Water-soluble polyketone catalyst ligand and synthesis method thereof

Abstract

The invention provides a water-soluble polyketone catalyst ligand and a synthesis method thereof. The synthesis method comprises the following steps: sequentially carrying out hydrolysis reaction and sulfonation reaction on 5, 5-bis [bis-(2-methoxyphenyl) phosphinomethyl]-2, 2-dimethyl-1, 3-dioxane, so as to obtain a water-soluble polyketone catalyst ligand; or 5, 5-bis [bis-(2-methoxyphenyl) phosphinomethyl]-2, 2-dimethyl-1, 3-dioxane is sequentially subjected to a hydrolysis reaction, a sulfonation reaction and a neutralization reaction, and the water-soluble polyketone catalyst ligand is obtained. Compared with the prior art, specific raw materials are selected to synthesize the water-soluble polyketone catalyst ligand according to specific process steps, overall good interaction is achieved, the synthesis method is simple and efficient in synthesis route, high in yield and few in by-product, the synthesized ligand is novel in structure, and the catalyzed polyketone polymerization reaction process is economical, safe, green and environmentally friendly; and the obtained polyketone product has high apparent density, and the catalytic activity is up to 18-25kg. (g.h) <-1 >.

Description

Technical Field

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

[0002] Polyketone (POK) is a new type of green polymer material synthesized from carbon monoxide and olefins (ethylene, propylene, styrene). Polyketone has photodegradation and biodegradation properties, and can be further chemically modified. Its excellent and wide performance makes it a "natural" thermoplastic engineering plastic. The synthesis of polyketone has mainly experienced the development of three catalytic systems: free radical initiation system, γ-ray induced initiation system and eighth group transition metal initiation system. Up to now, the eighth group transition metal catalytic system has dominated the market. The system consists of six parts: transition metal compounds, bidentate ligands, strong acids and their anions, oxidants, co-catalysts and solvents. Initially, the palladium acetate / 1,3-bis[bis(2-methoxyphenyl)phosphino]propane / trifluoroacetic acid catalytic system developed by Shell Company has high catalytic activity for ethylene and carbon monoxide polyketone, and the development of new bidentate ligands in the polymerization catalytic system plays an important role in improving the catalytic activity of polyketone polymerization. Since then, ST Pharmaceutical Co., Ltd. has successively 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), which all showed higher catalytic activity than 1,3-bis[bis(2-methoxyphenyl)phosphino]propane in the process of polyketone synthesis. However, the solvents used in the polymerization reaction process for the catalysts synthesized by these ligands are mostly alcohol solvents, especially methanol, which is the best. However, alcohol solvents are flammable and explosive, which makes the polymerization process have great safety risks when it is industrialized. In addition, a large amount of methanol will be adsorbed during the polymerization of polyketone, so that the polyketone particles are wrapped with a large number of methanol molecules during the growth process, resulting in a large number of cavities inside the polyketone powder particles, a low apparent density, and then causing scaling of the reactor. Water has great advantages as an economical, safe, green and environmentally friendly solvent to replace alcohol solvents in the polymerization process. 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 above-mentioned types of non-water-soluble ligands. 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, wherein the synthesis method has a simple and efficient synthesis route, a high yield, few by-products, a novel structure of the synthesized ligand, and a catalytic 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 18-25 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 3 / 4 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] The 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] The 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl 1,3-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; then an acid is added to hydrolyze 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 1h to 6h.

[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 is carried out at a temperature of 25°C to 70°C and for a time of 12h to 48h.

[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-dimethyl1,3-dioxane to hydrolysis reaction and sulfonation reaction in sequence to obtain a water-soluble polyketone catalyst ligand; or, subjecting 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl1,3-dioxane to hydrolysis reaction, sulfonation reaction and 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, 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, and the obtained polyketone product has a high apparent density and a catalytic activity of up to 18-25 kg·(g·h) -1 . DETAILED DESCRIPTION

[0021] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work 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), which 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 3 / 4 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, 2,2-bis[bis-(2-methoxy-5-sulfonic acid X-phenyl)phosphinomethyl]-propylene glycol sulfate; 4 / 4 of X 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. 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] The 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] The 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl 1,3-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 subjectes 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl 1,3-dioxane to hydrolysis and sulfonation to obtain a water-soluble polyketone catalyst ligand; the steps specifically include:

