WO2013075300A1

WO2013075300A1 - Copolymer for use in low-temperature diesel fluidity improving agent and method for synthesizing the copolymer

Info

Publication number: WO2013075300A1
Application number: PCT/CN2011/082726
Authority: WO
Inventors: 熊靓
Original assignee: Xiong Liang
Priority date: 2011-11-23
Filing date: 2011-11-23
Publication date: 2013-05-30
Also published as: CN103635498B; CN103635498A

Abstract

Provided in the present invention application is a copolymer for use in a low-temperature diesel fluidity improving agent. The structure of the copolymer is as represented by formula (I), where n is an integer between 2 and 30, m is an integer between 2 and 20, k is an integer between 1 and 10, and R is an alkane having 8 to 20 carbons. Also provided in the present invention application is a method for synthesizing the copolymer. The method comprises the following steps: 1) synthesis of maleinamic acid: dissolving aliphatic amine and maleic anhydride at equimolar ratio into a solvent, heating to a temperature between 60°C and 120°C, refluxing for two to three hours, acquiring a reaction product, which is a mixture of maleinamic acid and a partially organic solvent; 2) synthesis of a terpolymer: adding in proportion the reaction product from step 1), ethylene, vinyl acetate, and a solvent into a polymerizer, reacting the copolymer acquired by synthesis for four to five hours under the effect of an initiator, where the molar ratio of three raw materials, namely ethylene, vinyl acetate, and meleiamic acid, is 6-20:1-5:0.05-0.1; and 3) distilling the polymerization solvent at a temperature between 60°C and 120°C, mixing the reactants with an aromatic solvent of a weight ratio between 45% and 60% to acquire the polymer. The copolymer reduces the condensation point and cold filter plugging point of diesels, provides for strong adaptability to diesels having high wax content, and obviates a need for compounding in allowing for great effects in lowering the condensation point and cold filter plugging point.

Description

Copolymer for diesel low temperature fluidity improver and synthesis method thereof

The invention relates to a copolymer for a diesel low-temperature fluidity improver and a synthesis method thereof, in particular to an ethylene-vinyl acetate-s-butamic acid triester for a diesel low-temperature fluidity improver Meta-copolymer and its synthesis process.

Background technique

Diesel low temperature flow improver (DFI) is an important modified polymer in petroleum additives. The addition of trace amounts of DFI to diesel fuel can effectively reduce the freezing point and cold filter point of diesel fuel, improve the low-temperature flow performance of diesel fuel, and has important practical significance for increasing diesel production, increasing production flexibility and economic benefits.

As the world's crude oil reserves and quality decline, the quality of diesel fuel, especially its low-temperature flow performance, is affected by a large impact. Therefore, adding DFI to diesel is a commonly used technology. International DFI research began in 1931. In 1960, Esso produced the first DFI Baladen-20 (ethylene-vinyl acetate copolymer). With the increase in crude oil transportation methods and the increasing demand for low-sulfur and high-wax crude oil, the requirements for DFI are getting higher and higher. Some large companies in the world have modified or compounded their original products to expand their adaptation to crude oil, making them suitable for a variety of refined oils and various high-wax crude oils. Tack et al. modified the ethylene glycol diacid of a polyalkylene; Maged copolymerized isobutylene with ethylene-vinyl acetate to form a terpolymer.

China began to use low-temperature flow improvers in diesel in the 1980s. The main component of DFI is a polymer with a certain structure and molecular weight. The main polymers in the commercially available DFI are as follows: 1. Alkyl aromatic hydrocarbons; 2. Ethylene - vinyl acetate; 3, vinyl acetate-fumarate copolymer; 4, a composite additive containing alkenyl succinic acid as a main component. The existing additives mainly reduce the freezing point, and the effect on reducing the cold filter point is not obvious, and with the change of diesel composition, the diesel low-temperature flow improver has poor adaptability to diesel, and it needs to be compounded to have an effect. Summary of the invention

The application of the present invention is directed to the above-mentioned deficiencies in the present diesel low-temperature fluidity improver, and provides a copolymer for a diesel low-temperature fluidity improver and a synthesis method thereof, which can reduce the freezing point of diesel oil and The cold filter point has strong adaptability to diesel with high wax content, and it has good effect of lowering the freezing point and lowering the cold filter point without compounding.

It is an object of the present invention to provide a copolymer for a diesel low temperature fluidity improver which is achieved by the following technical solutions:

In particular, the present application provides a copolymer for a diesel low temperature fluidity improver having the following structure:

Wherein n is an integer from 2 to 30, m is an integer from 2 to 20, k is an integer from 1 to 10, and R is an alkane having 8 to 20 carbons.

Preferably, n is an integer from 6 to 20.

Preferably, m is an integer from 6 to 15 .

Preferably, k is an integer from 2 to 7.

