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl) phosphinomethyl]-propylene glycol sulfate; 3 / 4 of X is K, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate, wherein 1 / 4 of X is H; 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate, wherein 4 / 4 of X is K; 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate Y, wherein 4 / 4 of X is K, 1 / 2 of Y is K, and 1 / 2 of Y is H; 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate Y, wherein 4 / 4 of X is K and 2 / 2 of Y is K.

[0030] It has a novel structure, a simple and efficient synthesis route, a high yield, and few by-products. The catalytic polyketone polymerization process is economical, safe, green and environmentally friendly, and the product has a high apparent density and high catalytic activity.

[0031] The present invention also provides a method for synthesizing the water-soluble polyketone catalyst ligand described in the above technical solution, comprising the following steps:

[0032] 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane is subjected to a hydrolysis reaction and a sulfonation reaction in sequence to obtain a water-soluble polyketone catalyst ligand;

[0033] or,

[0034] 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl1,3-dioxane is subjected to hydrolysis reaction, sulfonation reaction and neutralization reaction in sequence to obtain a water-soluble polyketone catalyst ligand.

[0035] In one aspect, the present invention sequentially hydrolyzes and sulfonates 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane to obtain a water-soluble polyketone catalyst ligand; the method specifically comprises the following steps:

[0036] a) hydrolysis of 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane to obtain 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol;

[0037] b) Sulfonation of the above 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol to obtain 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol sulfate.

[0038] On the other hand, 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane is subjected to a hydrolysis reaction, a sulfonation reaction, and a neutralization reaction in sequence to obtain a water-soluble polyketone catalyst ligand; namely:

[0039] c) neutralizing the 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol sulfate to obtain 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate, which may specifically include partially neutralized and fully neutralized sulfonate products, i.e., in formula (I), X is partially or entirely an alkali metal ion; further, after X is completely neutralized to form an alkali metal ion, continuing the neutralization reaction to obtain 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate Y.

[0040] In the present invention, the hydrolysis reaction preferably involves a ketal hydrolysis reaction under the action of an acid and water; the acid is preferably selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, formic acid, acetic acid, and oxalic acid, more preferably hydrochloric acid, phosphoric acid, or trifluoroacetic acid. The source of the acid is not particularly limited, and commercially available products known to those skilled in the art may be used.

[0041] In the present invention, the process of the hydrolysis reaction is preferably specifically as follows:

[0042] 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl1,3-dioxane is dispersed in an ethanol and water system to obtain a suspension of 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl1,3-dioxane; acid is then added to hydrolyze the mixture to obtain 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol.

[0043] In the present invention, the molar ratio of the 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane to the acid is preferably 1:(1-10), more preferably 1:(1-6); as the amount of acid increases, the reaction time of the hydrolysis reaction will be correspondingly shortened, and the reaction temperature can also be appropriately lowered, but the excess acid needs to be neutralized after the hydrolysis reaction is completed.

[0044] In the present invention, the hydrolysis reaction is preferably carried out under anhydrous and oxygen-free conditions; the acid is added slowly, and in order to avoid a violent reaction of concentrated acid into water, the addition rate should be such as to control the temperature rise of the reaction system to 5°C.

[0045] In the present invention, the temperature of the hydrolysis reaction is preferably 25°C to 80°C, specifically 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, more preferably 40°C to 60°C; an increase in temperature will significantly accelerate the reaction process of the hydrolysis reaction, but when the temperature is higher than 80°C, the yield of 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol will decrease. When the temperature is lower than 25°C, the hydrolysis reaction proceeds too slowly; the time of the hydrolysis reaction is preferably 1h to 6h, specifically 1h, 2h, 3h, 4h, 5h, 6h; as the reaction proceeds, the reaction solution gradually becomes clear.

[0046] In the present invention, after the hydrolysis reaction is completed, the following post-treatment technical means are preferably used to obtain 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol:

[0047] After the hydrolysis reaction is completed, ethanol is removed under reduced pressure, and a saturated sodium bicarbonate solution is added to the residual liquid until it becomes neutral, and a large amount of white solid precipitates. The residual liquid is extracted with dichloromethane several times, and the organic phases are combined, dried over anhydrous magnesium sulfate, filtered, and the solvent is dried by spin drying. The remaining oily solid is recrystallized with ethyl acetate and petroleum ether to obtain a white 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol solid.

[0048] Then, the present invention performs a sulfonation reaction on the 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol to obtain 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl)phosphinomethyl]-propylene glycol sulfate.

[0049] In the present invention, the sulfonation reaction is preferably carried out in the presence of a sulfonating agent; the sulfonating agent preferably comprises concentrated sulfuric acid, fuming sulfuric acid, or a mixed acid system of other acids and concentrated sulfuric acid, wherein the mass concentration of the concentrated sulfuric acid is preferably 92% to 98%, and the content of sulfur trioxide in the fuming sulfuric acid is preferably 20% to 30%, more preferably concentrated sulfuric acid.