[0036] a) hydrolyzing 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 hydrolysis reaction, sulfonation reaction and 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., X in formula (I) is partially or fully an alkali metal ion; further, after X is fully 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 undergoes 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 present invention has no particular limitation on the source of the acid, 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; then an acid is added to hydrolyze 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); when the amount of acid is increased, the reaction time of the hydrolysis reaction will be shortened accordingly, 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 that the temperature rise of the reaction system is controlled to be 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, and 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 is neutral, and a large amount of white solid is precipitated. 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 conducts 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 includes concentrated sulfuric acid, oleum 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 oleum 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. A white solid is obtained after filtration. The solid is washed once with n-butyl ketone and ether respectively, and then dried in vacuum 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. The suspension was filtered, and the filtrate was spin-dried. Then methanol was added to the residual solid again, and the residual sodium sulfate was filtered out. 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 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 The synthesis method of 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl)phosphinomethyl]-propylene glycol sulfate comprises the following steps: a) hydrolyzing 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 synthesis method of 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate further comprises: 2,2-bis[bis-(2-methoxy-5-sulfonic acid phenyl) phosphinomethyl]-propylene glycol sulfate is further subjected to a neutralization reaction 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: 2,2-bis[bis-(2-methoxy-5-sulfonic acid X phenyl) phosphinomethyl]-propylene glycol sulfate is further subjected to a neutralization reaction 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 apparent density is>0.26g / cm 3 , catalytic activity up to 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-dimethyl1,3-dioxane to hydrolysis reaction and sulfonation reaction in sequence to obtain a water-soluble polyketone catalyst ligand; or, subjecting 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl1,3-dioxane to hydrolysis reaction, sulfonation reaction and 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, 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, and the obtained polyketone product has a high apparent density and a catalytic activity of up to 18-25 kg·(g·h) -1 .

