CN114292355A

CN114292355A - Synthesis of polyolefin lubricating oil viscosity index improver

Info

Publication number: CN114292355A
Application number: CN202210065961.5A
Authority: CN
Inventors: 方昱炜; 李兆顺
Original assignee: Individual
Current assignee: Individual
Priority date: 2022-01-20
Filing date: 2022-01-20
Publication date: 2022-04-08

Abstract

The invention discloses synthesis of a polyolefin lubricating oil viscosity index improver, and relates to the technical field of poly alpha-olefin copolymers and preparation methods thereof. The synthesis of the polyolefin lubricating oil viscosity index improver comprises an amorphous alpha polyolefin copolymer obtained by copolymerizing ethylene, propylene and 1-butene, wherein the ethylene accounts for 10-15% of the total raw material consumption; the propylene accounts for 55-60% of the total raw material; the 1-butene accounts for 25-30% of the total raw material dosage, and the 1-decene accounts for 1-15% of the total raw material. The preparation method comprises the following steps: taking straight-chain saturated alkane as a solvent, adding a raw material, adding a main catalyst and a cocatalyst, introducing hydrogen, and carrying out copolymerization reaction under the conditions of pressure of 0.6-2.0 MPa and temperature of 60-100 ℃. When the poly alpha olefin copolymer is used for a lubricating oil viscosity improver, the application temperature range is wide, the lubricating effect is good, the infiltration effect on metal is good, and the poly alpha olefin copolymer is suitable for automatic large-scale production and can meet small-scale production.

Description

Synthesis of polyolefin lubricating oil viscosity index improver

Technical Field

The invention relates to the technical field of viscosity of polyolefin lubricating oil, in particular to synthesis of a viscosity index improver of the polyolefin lubricating oil.

Background

Viscosity index improvers generally refer to oil-soluble polymeric compounds, which are generally rubbery or solid at room temperature. Compared with single-stage oil with the same viscosity, the multi-stage oil added with the viscosity index improver has higher viscosity index and smooth viscosity-temperature curve. The low-temperature startability of the lubricating oil and the maintenance of an appropriate high-temperature viscosity can be ensured.

Common types at present include HSD, PMA, PIB and OCP, and the current mainstream research and development direction is OCP in terms of cost performance; foreign suppliers, represented by LUbrizol, Oronite, etc., have long affected and dominated the lubricant additive market with their powerful research and development capabilities. The bench test and the driving test are long in time, so that the suppression of domestic technology research and development is objectively formed. Meanwhile, the factory for producing the OCP viscosity index improver in China is mainly in a lucky state, and the device has the advantages of long introduction time, low production flexibility, incapability of covering all required brands and no greater influence on the market.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides the synthesis of the polyolefin lubricating oil viscosity index improver, which solves the problem that for a long time, foreign suppliers represented by LUbrizol, Oronite and the like influence and lead the lubricating oil additive market by the strong research and development capability of the foreign suppliers. The bench test and the driving test are long in time, so that the suppression of domestic technology research and development is objectively formed. Meanwhile, the factory for producing the OCP viscosity index improver in China is mainly in a lucky state, and has the problems that the device is long in introduction time and low in production flexibility, all required brands cannot be covered, and the market is not influenced greatly.

(II) technical scheme

In order to achieve the purpose, the invention is realized by the following technical scheme: the synthesis of the viscosity index improver for the polyolefin lubricating oil comprises an amorphous alpha-olefin copolymer obtained by copolymerizing ethylene, propylene, 1-butene and 1-decene, and is prepared by taking the ethylene, the propylene, the 1-butene and the 1-decene as raw materials, wherein the ethylene accounts for 12% of the total raw material; the propylene accounts for 58 percent of the total raw material amount; 1-butene accounts for 20% of the total raw material dosage, and 1-decene accounts for 10% of the total raw material dosage;

the synthesis and preparation method of the polyolefin lubricating oil viscosity index improver comprises the following steps:

s1: preparing an index improver, namely adding raw materials of ethylene, propylene, 1-butene and 1-decene into normal heptane serving as a solvent, adding a main catalyst and a cocatalyst into the normal heptane, introducing hydrogen serving as a molecular weight regulator into the normal heptane, carrying out copolymerization reaction at the pressure of 1.2MPa and the temperature of 80 ℃, reacting for 5 hours, distilling the solvent, and obtaining the alpha-olefin copolymer serving as the lubricating oil viscosity index improver.