[0050] In the present invention, during the sulfonation reaction, the molar ratio of 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol to the sulfonation reagent is preferably 1:(10-60); to avoid a violent initial reaction, 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol is added to the sulfonation reagent in batches.

[0051] In the present invention, the temperature of the sulfonation reaction is preferably 25°C to 70°C, specifically 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, and the time is preferably 12h to 48h, specifically 12h, 16h, 18h, 24h, 36h, 48h.

[0052] In the present invention, after the sulfonation reaction is completed, the following post-treatment technical means are preferably used to obtain 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl)phosphinomethyl]-propylene glycol sulfate:

[0053] After the sulfonation reaction is completed, the reaction solution is poured into ice water in batches, and then cooled to below 4°C for crystallization. After filtration, a white solid is obtained, which is washed once with n-butyl ketone and diethyl ether respectively, and then vacuum dried to obtain 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl)phosphinomethyl]-propylene glycol sulfate.

[0054] In the present invention, the above-mentioned 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate is further neutralized to obtain 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate and 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate Y.

[0055] In the present invention, the neutralization reaction is preferably carried out in the presence of a neutralizing agent; the neutralizing agent is preferably an alkali metal base or an alkaline alkali metal carbonate, specifically one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. The present invention has no particular limitation on the source of the neutralizing agent, and commercially available products known to those skilled in the art may be used.

[0056] In the present invention, the molar ratio of the 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate to the neutralizing agent is preferably 1:(1-6), more preferably 1:(2-6); preferably, the 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate is first dissolved in water to obtain an aqueous solution of 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate, and then the neutralizing agent is added to the reaction solution in batches.

[0057] In the present invention, the neutralization reaction temperature is preferably 15° C. to 40° C., and the time is 0.1 h to 1 h.

[0058] In the present invention, after the neutralization reaction is completed, the following post-treatment technical means are preferably used to obtain a water-soluble polyketone catalyst ligand:

[0059] The mixture was dehydrated under reduced pressure, methanol was added to the concentrate, and after sufficient stirring, a suspension of precipitated sodium sulfate was obtained, which was filtered and the filtrate was spin-dried. Then, methanol was added to the residual solid again, the residual sodium sulfate was filtered out, and the filtrate was further spin-dried to obtain a white solid, which was vacuum dried to obtain a water-soluble polyketone catalyst ligand.

[0060] The present invention provides a method for synthesizing a water-soluble polyketone polymerization catalyst ligand. The water-soluble polyketone catalyst ligand comprises 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate and 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate Y; wherein the water-soluble polyketone catalyst ligand comprises 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate Y. The synthesis method of 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate comprises the following steps: a) hydrolysis of 5,5-bis[bis-(2-methoxyphenyl) phosphinomethyl]-2,2-dimethyl 1,3-dioxane to obtain 2,2-bis[bis-(2-methoxyphenyl) phosphinomethyl]-propylene glycol; b) the 2,2-bis[bis-(2-methoxyphenyl) phosphinomethyl]-propylene glycol is synthesized by a reaction of: The synthesis method of 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate further comprises: further neutralizing 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate to obtain 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate; The synthesis method of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate Y further comprises: further neutralizing 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate to obtain 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate Y. Experimental results show that the water-soluble polyketone polymerization catalyst ligand provided by the present invention has a novel structure, a simple and efficient synthesis route, few by-products, and a high yield (>86%). The catalyzed polyketone polymerization reaction process is economical, safe, green and environmentally friendly, and the product has an apparent density of >0.26g / cm 3 , catalytic activity is as high as 18~25kg·(g·h) -1 .

[0061] The present invention provides a water-soluble polyketone catalyst ligand and a synthesis method thereof. The synthesis method comprises the following steps: subjecting 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane to a hydrolysis reaction and a sulfonation reaction in sequence to obtain a water-soluble polyketone catalyst ligand; or, subjecting 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane to a hydrolysis reaction, a sulfonation reaction, and a neutralization reaction in sequence to obtain a water-soluble polyketone catalyst ligand. Compared with the prior art, the present invention selects specific raw materials and synthesizes the water-soluble polyketone catalyst ligand according to specific process steps, achieving better overall interaction. The synthesis method has a simple and efficient synthesis route, high yield, few by-products, and a novel structure of the synthesized ligand. The catalyzed polyketone polymerization reaction process is economical, safe, green, and environmentally friendly, with little reactor fouling. The resulting polyketone product has a high apparent density and a catalytic activity of up to 18 to 25 kg·(g·h). -1 .