[0062] In order to further illustrate the present invention, the following examples are used for detailed description. The specific sources of the raw materials used in the following examples of the present invention are commercially available 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) in a nitrogen atmosphere, bis(2-methoxyphenyl)phosphine and dimethyl sulfoxide (DMSO) are placed in a reaction container, 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 methyl sulfoxide and 2,2-dimethyl-1,3-dioxane-5,5-diyl to the obtained mixture and stirring it to react; (c) injecting methanol and stirring after the reaction is completed; (d) adding toluene and water, after separating the oil layer from the water, washing the oil layer with water, and then drying it 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 refer 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, the synthesis route of which 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, and stirred to make it fully dispersed. 3ml of hydrochloric acid (36.5%) (0.0354mol) was slowly added. The addition rate was preferably to control 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. A large amount of white solid precipitated. The residual liquid was extracted with dichloromethane three times, 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 in total) to obtain 4.39 g of white 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol solid (yield 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 preferably such that the temperature rise of the system was controlled 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 P NMR tracking 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. A white solid was obtained after filtration. After washing with 20 ml of n-butyl ketone and ether respectively, 7.23 g was obtained after vacuum drying at 80°C, 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, the synthesis route of which 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 make it fully dispersed. 3ml of hydrochloric acid (36.5%) (0.0354mol) was slowly added. The addition rate was preferably to control 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. A large amount of white solid precipitated. The residual liquid was extracted with dichloromethane three times, 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 in total) to obtain 4.26 g of white 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol solid (yield 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 preferably such that the temperature rise of the system was controlled 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 P NMR tracking 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. A white solid was obtained after filtration. After washing with 20 ml of n-butyl ketone and ether respectively, 7 g was obtained after vacuum drying at 80°C, 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, the synthesis route of which 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 make it fully dispersed. 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 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. A large amount of white solid precipitated. The residual liquid was extracted with dichloromethane three times, 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 in total) 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 P NMR tracking 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. A white solid was obtained after filtration. After washing with 20 ml of n-butyl ketone and ether respectively, 7.03 g was obtained after vacuum drying at 80°C, 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, the synthesis route of which 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, add 5g (0.0079mol) of 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl-1,3-dioxane to 40mL of ethanol and 10ml of water, stir to fully disperse it, and slowly add 5ml of trifluoroacetic acid (0.038mol). The addition rate is preferably to control the temperature rise of the reaction system to be below 5°C. After the addition is completed, the reaction system is heated to 45°C and the reaction is continued for 4h. As the reaction proceeds, the reaction solution gradually becomes 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. The residual liquid was extracted with dichloromethane three times, 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 in total) to obtain 4.24 g of white 2,2-bis[bis-(2-methoxyphenyl)phosphinomethyl]-propylene glycol solid (yield 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 P NMR tracking 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. A white solid was obtained after filtration. After washing with 20 ml of n-butyl ketone and ether respectively, 6.85 g was obtained after vacuum drying at 80°C, 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, the synthesis route of which 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 conditions. The addition rate was preferably to control the temperature rise of the reaction system to be below 5°C. After the addition was completed, the reaction was continued to be stirred at room temperature of 25°C for 0.5 h. The concentrated solution was dehydrated under reduced pressure. 20 ml of methanol was added to the concentrated solution. After sufficient stirring, a suspension of precipitated sodium sulfate was obtained. The suspension was filtered and the filtrate was dried by rotation. Then 20 ml of methanol was added to the residual solid again. The residual sodium sulfate was filtered off. The filtrate was further dried by rotation 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, in which 1 / 4 X was Na and 3 / 4 X was 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, the synthesis route of which 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 conditions. The addition rate was preferably to control the temperature rise of the reaction system to be below 5°C. After the addition was completed, the reaction was continued to be stirred at room temperature of 25°C for 0.5 h. The concentrated solution was dehydrated under reduced pressure. 20 ml of methanol was added to the concentrated solution. After sufficient stirring, a suspension of precipitated sodium sulfate was obtained. The suspension was filtered and the filtrate was dried by rotation. Then 20 ml of methanol was added to the residual solid again. The residual sodium sulfate was filtered off. The filtrate was further dried by rotation 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, in which 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, the synthesis route of which 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 conditions. The addition rate was preferably to control the temperature rise of the reaction system to be below 5°C. After the addition was completed, the reaction was continued to be stirred at room temperature of 25°C for 0.5 h. The concentrated solution was dehydrated under reduced pressure. 20 ml of methanol was added to the concentrated solution. After sufficient stirring, a suspension of precipitated sodium sulfate was obtained. The suspension was filtered and the filtrate was dried by rotation. Then 20 ml of methanol was added to the residual solid again. The residual sodium sulfate was filtered off. The filtrate was further dried by rotation 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 was Na and 1 / 4 X was 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, the synthesis route of which 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 conditions. The addition rate was preferably to control the temperature rise of the reaction system to be below 5°C. After the addition was completed, the reaction was continued to be stirred at room temperature of 25°C for 0.5 h. The concentrated solution was dehydrated under reduced pressure. 20 ml of methanol was added to the concentrated solution. After sufficient stirring, a suspension of sodium sulfate was obtained. The solution was filtered and the filtrate was dried by rotation. Then, 20 ml of methanol was added to the residual solid again. The residual sodium sulfate was filtered off. The filtrate was further dried by rotation 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 synthesis 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 preferably to control the temperature rise of the reaction system to be below 5°C. After the addition was completed, the reaction was continued to stir at room temperature of 25°C for 0.5 h. The concentrated solution was dehydrated under reduced pressure. 20 ml of methanol was added to the concentrated solution. After sufficient stirring, a suspension of precipitated sodium sulfate was obtained. The suspension was filtered and the filtrate was dried by rotation. Then 20 ml of methanol was added to the residual solid again. The residual sodium sulfate was filtered off. The filtrate was further dried by rotation 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, in which 4 / 4 X was Na, 1 / 2 Y was Na, and 1 / 2 Y was H. The yield was 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)phosphinemethyl]-propylene glycol sulfate Y, wherein the synthesis route 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, and 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 is obtained, 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 embodiments, 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. The above ligands are used to prepare the catalyst and carry out polymerization experiments (see the following experimental examples). Under the same polymerization conditions, the catalytic activity can reach up to 18 kg / (g-Pd·h), which is higher than the catalytic activity of the catalyst prepared by the existing known water-soluble polyketone catalyst ligand.

[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, and the specific steps are as follows:

[0130] In a 500 mL autoclave were added 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 acid phenyl)phosphinomethyl]-propylene glycol sulfate.

