CN101200522A - Polyester oil and method for preparing the same - Google Patents

Abstract

The present invention relates to polyester oil and the preparation method. The chemical composition of the polyester oil is the right formula and n is 100 to 110. Compared with the other polyester oils, the polyester oil prepared by the present invention has the advantages of high thermal and hydrolytic stability, lubricity and viscosity. The present invention is mainly used in the fields requiring high lubricity and stability as well as high price performance, including all automobile internal-combustion engine oil, gear oil and heavy-load metal processing oil. The adopted materials are biological materials which can be regenerated; the adopted two-step process of initiated polymerization and hydrogenation has the advantages of stable production performance and high production rate.

Description

A kind of polyester oil and preparation method thereof

Technical field

The present invention relates to a kind of polyester oil and preparation method thereof, belong to polyester synthetic oil field in the synthetic lubricant.

Background technology

Polyester is the multipolymer of alpha-olefin and unsaturated diester, and molecular structure is: being connected on the hydrocarbon skeleton is alternate hydrocarbon side chain and paired ester pendant groups.Polyester is new relatively gang's synthetic lubricant base oil, has features such as excellent oilness, viscosity-temperature characteristics, stability, sealing material consistency.Polyester is mainly used in the field that requires high lubricity and stability, can show the high performance-price ratio advantage, comprise all automobile internal machine oil, gear oil and heavy loading metalworking fluid, at present, Bao Dao polyester oil production is that the multipolymer of alpha-olefin and unsaturated ester (acrylate) does not belong to polyester oils by alpha-olefin and toxilic acid or fumarate copolymerization abroad.

The present invention is that raw material is produced polyester oil with 2-Ethylhexyl Alcohol fumarate and 1-butylene, with ester class oil phase ratio, has high heat and hydrolysis stability, oilness, high viscosity.

Summary of the invention

The purpose of this invention is to provide a kind of and ester class oil phase ratio, have high heat and hydrolysis stability, oilness, full-bodied be polyester oil of producing of raw material and preparation method thereof with 2-Ethylhexyl Alcohol fumarate and 1-butylene.

Polyester oil of the present invention, its chemical constitution is:

(2-ethylhexyl base): polymerization degree n=100～110.

Polyester oil of the present invention is to be raw material with 2-Ethylhexyl Alcohol fumarate that derives from fumaric acid and 2-Ethylhexyl Alcohol esterification reaction product and 1-butylene, through polymerization, hydrogenation preparing.

Concrete step of preparation process is as follows:

(1) initiated polymerization: the 2-Ethylhexyl Alcohol fumarate is dropped into reactor, adding quality then at twice is the initiator dicumyl peroxide (DCP) of fumarate 1～2%, 3～5 minutes timed intervals, close feeding cover, heat temperature raising, starting agitator stirs, react after 5～10 minutes, add 1-butylene, begin simultaneously to be evacuated to 0.099～0.1MPa with vacuum pump, 110～130 ℃ of temperature in the kettle, the high vacuum polymerization time is 2～5h, and temperature in the kettle begins discharging when reaching 70～80 ℃, continues the reacting by heating still, temperature in the kettle reaches 120～150 ℃ and has gone out theoretical polyester amount, and discharging time is 1～2h;

(2) DCP is taken off in crystallization: reactant cools to 30～35 ℃ via heat exchange after the still underflow goes out, white crystals occurs, separates out dicumyl peroxide after filtration, realizes solid-liquid separation, and dicumyl peroxide can recycle as initiator after further separating purification;

(3) hydrogenation: polyester contains residual double bonds behind the polymerization procedure, polymerization oil plant later, through volume pump with 25～30m ³/ h flow enters reactor from the top, inlet pressure remains on 0.20～0.25MPa, temperature is between 50～70 ℃, the catalyzer that adopts is a ternary Cu-Cr-Mn catalyzer, its add-on is the 0.02～0.15wt% that enters the oil plant of reactor, oil plant with enter catalytic bed after hydrogen mixes and react, temperature of reaction is 80～120 ℃, pressure 0.4～1.3MPa, the oil plant air speed remains on 0.9～1.0h ^-1, by the hydrogenation saturated reaction, it is saturated that part contains two key polyester hydrogenation, and reaction must be controlled iodine value 90～97,15～20 minutes reaction times;

(4) gas-liquid separation: behind the hydrogenation in the material except that polyester, also contain excessive saturated C _12～16Alkane, unreacting hydrogen, a small amount of side reaction product lighter hydrocarbons, aldehyde and ketone, reactant are cooled to 40～45 ℃ through heat exchange and enter cold high score and carry out gas-liquid separation, under 13～16MPa pressure, leave standstill extracting with the H in the reaction product by high pressure ₂Separate with oil ingredient, cold high score bottom feed liquid is directly sent to cold low branch, under 1.0～2.0MPa operating pressure, oil is separated with cut gas, the hydrogen that contains 90～95v% at isolated gas, most of as the recycle hydrogen use after the recycle compressor supercharging, residue cut gas enters heating network;