[0062] In order to further illustrate the present invention, the following examples are provided for detailed description. The raw materials used in the following examples of the present invention are specifically sourced from commercial sources or homemade; wherein, the method for preparing 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane is not particularly limited, and the compound can be prepared by a typical method in the relevant field, (a) under a nitrogen atmosphere, bis(2-methoxyphenyl)phosphine and dimethyl sulfoxide (DMSO) are placed in a reaction vessel, and then sodium hydride is added at room temperature, and then the mixture is stirred; (b) 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane is added. (c) adding 2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene)bis(bis(2-methoxyphenyl)phosphine) to the obtained mixture, and then stirring to react; (d) adding toluene and water, and after separating the oil layer from the water, washing the oil layer with water, and then drying with anhydrous sodium sulfate, thereby performing reduced pressure filtration and reduced pressure concentration; and (e) recrystallizing the residue with methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine); the specific method can be referred to patent CN105518056B.

[0063] Example 1

[0064] A method for synthesizing a water-soluble polyketone polymerization catalyst ligand, 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl)phosphinomethyl]-propylene glycol sulfate, is provided. The synthetic route is as follows:

[0065] .

[0066] The specific steps are:

[0067] (1) Preparation of 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol:

[0068] Under anhydrous and oxygen-free conditions, 5g (0.0079mol) of 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane was added to 40mL of ethanol and 10ml of water, stirred to fully disperse, and 3ml of hydrochloric acid (36.5%) (0.0354mol) was slowly added. The addition rate was suitable for controlling the temperature rise of the reaction system to be below 5°C. After the addition was completed, the reaction system was heated to 40°C and the reaction was continued for 5h. As the reaction proceeded, the reaction solution gradually became clear. 31 P NMR tracking: After the hydrolysis was completed, ethanol was removed under reduced pressure, and saturated sodium bicarbonate solution was added to the residual liquid to pH = 7, and a large amount of white solid precipitated. The residual liquid was extracted three times with dichloromethane, and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was dried by spin drying. The remaining oily solid was recrystallized with ethyl acetate: petroleum ether = 1:3 (40 ml), to obtain 4.39 g of white 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol solid, with a yield of 93.8%.

[0069] (2) Preparation of 2,2-bis[bis-(2-methoxy-5-sulfonylphenyl)phosphinomethyl]-propylene glycol sulfate:

[0070] Under anhydrous and oxygen-free conditions, 4.39 g (0.0074 mol) of 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol was slowly added in batches to 20 ml (0.368 mol) of concentrated sulfuric acid. The addition rate was suitable for controlling the temperature rise of the system to be below 5°C. After the addition was completed, the room temperature was maintained at 25°C and the reaction was continued for 18 hours. 31 After the reaction was completed, the reaction solution was poured into 300 ml of ice water in batches, and then cooled to below 4°C for crystallization. After filtration, a white solid was obtained. The solid was washed once with 20 ml of n-butyl ketone and 20 ml of ether, respectively, and dried in vacuo at 80°C to obtain 7.23 g of solid with a yield of 91.06%.

[0071] NMR data: 31 P NMR (121.5 MHz, Methanol-d3): δ-2.49; 1 H NMR (400 MHz, Methanol-d6): δ9.35 (s, 2H, SO3H), 8.86 (s, 2H, SO3H), 7.91 (m, 4H, CH), 7.82(m, 4H, CH), 7.03 (m, 4H, CH), 3.88(s, 4H, OCH2), 3.72(s,12H,OCH3), 2.84(d,4H,PCH2).

[0072] Example 2

[0073] A method for synthesizing a water-soluble polyketone polymerization catalyst ligand, 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl)phosphinomethyl]-propylene glycol sulfate, is provided. The synthetic route is as follows:

[0074] .

[0075] The specific steps are:

[0076] (1) Preparation of 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol:

[0077] Under anhydrous and oxygen-free conditions, 5g (0.0079mol) of 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane was added to 40mL of ethanol and 10ml of water, and stirred to fully disperse the mixture. 3ml of hydrochloric acid (36.5%) (0.0354mol) was slowly added at a rate that controlled the temperature rise of the reaction system to be below 5°C. After the addition was completed, the reaction system was heated to 55°C and the reaction was continued for 4h. As the reaction proceeded, the reaction solution gradually became clear. 31 P NMR tracking: After the hydrolysis was completed, ethanol was removed under reduced pressure, and saturated sodium bicarbonate solution was added to the residual liquid to pH = 7, and a large amount of white solid precipitated. The residual liquid was extracted three times with dichloromethane, and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was spin-dried. The remaining oily solid was recrystallized with ethyl acetate: petroleum ether = 1:3 (40 ml), to obtain 4.26 g of white 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol solid, with a yield of 91.0%.

