阅读说明：本技术 一种复配催化剂和聚酮的制备方法 (Preparation method of compound catalyst and polyketone ) 是由 王旭亮 裴立军 曹丽艳 王朋朋 高秀云 郭龙龙 刘英贤 于 2020-06-24 设计创作，主要内容包括：本发明属于聚合物合成领域,尤其涉及一种复配催化剂和聚酮的制备方法。本发明提供的复配催化剂包括钯化合物、1,3-双[二(2-甲氧基苯基)膦基]丙烷和ZSM-5分子筛。本发明通过对催化剂的成分组成进行优化设计,获得了性能优异的复配催化剂,采用该复配催化剂制备聚酮时,可以有效改善制备过程中聚酮在反应釜内壁附着的问题,并且还可以提高制得的聚酮产品的堆积密度。实验结果表明,采用本发明复配催化剂制备的聚酮的堆密度最高可达0.3g/cm<Sup>3</Sup>。(The invention belongs to the field of polymer synthesis, and particularly relates to a preparation method of a compound catalyst and polyketone. The compound catalyst provided by the invention comprises a palladium compound and 1, 3-bis [ di (2-methoxyphenyl) phosphino]Propane and ZSM-5 molecular sieves. According to the invention, the component composition of the catalyst is optimally designed, so that the compound catalyst with excellent performance is obtained, when the compound catalyst is used for preparing polyketone, the problem that the polyketone is adhered to the inner wall of a reaction kettle in the preparation process can be effectively solved, and the bulk density of the prepared polyketone product can be improved. Experimental results show that the maximum bulk density of the polyketone prepared by adopting the compound catalyst can reach 0.3g/cm 3 。)

1. A composite catalyst contains Pd compound, 1, 3-bis [ di (2-methoxyphenyl) phosphino ] propane and ZSM-5 molecular sieve.

2. The built catalyst of claim 1, wherein the palladium compound comprises one or more of palladium trifluoroacetate, palladium acetyl chloride, palladium chloride, bis (N, N-diethylamino methyl acetate) bis (diethylamine) palladium, and palladium sulfate.

3. The built catalyst of claim 1, wherein the ZSM-5 molecular sieve contains SiO₂And Al₂O₃The molar ratio of (30-400): 1.

4. the compound catalyst according to claim 1, wherein the ZSM-5 molecular sieve has a bulk density of 0.5-0.6 g/mL and a specific surface area of not less than 400m²The crystallinity is more than or equal to 85 percent per gram.

5. The built catalyst according to claim 1, wherein the molar ratio of the palladium compound to 1, 3-bis [ di (2-methoxyphenyl) phosphino ] propane is 1: (0.1 to 3);

the mass ratio of the palladium compound to the ZSM-5 molecular sieve is 1: (10-1000).

6. The built catalyst of claim 5, wherein the molar ratio of the palladium compound to 1, 3-bis [ di (2-methoxyphenyl) phosphino ] propane is 1: 1.2;

the mass ratio of the palladium compound to the ZSM-5 molecular sieve is 1: 100.

7. A preparation method of polyketone comprises the following steps:

in the presence of a catalyst, reacting carbon monoxide with an alkenyl compound in an organic solvent to obtain polyketone;

the catalyst is the compound catalyst of any one of claims 1-6.

8. The method of claim 7, wherein the alkenyl compound comprises one or more of an alpha-olefin, an alkenyl aromatic compound, a cyclic olefin, a halogenated olefin, and an olefinic acid ester.

9. The method of claim 8, wherein the alpha-olefin comprises one or more of ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and vinylcyclohexane;

the alkenyl aromatic compound comprises styrene and/or alpha-methyl styrene;

the cyclic olefin comprises one or more of cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene and 8-ethyltetracyclododecene;

the halogenated olefin comprises vinyl chloride;

the alkenoic acid ester comprises ethyl acrylate and/or methyl acrylate.

10. The production method according to claim 7, wherein the pressure of the reaction is from normal pressure to 20 MPa; the reaction temperature is 40-180 ℃; the reaction time is 1-5 h.

Technical Field

The invention belongs to the field of polymer synthesis, and particularly relates to a preparation method of a compound catalyst and polyketone.