(5) vacuum fractionation: separate the back material and promptly enter the vacuum fractionation tower continuously, 100～102 ℃ of control fractionation tower temperatures are evacuated to 0.01～0.05MPa with vacuum pump, and temperature is 400～420 ℃ at the bottom of the still, obtain different components through decompression separation, 160～210 ℃ of isolated C of side line _12～16Alkane is controlled carbonatoms C after the heat exchange condensation process _12～14Enter storage tank and preserve, polyester oil is cooled to 30～35 ℃ of uses through heat exchange.

Reaction formula is:

Beneficial effect

The polyester oil and other ester class oil phase ratio of preparation have high heat and hydrolysis stability, oilness, high viscosity.Be mainly used in the field that requires high lubricity and stability, can show the high performance-price ratio advantage, comprise all automobile internal machine oil, gear oil and heavy loading metalworking fluid.The raw material that adopts is an organism-based raw material, and resource is renewable, adopts initiated polymerization and hydrogenation two-step process, and product property is stable, the productive rate height.

Every index of polyester oil of the present invention is as follows:

Project	Quality index	Test method
			Density g/cm 3	0.93～0.99	ASTM D-1217
Viscosity (100 ℃)/(mm 2/s)	15～260	ASTM D-445
			Viscosity (40 ℃)/(mm 2/s)	150～4000	ASTM D-445
Viscosity index	140～200	ASTM D-2270
			Pour point/℃	-28～-15	ASTM D-97
Flash-point/℃	250～260	ASTM D-92
			Total acid value/(mgKOH/g)	0.1～0.3	ASTM D-974
Thermal oxidation stability (200 ℃, 12h, 15L air) viscosity increase/%	90～110	IP48
			Seal compatibility	Neutral	CEC-L-39-X-95
NOACK volatility/%	2～3	DIN 51581
			Biodegradable/%	60～70	ISO14593

Description of drawings

Fig. 1 is the total process flow sheet of the present invention.

Embodiment

The present invention is a raw material with 2-Ethylhexyl Alcohol fumarate and 1-butylene, through polymerization, hydrogenation preparing polyester oil.(total process flow sheet as shown in Figure 1)

Be raw material with 2-Ethylhexyl Alcohol fumarate and the butanols dewatered product 1-butylene that derives from fumaric acid and 2-Ethylhexyl Alcohol esterification reaction product below,, be described in further detail below in conjunction with the accompanying drawings particular content of the present invention:

(1) initiated polymerization: the 2-Ethylhexyl Alcohol fumarate is dropped into reactor, adding quality then at twice is the initiator dicumyl peroxide (DCP) of fumarate 1.4%, in 4 minutes timed intervals, close feeding cover, heat temperature raising, starting agitator stirs, react after 7 minutes, add 1-butylene, begin simultaneously to be evacuated to 0.099～0.1MPa with vacuum pump, 110 ℃ of temperature in the kettle, high vacuum polymerization time are 2～5h.Temperature in the kettle begins discharging when reaching 70 ℃, continue the reacting by heating still, and temperature in the kettle reaches 120 ℃ and gone out theoretical polyester amount, and discharging time is 1h.

(2) DCP is taken off in crystallization: reactant cools to 35 ℃ via heat exchange after the still underflow goes out, white crystals occurs, separates out dicumyl peroxide after filtration, realizes solid-liquid separation, and dicumyl peroxide can recycle as initiator after further separating purification.

(3) hydrogenation: polyester contains residual double bonds behind the polymerization procedure, polymerization oil plant later, through volume pump with 25m ³/ h flow enters reactor from the top, and inlet pressure remains on 0.20MPa, and temperature is about 50 ℃.The catalyzer that adopts is novel tertiary Cu-Cr-Mn catalyzer (add-on is for entering oil plant 0.08%), oil plant with enter catalytic bed after hydrogen mixes and react, temperature of reaction is 80 ℃, pressure 0.8MPa, the oil plant air speed remains on 1.0h ^-1, by the hydrogenation saturated reaction, it is saturated that part contains two key polyester hydrogenation.Reaction must be controlled iodine value 92,16 minutes reaction times.

(4) gas-liquid separation: behind the hydrogenation in the material except that polyester, also contain excessive saturated C _12～16Alkane, unreacting hydrogen, a small amount of side reaction product lighter hydrocarbons, aldehyde and ketone, reactant are cooled to 40 ℃ through heat exchange and enter cold high score and carry out gas-liquid separation, under 15MPa pressure, leave standstill extracting with the H in the reaction product by high pressure ₂Separate with oil ingredient.Cold high score bottom feed liquid is directly sent to cold low branch, under the 2MPa operating pressure, oil is separated with cut gas.Contain the hydrogen of 90～95v% at isolated gas, most ofly after the recycle compressor supercharging use as recycle hydrogen.Residue cut gas enters heating network.