[0078] (2) Preparation of 2,2-bis[bis-(2-methoxy-5-sulfonylphenyl)phosphinomethyl]-propylene glycol sulfate:

[0079] Under anhydrous and oxygen-free conditions, 4.26 g (0.00719 mol) of 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol was slowly added in batches to 12 ml (0.22 mol) of concentrated sulfuric acid. The addition rate was suitable for controlling the temperature rise of the system to be below 5°C. After the addition was completed, the room temperature was maintained at 25°C and the reaction was continued for 36 hours. 31 After the reaction was completed, the reaction solution was poured into 200 ml of ice water in batches, and then cooled to below 4°C for crystallization. After filtration, a white solid was obtained. The solid was washed once with 20 ml of n-butyl ketone and ether, respectively, and then dried in vacuo at 80°C to obtain 7 g of the solid with a yield of 90.7%.

[0080] Example 3

[0081] A method for synthesizing a water-soluble polyketone polymerization catalyst ligand, 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl)phosphinomethyl]-propylene glycol sulfate, is provided. The synthetic route is as follows:

[0082] .

[0083] The specific steps are:

[0084] (1) Preparation of 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol:

[0085] Under anhydrous and oxygen-free conditions, 5g (0.0079mol) of 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane was added to 40mL of ethanol and 10ml of water, and stirred to fully disperse the mixture. 2ml of phosphoric acid (0.038mol) was slowly added at a rate that controlled the temperature rise of the reaction system to be below 5°C. After the addition, the reaction system was heated to 55°C and the reaction was continued for 4h. As the reaction proceeded, the reaction solution gradually became clear. 31 P NMR tracking: After the hydrolysis was completed, ethanol was removed under reduced pressure, and saturated sodium bicarbonate solution was added to the residual liquid to pH = 7, a large amount of white solid precipitated, and the residual liquid was extracted three times with dichloromethane, and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was spin-dried. The remaining oily solid was recrystallized with ethyl acetate: petroleum ether = 1:3 (40 ml), to obtain 4.31 g of white 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol solid, with a yield of 92.06%.

[0086] (2) Preparation of 2,2-bis[bis-(2-methoxy-5-sulfonylphenyl)phosphinomethyl]-propylene glycol sulfate:

[0087] Under anhydrous and oxygen-free conditions, 4.31 g (0.00727 mol) of 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol was slowly added in batches to 20 ml of 20% fuming concentrated sulfuric acid. The addition rate was appropriate to control the temperature rise of the system to be below 5°C. After the addition was completed, the room temperature was maintained at 25°C and the reaction was continued for 16 hours. 31 After the reaction was completed, the reaction solution was poured into 200 ml of ice water in batches, and then cooled to below 4°C for crystallization. After filtration, a white solid was obtained. The solid was washed once with 20 ml of n-butyl ketone and ether, respectively, and then dried in vacuo at 80°C to obtain 7.03 g of solid with a yield of 90.12%.

[0088] Example 4

[0089] A method for synthesizing a water-soluble polyketone polymerization catalyst ligand, 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl)phosphinomethyl]-propylene glycol sulfate, is provided. The synthetic route is as follows:

[0090] .

[0091] The specific steps are:

[0092] (1) Preparation of 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol:

[0093] Under anhydrous and oxygen-free conditions, 5g (0.0079mol) of 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane was added to 40mL of ethanol and 10ml of water, and stirred to fully disperse the mixture. 5ml of trifluoroacetic acid (0.038mol) was slowly added at a rate that controlled the temperature rise of the reaction system to be below 5°C. After the addition, the reaction system was heated to 45°C and the reaction was continued for 4h. As the reaction proceeded, the reaction solution gradually became clear. 31 P NMR tracking: After the hydrolysis was completed, ethanol was removed under reduced pressure, and saturated sodium bicarbonate solution was added to the residual liquid to pH = 7, and a large amount of white solid precipitated. The residual liquid was extracted three times with dichloromethane, and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was dried by spin drying. The remaining oily solid was recrystallized with ethyl acetate: petroleum ether = 1:3 (40 ml), to obtain 4.24 g of white 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol solid, with a yield of 90.6%.

[0094] (2) Preparation of 2,2-bis[bis-(2-methoxy-5-sulfonylphenyl)phosphinomethyl]-propylene glycol sulfate:

[0095] Under anhydrous and oxygen-free conditions, 4.24 g (0.00715 mol) of 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol was slowly added in batches to 12 ml of 30% fuming concentrated sulfuric acid. The addition rate was appropriate to control the temperature rise of the system to be below 5°C. After the addition was completed, the room temperature was maintained at 25°C and the reaction was continued for 16 hours. 31 After the reaction was completed, the reaction solution was poured into 200 ml of ice water in batches, and then cooled to below 4°C for crystallization. After filtration, a white solid was obtained. The solid was washed once with 20 ml of n-butyl ketone and 20 ml of ether, respectively, and dried in vacuo at 80°C to obtain 6.85 g of the solid with a yield of 89.3%.

[0096] Example 5

[0097] A method for synthesizing a water-soluble polyketone polymerization catalyst ligand, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate, is provided. The synthetic route is as follows:

[0098] .