Background

Because petroleum resources are increasingly reduced and the price of petroleum is continuously increased, the chemical industry taking coal as a raw material is emphasized, and monocarbonization is an important development project in the coal chemical industry. Carbon monoxide obtained from coal and methane, which are relatively abundant in reserves, becomes an important raw material for manufacturing organic chemical products such as methanol, ethanol and the like, and research on synthesis of high molecular materials by using CO is widely carried out at home and abroad.

The CO and α -olefin copolymerization can prepare functional polymer material polyketone with carbonyl in main chain, the photosensitivity of the carbonyl in the polyketone endows the polyketone with unique photodegradability, and the polyketone can be slowly and completely degraded into alkene and CO in natural environment₂And the polyketone is a novel environment-friendly material from the viewpoint of small molecules. Therefore, the research and development of polyketone are following the two requirements of energy conservation and environmental protection in the current era, and have very important practical significance and wide development prospect.

Research on polyketone synthesis technology has started as early as the early 50 s of the last century and can be prepared by three ways, namely, radical copolymerization, radiation copolymerization and catalytic copolymerization of an alkenyl compound and carbon monoxide. In recent years, catalytic copolymerization is mostly studied, however, at present, when polyketone is synthesized by adopting a catalytic copolymerization mode, polyketone products are easy to adhere to the inner wall of a reaction kettle, and the powder bulk density of the prepared polyketone products is low, so that the continuity and the production efficiency of a polyketone production process are seriously influenced, and the production cost is increased.

Disclosure of Invention

In view of the above, the present invention aims to provide a compound catalyst and a preparation method of polyketone, which can improve the adhesion problem of polyketone products on the inner wall of a reaction kettle and increase the bulk density of polyketone products when the polyketone is prepared by using the compound catalyst provided by the present invention.

The invention provides a compound catalyst, which comprises a palladium compound, 1, 3-bis [ di (2-methoxyphenyl) phosphino ] propane and a ZSM-5 molecular sieve.

Preferably, the palladium compound comprises one or more of palladium trifluoroacetate, palladium acetyl chloride, palladium chloride, bis (N, N-diethylamino methyl acetate) bis (diethylamine) palladium and palladium sulfate.

Preferably, theSiO in ZSM-5 molecular sieve₂And Al₂O₃The molar ratio of (30-400): 1.

preferably, the ZSM-5 molecular sieve has the bulk density of 0.5-0.6 g/mL and the specific surface area of more than or equal to 400m²The crystallinity is more than or equal to 85 percent per gram.

Preferably, the molar ratio of the palladium compound to 1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane is 1: (0.1 to 3);

the mass ratio of the palladium compound to the ZSM-5 molecular sieve is 1: (10-1000).

Preferably, the molar ratio of the palladium compound to 1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane is 1: 1.2;

the mass ratio of the palladium compound to the ZSM-5 molecular sieve is 1: 100.

The invention provides a preparation method of polyketone, which comprises the following steps:

in the presence of a catalyst, reacting carbon monoxide with an alkenyl compound in an organic solvent to obtain polyketone;

the catalyst is the compound catalyst of the technical scheme.

Preferably, the alkenyl compound includes one or more of an α -olefin, an alkenyl aromatic compound, a cyclic olefin, a halogenated olefin, and an olefinic acid ester.

Preferably, the alpha-olefin comprises one or more of ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and vinylcyclohexane;

the alkenyl aromatic compound comprises styrene and/or alpha-methyl styrene;

the cyclic olefin comprises one or more of cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene and 8-ethyltetracyclododecene;

the halogenated olefin comprises vinyl chloride;

the alkenoic acid ester comprises ethyl acrylate and/or methyl acrylate.

Preferably, the pressure of the reaction is normal pressure to 20 MPa; the reaction temperature is 40-180 ℃; the reaction time is 1-5 h.