S2: preparing an index regulator, namely taking n-heptane as a solvent, adding raw materials of ethylene, propylene, 1-butene and 1-decene, adding a main catalyst and a cocatalyst, introducing hydrogen as a molecular weight regulator, carrying out copolymerization reaction under the conditions of pressure of 1.2MPa and temperature of 80 ℃ for 5 hours, and distilling the solvent to obtain a product, namely the lubricating oil viscosity index regulator;

s3: preparing lubricating oil, namely mixing and uniformly mixing 5-10% of modifier, 80-90% of base oil, 0.5-1% of antioxidant and other application and auxiliary agents of different scenes according to the weight percentage to prepare the lubricating oil;

preferably, the amount of the n-heptane is 2 times of the total weight of the raw materials.

Preferably, the main catalyst is the catalyst described in example 1 of the chinese patent with the publication number CN 101942053B.

Preferably, the cocatalyst is triethylaluminum.

Preferably, the amounts of the main catalyst and the cocatalyst are respectively 0.0005% and 0.0025% of the total weight of the raw materials.

Preferably, the hydrogen is used in an amount of 0.006% based on the total weight of the raw materials.

Preferably, the distillation temperature is controlled to be 80-130 ℃, and the pressure is 0.05 MPa.

(III) advantageous effects

The invention provides a synthesis of a polyolefin lubricating oil viscosity index improver. The method has the following beneficial effects:

the polyolefin lubricating oil viscosity index improver is synthesized by using ethylene, propylene and 1-butene as main comonomers and introducing 1-10 wt% of long-chain alpha olefin with 8-12 carbon atoms as a modified comonomer and polymerizing by a self-grinding catalytic system. The product is dissolved in 150SN base oil at the concentration of 5 percent and 10 percent respectively to compare the viscosity variation characteristic along with the temperature with the similar products at abroad, the performance of the product is found to be close to the foreign level and meet the domestic market requirement,

(II) the polyolefin lubricating oil viscosity index improver is synthesized by poly-alpha-olefin which has a plurality of specific properties, products with different properties can be obtained according to different chain segment combinations on molecular chain segments, for example, the ethylene-propylene-butylene combination can be used as a hot melt adhesive product, the ethylene-propylene combination can be used as a polyolefin PE/PP modifier, but the polyolefin added with long branched chains, particularly the poly-alpha-olefin with 6-10 carbon atoms, can be well dispersed in base oil, and the viscosity index improver can be used for improving the metal adsorption property of the lubricating oil at high and low temperatures

Drawings

FIG. 1: the viscosity ratio of the self-made product and foreign brands changes along with the temperature.

FIG. 2: the viscosity-temperature curve of the home-made product and the foreign product under the condition of 10 percent of addition amount of the base oil.

FIG. 3: the viscosity-temperature curve of the home-made product and the foreign product under the condition of 5 percent of addition amount of the base oil.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.

Referring to fig. 1-3, the present invention provides a technical solution:

example 1 preparation of an a-olefin copolymer copolymerized from ethylene, propylene, 1-butene and 1-decene

The relationship between the amounts of ethylene, propylene, 1-butene and 1-decene used as raw materials is shown in Table 1, and the preparation method is as follows:

using n-heptane as a solvent, adding ethylene, propylene, 1-butene and 1-decene as raw materials, adding a main catalyst and a cocatalyst, introducing hydrogen (as a molecular weight regulator), carrying out copolymerization reaction under the conditions of pressure of 1.2MPa and temperature of 80-90 ℃ (see table 1), reacting for 5 hours, distilling out the solvent, wherein the obtained product is the lubricating oil viscosity index improver, the using amount of the n-heptane is 2 times of the total weight of the raw materials, the main catalyst is the catalyst described in example 1 in the Chinese patent with the grant publication number of C101942053B, the cocatalyst is triethylaluminum, the using amounts of the main catalyst and the cocatalyst are respectively 0.0005% and 0.0025% of the total weight of the raw materials, the using amount of the hydrogen is 0.008% of the total weight of the raw materials, and the distillation temperature is controlled at 80-130 ℃ and the pressure is 0.05 MPa.