[0099] The specific steps are:

[0100] 5.36 g (0.005 mol) of 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate was added to 30 ml of water. 0.2 g of sodium hydroxide was slowly added to the above solution in batches under stirring. The addition rate was preferably such that the temperature rise of the reaction system was controlled to be below 5°C. After the addition was completed, the reaction was continued with stirring at room temperature at 25°C for 0.5 h. The solution was dehydrated under reduced pressure. 20 ml of methanol was added to the concentrate and stirred thoroughly to obtain a suspension of precipitated sodium sulfate. The suspension was filtered and the filtrate was dried by rotary evaporation. 20 ml of methanol was added to the residual solid again to filter out the residual sodium sulfate. The filtrate was further dried by rotary evaporation to obtain a white solid. After vacuum drying at 60°C, 5.19 g of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl) phosphinomethyl]-propylene glycol sulfate was obtained, wherein 1 / 4 X is Na and 3 / 4 X is H, with a yield of 94.8%.

[0101] Example 6

[0102] A method for synthesizing a water-soluble polyketone polymerization catalyst ligand, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate, is provided. The synthetic route is as follows:

[0103] .

[0104] The specific steps are:

[0105] 5.36 g (0.005 mol) of 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate was added to 30 ml of water. 0.56 g of potassium hydroxide was slowly added to the above solution in batches under stirring. The addition rate was suitable for controlling the temperature rise of the reaction system to be below 5°C. After the addition was completed, the reaction was continued with stirring at room temperature at 25°C for 0.5 h. The solution was dehydrated under reduced pressure. 20 ml of methanol was added to the concentrate and stirred thoroughly to obtain a suspension of precipitated sodium sulfate. The suspension was filtered and the filtrate was dried by rotary evaporation. 20 ml of methanol was added to the residual solid again to filter out the residual sodium sulfate. The filtrate was further dried by rotary evaporation to obtain a white solid. After vacuum drying at 60°C, 5.42 g of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl) phosphinomethyl]-propylene glycol sulfate was obtained, wherein 2 / 4 X was K and 2 / 4 X was H, with a yield of 94.3%.

[0106] Example 7

[0107] A method for synthesizing a water-soluble polyketone polymerization catalyst ligand, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate, is provided. The synthetic route is as follows:

[0108] .

[0109] The specific steps are:

[0110] 5.36 g (0.005 mol) of 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate was added to 30 ml of water. 1.59 g of sodium carbonate was slowly added to the above solution in batches under stirring. The addition rate was preferably such that the temperature rise of the reaction system was controlled to be below 5°C. After the addition was completed, the reaction was continued with stirring at room temperature at 25°C for 0.5 h. The solution was dehydrated under reduced pressure. 20 ml of methanol was added to the concentrate and stirred thoroughly to obtain a suspension of precipitated sodium sulfate. The suspension was filtered and the filtrate was dried by rotary evaporation. 20 ml of methanol was added to the residual solid again to filter out the residual sodium sulfate. The filtrate was further dried by rotary evaporation to obtain a white solid. After vacuum drying at 60°C, 5.35 g of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl) phosphinomethyl]-propylene glycol sulfate was obtained, wherein 3 / 4 X is Na and 1 / 4 X is H, with a yield of 93.95%.

[0111] Example 8

[0112] A method for synthesizing a water-soluble polyketone polymerization catalyst ligand, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate, is provided. The synthetic route is as follows:

[0113] .

[0114] The specific steps are:

[0115] 5.36 g (0.005 mol) of 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate was added to 30 ml of water. 2.76 g of potassium bicarbonate was slowly added to the above solution in batches under stirring. The addition rate was suitable for controlling the temperature rise of the reaction system to be below 5°C. After the addition was completed, the reaction was continued with stirring at room temperature at 25°C for 0.5 h. The solution was dehydrated under reduced pressure, and 20 ml of methanol was added to the concentrate. After sufficient stirring, a suspension of precipitated sodium sulfate was obtained. The solution was filtered and the filtrate was dried by rotary evaporation. Then, 20 ml of methanol was added to the residual solid again to filter out the residual sodium sulfate. The filtrate was further dried by rotary evaporation to obtain a white solid. After vacuum drying at 60°C, 5.73 g of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate with 4 / 4 X being K was obtained, with a yield of 93.5%.

[0116] NMR data: 31 P NMR (121.5 MHz, Methanol-d3): δ-31.21; 1H NMR (400 MHz, Methanol-d6): δ8.90 (s, 2H, SO3H), 7.78 (m, 4H, CH), 7.54 (m, 4H, CH), 6.89 (m,4H, CH), 3.66 (s, 4H, OCH2), 3.42 (s,12H, OCH3), 2.39 (d, 4H, PCH2).

[0117] Example 9

[0118] A method for synthesizing a water-soluble polyketone polymerization catalyst ligand 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate Y, the synthetic route of which is as follows:

[0119] .