(5) vacuum fractionation: separate the back material and promptly enter the vacuum fractionation tower continuously, 102 ℃ of control fractionation tower temperatures are evacuated to 0.02MPa with vacuum pump, and temperature is 420 ℃ at the bottom of the still, obtains different components through decompression separation.160～210 ℃ of isolated C of side line _12～16Alkane is controlled carbonatoms C after the heat exchange condensation process _12～14Enter storage tank and preserve, polyester oil is cooled to 35 ℃ of uses through heat exchange.

Prepared polyester oil quality index is as follows:

Project	Quality index	Test method
			Density g/cm 3	0.946	ASTM D-1217
Viscosity (100 ℃)/(mm 2/s)	45	ASTM D-445
			Viscosity (40 ℃)/(mm 2/s)	350	ASTM D-445
Viscosity index	160	ASTM D-2270
			Pour point/℃	-22	ASTM D-97
Flash-point/℃	260	ASTM D-92
			Total acid value/(mgKOH/g)	0.1	ASTM D-974
Thermal oxidation stability (200 ℃, 12h, 15L air) viscosity increase/%	93	IP48

Seal compatibility	Neutral	CEC-L-39-X-95
			NOACK volatility/%	2	DIN 51581
Biodegradable/%	60	ISO14593

Claims (3)

1. polyester oil, it is characterized in that: the chemical constitution of polyester oil is:

n＝100～110。

2. polyester oil according to claim 1 is characterized in that: 100 ℃ of viscosity: 15～260mm ²/ s, pour point :-28～-15 ℃, flash-point: 250～260 ℃, total acid value: 0.1～0.3mgKOH/g.

3. the preparation method of polyester oil according to claim 1 is characterized in that: polyester oil is to be raw material with 2-Ethylhexyl Alcohol fumarate that derives from fumaric acid and 2-Ethylhexyl Alcohol esterification reaction product and 1-butylene, through polymerization, hydrogenation preparing,

Concrete step of preparation process is as follows:

(1) initiated polymerization: the 2-Ethylhexyl Alcohol fumarate is dropped into reactor, adding quality then at twice is the initiator dicumyl peroxide of fumarate 1～2%, 3～5 minutes timed intervals, close feeding cover, heat temperature raising, starting agitator stirs, react after 5～10 minutes, add 1-butylene, begin simultaneously to be evacuated to 0.099～0.1MPa with vacuum pump, 110～130 ℃ of temperature in the kettle, the high vacuum polymerization time is 2～5h, and temperature in the kettle begins discharging when reaching 70～80 ℃, continues the reacting by heating still, 120～150 ℃ of temperature in the kettle, discharging time are 1～2h;

(2) dicumyl peroxide is taken off in crystallization: reactant cools to 30～35 ℃ via heat exchange after the still underflow goes out, white crystals occurs, separates out dicumyl peroxide after filtration, realizes solid-liquid separation;

(3) hydrogenation: polymerization oil plant later, through volume pump with 25～30m ³/ h flow enters reactor from the top, inlet pressure remains on 0.20～0.25MPa, temperature is between 50～70 ℃, the catalyzer that adopts is a ternary Cu-Cr-Mn catalyzer, its add-on is the 0.02～0.15wt% that enters the oil plant of reactor, oil plant with enter catalytic bed after hydrogen mixes and react, temperature of reaction is 80～120 ℃, pressure 0.4～1.3MPa, the oil plant air speed remains on 0.9～1.0h ^-1, by the hydrogenation saturated reaction, it is saturated that part contains two key polyester hydrogenation, and reaction must be controlled iodine value 90～97,15～20 minutes reaction times;

(4) gas-liquid separation: reactant is cooled to 40～45 ℃ through heat exchange and enters cold high score and carry out gas-liquid separation, under 13～16MPa pressure, leaves standstill extracting with the H in the reaction product by high pressure ₂Separate with oil ingredient, cold high score bottom feed liquid is directly sent to cold low branch, under 1.0～2.0MPa operating pressure, oil is separated with cut gas;

(5) vacuum fractionation: separate the back material and promptly enter the vacuum fractionation tower continuously, 100～102 ℃ of control fractionation tower temperatures are evacuated to 0.01～0.05MPa with vacuum pump, and temperature is 400～420 ℃ at the bottom of the still, obtain different components through decompression separation, 160～210 ℃ of isolated C of side line _12～16Alkane is controlled carbonatoms C after the heat exchange condensation process _12～14Enter storage tank and preserve, polyester oil is cooled to 30～35 ℃ of uses through heat exchange.

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