The molecular weight, melt viscosity, softening point, penetration and the like of the obtained lubricating oil viscosity index improver are shown in Table 1.

Example 2 preparation of amorphous alpha-olefin copolymer copolymerized from ethylene, propylene, and 1-butene, 1-decene

The amounts of ethylene, propylene, 1-butene and 1-decene used as raw materials are shown in Table 1, and the rest is the same as in example 1.

Example 3 preparation of amorphous alpha-olefin copolymer copolymerized from ethylene, propylene, and 1-butene, 1-decene

The amounts of ethylene, propylene, 1-butene and 1-decene used as starting materials are shown in Table 1, otherwise the same as in example 1.

The polyolefin product is polymerized by a self-grinding catalytic system by using ethylene, propylene and 1-butylene as main comonomers and introducing 1-10 wt% of long-chain alpha olefin with 8-12 carbon atoms as a modified comonomer. Product example 3 was compared to imported brand a 0500R and imported brand B7067C in 150SN base oil at 5% and 10% concentrations, respectively, for viscosity as a function of temperature: (Note: percentage ratio is self-made sample viscosity/imported sample viscosity all viscosity determination uses the Brookfield viscometer)

All the results show that the thickening effect of the Kjeldahl sample is not as obvious as that of the imported sample under the low-temperature state, but the thickening effect is obvious along with the temperature rise, and particularly the thickening effect is close to or even exceeds that of the imported sample above 130 ℃, which is also required by the lubricating oil viscosity regulator.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. The term "comprising", without further limitation, means that the element so defined is not excluded from the group consisting of additional identical elements in the process, method, article, or apparatus that comprises the element.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims

1. The synthesis of the viscosity index improver of the polyolefin lubricating oil comprises an amorphous alpha-olefin copolymer obtained by copolymerizing ethylene, propylene, 1-butene and 1-decene, and is characterized in that: the ethylene-propylene composite material is prepared by taking ethylene, propylene, 1-butene and 1-decene as raw materials, wherein the ethylene accounts for 12% of the total raw material; the propylene accounts for 58 percent of the total raw material amount; 1-butene accounts for 20% of the total raw material dosage, and 1-decene accounts for 10% of the total raw material dosage;

s3: the lubricating oil is prepared by mixing and uniformly mixing 5-10% of modifier, 80-90% of base oil, 0.5-1% of antioxidant and other application and auxiliary agents of different scenes according to weight percentage.

2. The synthesis of a polyolefin-based lubricating oil viscosity index improver according to claim 1, characterized in that: the dosage of the n-heptane is 2 times of the total weight of the raw materials.

3. The synthesis of a polyolefin-based lubricating oil viscosity index improver according to claim 1, characterized in that: the main catalyst is the catalyst described in example 1 in the Chinese patent with the publication number of CN 101942053B.

4. The synthesis of a polyolefin-based lubricating oil viscosity index improver according to claim 1, characterized in that: the cocatalyst is triethyl aluminum.

5. The synthesis of a polyolefin-based lubricating oil viscosity index improver according to claim 1, characterized in that: the dosages of the main catalyst and the cocatalyst are respectively 0.0005% and 0.0025% of the total weight of the raw materials.

6. The synthesis of a polyolefin-based lubricating oil viscosity index improver according to claim 1, characterized in that: the amount of the hydrogen is 0.006 percent of the total weight of the raw materials.

7. The synthesis of a polyolefin-based lubricating oil viscosity index improver according to claim 1, characterized in that: the distillation temperature is controlled to be 80-130 ℃, and the pressure is 0.05 MPa.