[0120] The specific steps are:

[0121] 5.36 g (0.005 mol) of 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate was added to 30 ml of water. 1 g of sodium hydroxide was slowly added to the above solution in batches under stirring. The addition rate was suitable for controlling the temperature rise of the reaction system to be below 5°C. After the addition was completed, the reaction was continued with stirring at room temperature at 25°C for 0.5 h. The solution was dehydrated under reduced pressure. 20 ml of methanol was added to the concentrate and stirred thoroughly to obtain a suspension of precipitated sodium sulfate. The suspension was filtered and the filtrate was dried by rotary evaporation. 20 ml of methanol was added to the residual solid again to filter out the residual sodium sulfate. The filtrate was further dried by rotary evaporation to obtain a white solid. After vacuum drying at 60°C, 5.45 g of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate Y was obtained, wherein 4 / 4 X is Na, 1 / 2 Y is Na, and 1 / 2 Y is H, with a yield of 92.15%.

[0122] Example 10

[0123] A method for synthesizing a water-soluble polyketone polymerization catalyst ligand 2,2-bis[bis-(2-methoxy-5-sodium sulfonate phenyl)phosphinomethyl]-propylene glycol sulfate Y, the synthetic route of which is as follows:

[0124] .

[0125] The specific steps are the same as Example 9, except that the amount of sodium hydroxide added is 1.2 g, to obtain 5.56 g of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate Y in which 4 / 4 X is Na and 2 / 2 Y is Na, with a yield of 92.3%.

[0126] NMR data: 31P NMR (121.5 MHz, Methanol-d3): δ-32.56; 1 H NMR (400 MHz, Methanol-d6): δ7.72 (m, 4H, CH), 7.74 (m, 4H, CH), 6.78 (m, 4H, CH), 3.62 (s,4H, OCH2), 3.45 (s,12H, OCH3), 2.38 (d, 4H, PCH2).

[0127] Through the above examples, a water-soluble polyketone polymerization catalyst ligand can be obtained, including 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate, and 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate Y; the specific structure is shown in the structure of the final product of the synthesis route. Polymerization experiments were carried out using the above ligand to prepare a catalyst (see the following experimental examples). Under the same polymerization conditions, the catalytic activity reached a maximum of 18 kg / (g-Pd·h), which is higher than the catalytic activity of catalysts prepared with existing known water-soluble polyketone catalyst ligands.

[0128] Experimental Example 1

[0129] The polymerization reaction was carried out using the ligand 2,2-bis[bis-(2-methoxy-5-sulfonylphenyl)phosphinomethyl]-propylene glycol sulfate. The specific steps are as follows:

[0130] In a 500 mL autoclave, 250 mL of water, 9.7 mg of p-benzoquinone, 1.68 mg of palladium acetate, 1% of trifluoromethanesulfonic acid by weight of water, and 8.05 mg of 2,2-bis[bis-(2-methoxy-5-sulfonic acidphenyl)phosphinomethyl]-propylene glycol sulfate were added.

[0131] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace, then filled with 15g of propylene, and filled with a mixture of CO and C2H4 with a mass ratio of 1:1.1 to 5MPa, and began to heat up, set the temperature to 85℃, and stir at a speed of 400r / min. When the temperature rose to 85℃, CO and C2H4 with a mass ratio of 1:1.1 were continuously fed into the autoclave, maintaining the reaction pressure at 5.0MPa, and the reaction time was 6h. The mass of the treated and dried product was 88g, the catalytic activity was 18.45kg / (g-Pd·h), and the apparent density of the product was 0.31g / cm 3 .

[0132] Experimental Example 2

[0133] The polymerization reaction was carried out using the ligand 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate, where 1 / 4 of the X is Na and 3 / 4 of the X is H. The specific steps are as follows:

[0134] In a 500 mL autoclave, 250 mL of water, 9.7 mg of p-benzoquinone, 1.68 mg of palladium acetate, 1% of trifluoromethanesulfonic acid by weight of water, and 8.21 mg of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate were added, where 1 / 4 of X was Na and 3 / 4 of X was H.

[0135] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace, then filled with 15g of propylene, and filled with a mixture of CO and C2H4 with a mass ratio of 1:1.1 to 5MPa, and began to heat up, set the temperature to 85℃, and stir at a speed of 400r / min. When the temperature rose to 85℃, CO and C2H4 with a mass ratio of 1:1.1 were continuously fed in, maintaining the reaction pressure at 5.0MPa, and the reaction time was 6h. The mass of the treated and dried product was 92g, the catalytic activity was 19.28kg / (g-Pd·h), and the apparent density of the product was 0.31g / cm 3 .

[0136] Experimental Example 3

[0137] The polymerization reaction was carried out using the ligand 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate, where 2 / 4 of the Xs were Na and 2 / 4 of the Xs were H. The specific steps are as follows:

[0138] In a 500 mL autoclave, 250 mL of water, 9.7 mg of p-benzoquinone, 1.68 mg of palladium acetate, 1% of trifluoromethanesulfonic acid by weight of water, and 8.38 mg of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate were added, where 2 / 4 of X was Na and 2 / 4 of X was H.