Another object of the present application is to provide a method for synthesizing the copolymer, which is achieved by the following technical solutions:

The synthesis method includes the following steps:

1. Synthesis of maleic acid: a fatty amine and maleic anhydride are dissolved in a solvent in an equimolar ratio, Heating to 60 ~ 120 ° C, refluxing for 2 ~ 3 hours, to obtain a mixture of the reaction product methacrylic acid and a part of the organic solvent;

2. Synthesis of terpolymer: The reaction product of step 1 is added to the polymerization vessel in proportion to ethylene, vinyl acetate and solvent, respectively, and the copolymer obtained by the reaction is reacted for 4-5 hours under the action of an initiator, wherein ethylene, The molar ratio of the three raw materials of vinyl acetate and maleic acid is 6 ~ 20: 1 ~

5: 0.05 ~ 0.1;

3. The polymerization solvent is distilled off at 60 to 120 ° C, and the reactant is mixed with an aromatic hydrocarbon solvent having a weight ratio of 45 to 60 % to obtain the polymer.

Further, in the above steps 1 and 2, the solvent comprises benzene, toluene, xylene, cyclohexane or petroleum ether in an amount of from 30 to 40% by weight based on the total weight of the added materials.

Further, in the above step 2, the polymerization pressure of the maleic acid and the ethylene, vinyl acetate and the solvent in the polymerization vessel is 8 to 15 MPa, and the temperature is 80 to 150 °C.

Further, in the above step 2, the initiator includes an azo or peroxy initiator, and the total molar ratio of the three raw materials (methacrylic acid, ethylene and vinyl acetate) is 0.01: 1 ~ 0.1: 1.

Further, the initiator is azobisisobutyronitrile or benzoyl peroxide.

The present application also provides the use of the above copolymers in diesel low temperature fluidity improvers.

The copolymer for diesel low temperature fluidity improver described in the present application has the following characteristics:

1. The long chain of ethylene in the polymer acts as a seed for providing wax crystals;

2. Maleic anhydride (also known as maleic anhydride) reacts directly with aliphatic amines, does not require other catalysts to participate in the reaction, and the product after the reaction does not require treatment, and is used directly for polymerization; maleic anhydride (MA) is a special five The elemental ring contains a large number of polar oxygen atoms, which can effectively prevent the adsorption of paraffin molecules. The fatty amines reacted with the lone pair of electrons can improve the effect of the modifier. The long side chain of the fatty amine can distort the paraffin. Crystalline shape, changing the direction of paraffin crystals, acting as a poisoning wax crystal; 3. The ester group of vinyl acetate (VA) can also provide polar segments to prevent wax crystals from growing and to improve the low temperature flow properties of diesel;

4. The above monomers are all industrial products, easy to obtain, cheap, and no pretreatment before use, which is convenient for industrial production.

detailed description

Hereinafter, the copolymer for diesel low-temperature fluidity improver and the synthesis method thereof described in the application of the present invention will be described in conjunction with specific embodiments, in order to better understand the technical solution described in the present application, instead of Limitations of the technical solution, in fact, on the same or similar principles, the modification, addition and derivative thereof of the copolymer have the same functions as the copolymer of the present application, and The improvement of the synthesis method of the copolymer, including the corresponding reagents, and the modification of the reaction conditions, are all within the technical content claimed in the application of the present application.

Example 1

37 g of dodecylamine, 20 g of maleic anhydride, and 25 g of toluene were reacted at 60 ° C for 2 hours to obtain a methacrylic acid product I.

500 ml of toluene was placed in a 1000 ml autoclave, and 70 ml of vinyl acetate, 4 g of azobisisobutyronitrile, 10 g of reactant I, and then heated to 80 ° C, and ethylene were injected to a pressure of 8 MPa, were added. After the start of the reaction, the temperature was maintained at 8Q ° C. After the reaction was carried out for 2 hours, the reaction temperature was raised to 11 Q ° C, and after 3 hours of reaction, the mixture was discharged, and after distillation at 60 ° C, it was mixed with 50% aromatic hydrocarbon to obtain a finished product 1 #. Example 2

Add 500ml of toluene to a 1000ml autoclave, add 90ml of vinyl acetate, azobisisobutyl Nitrile 5g, 15g of reactant I, was then warmed to 80 ° C and ethylene was injected to a pressure of 15 MPa. After the start of the reaction, the temperature was maintained at 80 ° C. After the reaction was carried out for 2 hours, the reaction temperature was raised to 120 ° C. After 2 hours of reaction, the mixture was discharged, and after distillation at 120 ° C, it was mixed with 55% aromatic hydrocarbon to obtain a finished product 2#. Example 3

48 g of hexadecylamine, 20 g of maleic anhydride, and 40 g of petroleum ether were reacted at a temperature of 100 ° C for 2.5 hours to obtain a cis-amic acid product II.

600 ml of petroleum ether was placed in a 1000 ml autoclave, and 70 ml of vinyl acetate, 6 g of azobisisobutyronitrile, and 20 g of reactant II were respectively added, and then the temperature was raised to 130 ° C, and ethylene was injected to bring the pressure to 10 MPa. After the reaction was started, the temperature was maintained at 13Q ° C. After the reaction was carried out for 2 hours, the reaction temperature was raised to 15 Q ° C, and after 2 hours of reaction, the material was discharged, and 8 (distilled under TC and then mixed with 45% aromatic hydrocarbon to obtain the finished product 3#.