Compared with the prior art, the invention provides a preparation method of a compound catalyst and polyketone. The compound catalyst provided by the invention comprises a palladium compound and 1, 3-bis [ di (2-methoxyphenyl) phosphino]Propane and ZSM-5 molecular sieves. According to the invention, the component composition of the catalyst is optimally designed, so that the compound catalyst with excellent performance is obtained, when the compound catalyst is used for preparing polyketone, the problem that the polyketone is adhered to the inner wall of a reaction kettle in the preparation process can be effectively solved, and the bulk density of the prepared polyketone product can be improved. Experimental results show that the maximum bulk density of the polyketone prepared by adopting the compound catalyst can reach 0.3g/cm³。

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a compound catalyst, which comprises a palladium compound, 1, 3-bis [ di (2-methoxyphenyl) phosphino ] propane and a ZSM-5 molecular sieve.

The compound catalyst provided by the invention comprises a palladium compound, 1, 3-bis [ di (2-methoxyphenyl) phosphino ] propane and a ZSM-5 molecular sieve. Wherein the palladium compound preferably comprises one or more of palladium trifluoroacetate, palladium acetyl chloride, palladium chloride, bis (N, N-diethylamino methyl acetate) bis (diethylamine) palladium and palladium sulfate. In the present invention, palladium chloride is most preferably used in terms of improving the catalyst activity and the intrinsic viscosity.

In the invention, SiO in the ZSM-5 molecular sieve₂And Al₂O₃The molar ratio (Si/Al ratio) of (A) to (B) is preferably (30-400): 1, specifically 30:1, 70:1, 100:1, 300:1 or 400: 1; bulk density of the ZSM-5 molecular sievePreferably 0.5-0.6 g/mL; the specific surface area of the ZSM-5 molecular sieve is preferably more than or equal to 400m²(ii)/g; the crystallinity of the ZSM-5 molecular sieve is preferably more than or equal to 85 percent; na of the ZSM-5 molecular sieve₂The O content is preferably less than or equal to 1 wt%; the ignition loss of the ZSM-5 molecular sieve at 550 ℃ is preferably less than or equal to 8 wt%.

In the present invention, in the built-up catalyst, the molar ratio of the palladium compound to 1, 3-bis [ bis (2-methoxyphenyl) phosphino ] propane is preferably 1: (0.1 to 3), more preferably 1: (1-3), specifically 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9 or 1: 3; the mass ratio of the palladium compound to the ZSM-5 molecular sieve is preferably 1: (10-1000), more preferably 1: (50-200), specifically 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:130, 1:140, 1:150, 1:160, 1:170, 1:180, 1:190 or 1: 200. In the invention, the molar ratio of the palladium compound to the 1, 3-bis [ di (2-methoxyphenyl) phosphino ] propane is most preferably 1:1.2, the mass ratio of the palladium compound to the ZSM-5 molecular sieve is most preferably 1:100, the compound catalyst in the ratio has the best use effect, polyketone prepared by the compound catalyst has the most satisfactory bulk density, and the obtained polyketone product is not attached to the inner wall of a reaction kettle at all.

According to the invention, the component composition of the catalyst is optimally designed, so that the compound catalyst with excellent performance is obtained, when the compound catalyst is used for preparing polyketone, the problem that the polyketone is adhered to the inner wall of a reaction kettle in the preparation process can be effectively solved, and the bulk density of the prepared polyketone product can be improved. Experimental results show that the maximum bulk density of the polyketone prepared by adopting the compound catalyst can reach 0.3g/cm³。

The invention also provides a preparation method of the polyketone, which comprises the following steps:

in the presence of a catalyst, reacting carbon monoxide with an alkenyl compound in an organic solvent to obtain polyketone;

the catalyst is the compound catalyst of the technical scheme.

In the preparation method provided by the invention, carbon monoxide and the alkenyl compound are firstly reacted in the presence of the catalyst in an organic solvent. Wherein the alkenyl compound preferably comprises one or more of an alpha-olefin, an alkenyl aromatic compound, a cyclic olefin, a halogenated olefin, and an olefinic acid ester; the alpha-olefin preferably comprises one or more of ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and vinylcyclohexane; the alkenyl aromatic compound preferably comprises styrene and/or alpha-methylstyrene; the cyclic olefin preferably comprises one or more of cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene and 8-ethyltetracyclododecene; the halogenated olefin preferably comprises vinyl chloride; the alkenoic acid ester preferably comprises ethyl acrylate and/or methyl acrylate. In the present invention, the alkenyl compound is more preferably an α -olefin, most preferably an α -olefin having 2 to 4 carbon atoms, and most preferably ethylene.