[0139] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace, then filled with 15g of propylene, and filled with a mixture of CO and C2H4 with a mass ratio of 1:1.1 to 5MPa, and began to heat up, set the temperature to 85℃, and stir at a speed of 400r / min. When the temperature rose to 85℃, CO and C2H4 with a mass ratio of 1:1.1 were continuously added to maintain the reaction pressure at 5.0MPa, and the reaction time was 6h. The mass of the treated and dried product was 98g, the catalytic activity was 20.54kg / (g-Pd·h), and the apparent density of the product was 0.31g / cm 3 .

[0140] Experimental Example 4

[0141] The polymerization reaction was carried out using the ligand 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate, where 3 / 4 of the X is Na and 1 / 4 of the X is H. The specific steps are as follows:

[0142] In a 500 mL autoclave, 250 mL of water, 9.7 mg of p-benzoquinone, 1.68 mg of palladium acetate, 1% of trifluoromethanesulfonic acid by weight of water, and 8.54 mg of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate were added, where 3 / 4 of X was Na and 1 / 4 of X was H.

[0143] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace, then filled with 15g of propylene, and filled with a mixture of CO and C2H4 with a mass ratio of 1:1.1 to 5MPa, and began to heat up, set the temperature to 85℃, and stir at a speed of 400r / min. When the temperature rose to 85℃, CO and C2H4 with a mass ratio of 1:1.1 were continuously fed into the autoclave, maintaining the reaction pressure at 5.0MPa, and the reaction time was 6h. The mass of the treated and dried product was 104g, the catalytic activity was 21.80kg / (g-Pd·h), and the apparent density of the product was 0.33g / cm 3 .

[0144] Experimental Example 5

[0145] The polymerization reaction was carried out using the ligand 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate, where 4 / 4 of X is Na. The specific steps are as follows:

[0146] In a 500 mL autoclave, 250 mL of water, 9.7 mg of p-benzoquinone, 1.68 mg of palladium acetate, 1% of trifluoromethanesulfonic acid by weight of water, and 8.71 mg of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate were added, where 4 / 4 of X was Na.

[0147] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace, then filled with 15g of propylene, and filled with a mixture of CO and C2H4 with a mass ratio of 1:1.1 to 5MPa, and began to heat up, set the temperature to 85℃, and stir at a speed of 400r / min. When the temperature rose to 85℃, CO and C2H4 with a mass ratio of 1:1.1 were continuously added to maintain the reaction pressure at 5.0MPa, and the reaction time was 6h. The mass of the treated and dried product was 116g, the catalytic activity was 24.32kg / (g-Pd·h), and the apparent density of the product was 0.35g / cm 3 .

[0148] Experimental Example 6

[0149] The polymerization reaction was carried out using the ligand 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate Y, where 4 / 4 of the X is Na, 1 / 2 of the Y is Na, and 1 / 2 of the Y is H. The specific steps are as follows:

[0150] In a 500 mL autoclave, 250 mL of water, 9.7 mg of p-benzoquinone, 1.68 mg of palladium acetate, 1% of trifluoromethanesulfonic acid by weight of water, and 8.87 mg of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate Y were added, where 4 / 4 of X was Na, 1 / 2 of Y was Na, and 1 / 2 of Y was H.

[0151] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace, then filled with 15g of propylene, and filled with a mixture of CO and C2H4 with a mass ratio of 1:1.1 to 5MPa, and began to heat up, set the temperature to 85℃, and stir at a speed of 400r / min. When the temperature rose to 85℃, CO and C2H4 with a mass ratio of 1:1.1 were continuously added to maintain the reaction pressure at 5.0MPa, and the reaction time was 6h. The mass of the treated and dried product was 109g, the catalytic activity was 22.85kg / (g-Pd·h), and the apparent density of the product was 0.30g / cm 3 .

[0152] Experimental Example 7

[0153] The polymerization reaction was carried out using the ligand 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate Y, where 4 / 4 of the Xs were Na and 2 / 2 of the Ys were Na. The specific steps are as follows:

[0154] In a 500 mL autoclave, 250 mL of water, 9.7 mg of p-benzoquinone, 1.68 mg of palladium acetate, 1% of trifluoromethanesulfonic acid by weight of water, and 9.04 mg of 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate Y, where 4 / 4 of X is Na and 2 / 2 of Y is Na, were added.

[0155] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace, then filled with 15g of propylene, and filled with a mixture of CO and C2H4 with a mass ratio of 1:1.1 to 5MPa, and began to heat up, set the temperature to 85℃, and stir at a speed of 400r / min. When the temperature rose to 85℃, CO and C2H4 with a mass ratio of 1:1.1 were continuously added to maintain the reaction pressure at 5.0MPa, and the reaction time was 6h. The mass of the treated and dried product was 106g, the catalytic activity was 22.22kg / (g-Pd·h), and the apparent density of the product was 0.32g / cm 3 .