Example 4 48 g of hexadecylamine, 20 g of maleic anhydride, and 40 g of petroleum ether were reacted at a temperature of 100 ° C for 2.5 hours to obtain a cis-amic acid product II.

550 ml of petroleum ether was placed in a 1000 ml autoclave, and 60 ml of vinyl acetate, 5 g of azobisisobutyronitrile, and 30 g of reactant II were respectively added, and then the temperature was raised to 120 ° C, and ethylene was injected to bring the pressure to 12 MPa. After the start of the reaction, the temperature was maintained at 12 Q ° C. After the reaction was carried out for 2 hours, the reaction temperature was raised to 135 ° C, and after 2 hours of reaction, the material was discharged, and 7 (distilled under TC and then mixed with 50% aromatic hydrocarbon to obtain a finished product 4#. Example 5

54 g of octadecylamine, 20 g of maleic anhydride, and 50 g of petroleum ether were reacted at 120 ° C for 2 hours to obtain a cis-amic acid product III. Add 600ml petroleum ether to 1000ml autoclave, add 80ml of vinyl acetate, peroxybenzene Formyl 9g, 30g of reactant III, was then heated to 130 ° C and ethylene was injected to a pressure of 9 MPa. After the start of the reaction, the temperature was maintained at 13Q ° C. After the reaction was carried out for 2 hours, the reaction temperature was raised to 135 ° C, and after 2 hours of reaction, the material was discharged, and 9 (distilled under TC and then mixed with 60% aromatic hydrocarbon to obtain a finished product 5 #.

Example 6 54 g of octadecylamine, 20 g of maleic anhydride, and 50 g of petroleum ether were reacted at 120 ° C for 2 hours to obtain a cis-amic acid product III. 600 ml of petroleum ether was placed in a 1000 ml autoclave, and 70 ml of vinyl acetate, 8 g of benzoyl peroxide, and 40 g of reactant III were respectively added, and then the temperature was raised to 120 ° C, and ethylene was injected to bring the pressure to 10 MPa. After the start of the reaction, the temperature was maintained at 12Q ° C, and after the reaction was carried out for 3 hours, the reaction temperature was raised to 15 Q ° C, and after 2 hours of reaction, the material was discharged, and 10 (distilled under TC and then mixed with 50% aromatic hydrocarbon to obtain a finished product 6#. The effect of reducing the diesel cold filter point of the product is shown in Table-1. The added amount in the table is 800μ. _§ . g-1 Table - 1 Additive 1#~6# Use effect (addition amount is 800μ _§ . g_l ) Diesel name Daqing 0 #独山子0# 榆林0

Blank (CFPP°C) -2 +2 +3

1#剂 -6 -8 0

2#agent -8 -12 -1

3# agent -5 -10 -2

4#agent -7 -9 -5

5#剂 -9 -6 -7

6#agent -4 -5 -6

Claims

A copolymer for use in a diesel low temperature fluidity improver, characterized in that: the copolymer has the following structure:

The copolymer according to claim 1, wherein: n is an integer of from 6 to 20.

The copolymer according to claim 1, wherein m is an integer of 6 to 15.

The copolymer according to claim 1, wherein k is an integer of 2 to 7.

5. A method for synthesizing a copolymer for a diesel low temperature fluidity improver according to any of claims 1-4, characterized in that the synthesis method comprises the following steps:

1) Synthesis of maleic acid: The fatty amine and maleic anhydride are dissolved in a solvent in an equimolar ratio, heated to 60 to 120 ° C, and refluxed for 2 to 3 hours to obtain a reaction product, maleic acid. a mixture with a portion of an organic solvent;

2) Synthesis of terpolymer: The reaction product of step 1 is added to the polymerization vessel in proportion to ethylene, vinyl acetate and solvent, and the copolymer obtained by reacting for 4 to 5 hours under the action of an initiator, wherein ethylene, The molar ratio of the three raw materials of vinyl acetate and maleic acid is 6 ~ 20: 1 ~

5 : 0. 05 ~ 0. 1 ;

3) The polymerization solvent is distilled off at 60 to 1 20 ° C, and the reactant is mixed with an aromatic solvent having a weight ratio of 45 to 60% to obtain the polymer.

6. The synthesis method according to claim 5, wherein in the above steps 1) and 2), the solvent comprises benzene, toluene, xylene, cyclohexane or petroleum ether, and the amount thereof is added to the material. The total weight is 30 ~ 40%.

7. The synthesis method according to claim 5, wherein in the above step 2), the polymerization pressure of the maleic acid and the ethylene, vinyl acetate and the solvent in the polymerization vessel is 8 to 15 MPa, and the temperature is It is 80 ~ 150 °C.

The synthesis method according to claim 5, wherein in the above step 2), the initiator comprises an azo or peroxy initiator, and the amount thereof is exemplified with methacrylic acid and ethylene, vinyl acetate. The total molar ratio is 0.01: 1 ~ 0.1: 1.

The method according to claim 5, wherein the initiator is azobisisobutyronitrile or benzoyl peroxide.

10. Use of the copolymer of claims 1-4 in a diesel low temperature fluidity improver.