In the preparation method provided by the invention, the organic solvent includes but is not limited to one or more of alcohol, phenol, amine, ketone, ether and nitrile; the alcohol preferably comprises one or more of ethanol, propanol, butanol, hexafluoroisopropanol and ethylene glycol; the phenol is preferably m-cresol; the amine is preferably aniline; the ketone preferably comprises acetone and/or methyl ethyl ketone; the ether preferably comprises one or more of diethyl ether, tetrahydrofuran and diglyme; the nitrile is preferably acetonitrile. In the present invention, the organic solvent is preferably an alcohol, more preferably ethanol, in terms of economy and stability of operation.

In the preparation method provided by the invention, the dosage ratio of the palladium compound in the compound catalyst to the organic solvent is preferably (0.01-100) mmol:1L, more preferably (0.01 to 10) mmol:1L, specifically 0.01mmol:1L, 0.02mmol:1L, 0.03mmol:1L, 0.04mmol:1L, 0.05mmol:1L, 0.06mmol:1L, 0.07mmol:1L, 0.08mmol:1L, 0.09mmol:1L, 0.1mmol:1L, 0.12mmol:1L, 0.15mmol:1L, 0.2mmol:1L, 0.5mmol:1L, 1mmol:1L, 1.5mmol:1L, 2mmol:1L, 2.5mmol:1L, 3mmol:1L, 4mmol:1L, 5mmol:1L, 6mmol:1L, 7mmol:1L, 8mmol:1L, 9mmol:1L or 10mmol: 1L.

In the preparation method provided by the invention, the reaction is carried out in a closed reaction kettle, and before the reaction, air in the closed reaction kettle is removed. In the present invention, the mass ratio of the carbon monoxide to the alkenyl compound in the closed reaction vessel is preferably 1: (0.5-2), specifically 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1: 2; the pressure of the reaction is preferably normal pressure to 20MPa, more preferably 4 to 15MPa, and specifically may be 4MPa, 4.5MPa, 5MPa, 5.5MPa, 6MPa, 6.5MPa, 7MPa, 7.5MPa, 8MPa, 8.5MPa, 9MPa, 9.5MPa, 10MPa, 10.5MPa, 11MPa, 11.5MPa, 12MPa, 12.5MPa, 13MPa, 13.5MPa, 14MPa, 14.5MPa or 15 MPa; the reaction temperature is preferably 40-180 ℃, more preferably 50-120 ℃, and specifically can be 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃; the reaction time is preferably 1-5 h, and specifically can be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5 h.

In the preparation method provided by the present invention, after the reaction is finished, the reaction product is post-treated, and the post-treatment process preferably includes: and sequentially filtering, washing and drying the reaction product. After the post-treatment is finished, polyketone is obtained.

According to the preparation method provided by the invention, the compound catalyst provided by the technical scheme of the invention is adopted to prepare the polyketone, so that the problem of adhesion of the polyketone on the inner wall of a reaction kettle in the preparation process can be effectively solved, and the bulk density of the prepared polyketone product can be improved. Experimental results show that the bulk density of the polyketone prepared by the preparation method can reach 0.3g/cm at most³。

For the sake of clarity, the following examples and comparative examples are described in detail below.

In the following examples and comparative examples provided by the present invention, catalystsActivity ═ weight of polyketone obtained by polymerization ÷ (weight of palladium × reaction time) in kg/(g-Pd · hr), bulk density ═ weight of polyketone obtained by polymerization ÷ volume of polyketone in g/cm³。

In the following examples and comparative examples provided by the present invention, the ZSM-5 molecular sieves used were provided by the catalyst factory of southern kaiki university, and the specifications are shown in table 1:

TABLE 1 technical indices of ZSM-5 molecular sieves

Index item	Unit of	ZSM-5
			Na2O	wt％	＜1
Bulk density	g/mL	0.5～0.6
			Specific surface area	m2/g	＞400
Degree of crystallinity	％	＞85
			Ignition loss at 550 ℃	wt％	＜8