[0131] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace, and then filled with 15g of propylene, CO and C 2 H 4 The mass ratio of the mixed gas is 1:1.1 to 5MPa, and the temperature is set to 85℃, and the stirring speed is 400r / min. When the temperature rises to 85℃, CO and C are continuously added. 2 H 4 The mass ratio of the mixed gas was 1:1.1, the reaction pressure was maintained 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, 1 / 4 of X was Na, and 3 / 4 of X was H. The specific steps were 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, wherein 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, and then filled with 15g of propylene, CO and C 2 H 4 The mass ratio of the mixed gas is 1:1.1 to 5MPa, and the temperature is set to 85℃, and the stirring speed is 400r / min. When the temperature rises to 85℃, CO and C are continuously added. 2 H 4 The mass ratio of the mixed gas was 1:1.1, the reaction pressure was maintained 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, 2 / 4 of X was Na, and 2 / 4 of X was H. The specific steps were 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, wherein 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, and then filled with 15g of propylene, CO and C 2 H 4 The mass ratio of the mixed gas is 1:1.1 to 5MPa, and the temperature is set to 85℃, and the stirring speed is 400r / min. When the temperature rises to 85℃, CO and C are continuously added. 2 H 4The mass ratio of the mixed gas was 1:1.1, the reaction pressure was maintained 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, 3 / 4 of X was Na, and 1 / 4 of X was H. The specific steps were 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, wherein 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, and then filled with 15g of propylene, CO and C 2 H 4 The mass ratio of the mixed gas is 1:1.1 to 5MPa, and the temperature is set to 85℃, and the stirring speed is 400r / min. When the temperature rises to 85℃, CO and C are continuously added. 2 H 4 The mass ratio of the mixed gas was 1:1.1, the reaction pressure was maintained 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 was Na, and the specific steps were 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, wherein 4 / 4 of X was Na.

[0147] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace, and then filled with 15g of propylene, CO and C 2 H 4The mixed gas with a mass ratio of 1:1.1 was heated to 5MPa and the temperature was set to 85℃ with a stirring speed of 400r / min. When the temperature reached 85℃, CO and C were continuously added. 2 H 4 The mass ratio of the mixed gas was 1:1.1, the reaction pressure was maintained 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, 4 / 4 of X was Na, 1 / 2 of Y was Na, and 1 / 2 of Y was 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, wherein 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, and then filled with 15g of propylene, CO and C 2 H 4 The mixed gas with a mass ratio of 1:1.1 was heated to 5MPa and the temperature was set to 85℃ with a stirring speed of 400r / min. When the temperature reached 85℃, CO and C were continuously added. 2 H 4 The mass ratio of the mixed gas was 1:1.1, the reaction pressure was maintained 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, 4 / 4 of X was Na, and 2 / 2 of Y was 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 were added, wherein 4 / 4 of X was Na and 2 / 2 of Y was Na.

[0155] After adding the above substances, the autoclave was filled with nitrogen to maintain pressure and replace, and then filled with 15g of propylene, CO and C 2 H 4 The mass ratio of the mixed gas is 1:1.1 to 5MPa, and the temperature is set to 85℃, and the stirring speed is 400r / min. When the temperature rises to 85℃, CO and C are continuously added. 2 H 4 The mass ratio of the mixed gas is 1:1.1, the reaction pressure is maintained at 5.0MPa, and the reaction time is 6h. The mass of the treated and dried product is 106g, the catalytic activity is 22.22kg / (g-Pd·h), and the apparent density of the product is 0.32g / cm 3 .

[0156] Comparative Experiment Example 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, and 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% of trifluoromethanesulfonic acid by weight of methanol, 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, and then filled with 15g of propylene, CO and C 2 H 4 The mass ratio of the mixed gas is 1:1.1 to 5MPa, and the temperature is set to 85℃, and the stirring speed is 400r / min. When the temperature rises to 85℃, CO and C are continuously added. 2 H 4 The mass ratio of the mixed gas was 1:1.1, the reaction pressure was maintained at 5.0MPa, and the reaction time was 6h. The mass of the treated and dried product was 104g, and the catalytic activity was 19.18kg / (g-Pd·h).

[0160] Comparative Experiment Example 2

[0161] The polymerization reaction was carried out using the ligand 1,3-bis[di(2-methoxyphenyl)phosphino]propane (BDOMPP), and 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% of trifluoromethanesulfonic acid by weight of methanol, 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, and then filled with 15g of propylene, CO and C 2 H 4 The mass ratio of the mixed gas is 1:1.1 to 5MPa, and the temperature is set to 85℃, and the stirring speed is 400r / min. When the temperature rises to 85℃, CO and C are continuously added. 2 H 4 The mass ratio of the mixed gas was 1:1.1, the reaction pressure was maintained at 5.0MPa, and the reaction time was 6h. The mass of the treated and dried product was 86g, and the catalytic activity was 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 were obtained and are shown in Table 1 below.

[0165] Table 1

[0166]

[0167] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those 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 will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A water-soluble polyketone catalyst ligand having a structure shown in 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 3 / 4 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 a water-soluble polyketone catalyst ligand according to any one of claims 1 to 3, comprising the following steps: The 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, The 5,5-bis[bis-(2-methoxyphenyl)phosphinomethyl]-2,2-dimethyl 1,3-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; then an acid is added to hydrolyze 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 1h to 6h.

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 includes concentrated sulfuric acid, fuming sulfuric acid or a mixed acid system of 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.

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