[0156] Comparative Experiment 1

[0157] The polymerization reaction was carried out using the ligand 3,3-bis-[bis-(2-methoxyphenyl)phosphinomethyl]-1,5-dioxa-spiro[5,5]undecane. The specific steps are as follows:

[0158] In a 500 mL autoclave were added 250 mL of methanol, 9.7 mg of p-benzoquinone, 1% by weight of methanol of trifluoromethanesulfonic acid, 1.68 mg of palladium acetate, and 5.04 mg of 3,3-bis-[bis-(2-methoxyphenyl)phosphinomethyl]-1,5-dioxa-spiro[5,5]undecane.

[0159] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace the mixture. Then, 15g of propylene was added, followed by a mixture of CO and C₂H₄ in a mass ratio of 1:1.1, to 5MPa. The temperature was then raised to 85°C, with a stirring speed of 400r / min. When the temperature reached 85°C, a mixture of CO and C₂H₄ in a mass ratio of 1:1.1 was continuously fed, maintaining the reaction pressure at 5.0MPa. The reaction time was 6h. The mass of the dried product was 104g, with a catalytic activity of 19.18kg / (g-Pd·h).

[0160] Comparative Experiment 2

[0161] The polymerization reaction was carried out using the ligand 1,3-bis[di(2-methoxyphenyl)phosphino]propane (BDOMPP). The specific steps are as follows:

[0162] In a 500 mL autoclave were added 250 mL of methanol, 9.7 mg of p-benzoquinone, 1% by weight of trifluoromethanesulfonic acid, 1.68 mg of palladium acetate, and 3.99 mg of 1,3-bis[di(2-methoxyphenyl)phosphino]propane.

[0163] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace the mixture. Then, 15g of propylene was added, followed by a mixture of CO and C₂H₄ in a mass ratio of 1:1.1, to 5MPa. The temperature was then raised to 85°C, with a stirring speed of 400r / min. When the temperature reached 85°C, a mixture of CO and C₂H₄ in a mass ratio of 1:1.1 was continuously added, maintaining the reaction pressure at 5.0MPa. The reaction time was 6h. The treated and dried product weighed 86g and had a catalytic activity of 18.03kg / (g-Pd·h).

[0164] The scaling rate of the kettle wall of each of the above experimental examples was also tested, and the test results are shown in Table 1 below.

[0165] Table 1

[0166]

[0167] The above description of the disclosed embodiments will enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is to be construed in the widest manner consistent with the principles and novel features disclosed herein.

Claims

1. A water-soluble polyketone catalyst ligand having a structure represented by formula (I): Formula (I); In formula (I), X and Y are independently selected from H, Na, K or other alkali metal ions.

2. The water-soluble polyketone catalyst ligand according to claim 1, characterized in that X is H, Na or K, and at most ¾ of X are H.

3. The water-soluble polyketone catalyst ligand according to claim 1, characterized in that Y is H, Na or K, and at most 1 / 2 of Y is H.

4. A method for synthesizing the water-soluble polyketone catalyst ligand according to any one of claims 1 to 3, comprising the following steps: 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane is subjected to a hydrolysis reaction and a sulfonation reaction in sequence to obtain a water-soluble polyketone catalyst ligand; or, 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl1,3-dioxane is subjected to hydrolysis reaction, sulfonation reaction and neutralization reaction in sequence to obtain a water-soluble polyketone catalyst ligand.

5. The synthesis method according to claim 4, characterized in that The hydrolysis reaction process is a ketal hydrolysis reaction under the action of acid and water; the acid is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, formic acid, acetic acid, and oxalic acid.

6. The synthesis method according to claim 5, characterized in that The process of the hydrolysis reaction is specifically as follows: 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl1,3-dioxane is dispersed in an ethanol and water system to obtain a suspension of 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl1,3-dioxane; acid is then added to hydrolyze the mixture to obtain 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol.

7. The synthesis method according to claim 4, characterized in that The temperature of the hydrolysis reaction is 25° C. to 80° C., and the time is 1 h to 6 h.

8. The synthesis method according to claim 4, characterized in that The sulfonation reaction is carried out in the presence of a sulfonation reagent; the sulfonation reagent is a mixed acid system of concentrated sulfuric acid, fuming sulfuric acid or other acids and concentrated sulfuric acid.

9. The synthesis method according to claim 4, characterized in that The temperature of the sulfonation reaction is 25° C. to 70° C., and the time is 12 h to 48 h.

10. The synthesis method according to claim 4, characterized in that The neutralization reaction is carried out in the presence of a neutralizing agent; the neutralizing agent is an alkali metal base or an alkaline alkali metal carbonate.

Images