CN105296059A - Application of myrcenyl ester compounds as lubricant and preparation method of myrcenyl ester compounds - Google Patents
Application of myrcenyl ester compounds as lubricant and preparation method of myrcenyl ester compounds Download PDFInfo
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- CN105296059A CN105296059A CN201510807456.3A CN201510807456A CN105296059A CN 105296059 A CN105296059 A CN 105296059A CN 201510807456 A CN201510807456 A CN 201510807456A CN 105296059 A CN105296059 A CN 105296059A
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- ester compound
- myrcenyl
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- lubricating oil
- myrcenyl ester
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Abstract
The invention discloses an application of myrcenyl ester compounds as a lubricant and a preparation method of the myrcenyl ester compounds. The formula of myrcenyl ester compounds is represented in the description, wherein the R represents a C8-C22 alkyl group. The myrcenyl ester compounds comprise a carbon-carbon double bond group and branch structure, so the compounds have good low temperature fluidity. The prepared lubricant has the characteristics of good low temperature properties, no toxicity, and degradable performance. The ester type oil can be used as lubricant base oil or lubricant additive.
Description
Technical field
The present invention relates to application and the preparation thereof of myrcenyl ester cpds, be specifically related to the application and preparation method thereof of a kind of myrcenyl ester compound as lubricating oil.
Background technology
China's resin resource enriches, particularly Guangdong and Guangxi Provinces and Yunnan Province, and wherein contain the beta-pinene up to 30.3% in the rosin of Yunnan, area, two river, industrial beta-pinene obtains myrcene through thermal isomerization.Abundant exploitation China resin resource is used for Development of Chemical Products, not only can reduce the harm that brings of Chemicals to environment, also improve the utilization ratio of China's resin resource.
Myrcene is the active natural product of a kind of chemical property, can be applied to the various fields of organic reaction.Containing the conjugated dienes structure of cis in myrcene, can with dienophile (as maleic anhydride), Diels-Alder reaction occurs, and reacted product can use as acid anhydrides.Containing "-C=C-" group and branched structure in the acid anhydrides of this improvement, good low-temperature fluidity will be had with alcohol Reactive Synthesis Esters oil.
At present, on market, refrigerator oil selects ester oil mostly.But containing a large amount of branched acids and odd number carbonic acid in the structure of synthesizing ester refrigerator oil, these two kinds of acid content in natural product is extremely low, needs chemical industry to synthesize, main from import at present, and price is high.
Summary of the invention
The technical problem to be solved in the present invention is to provide the application and preparation method thereof of a kind of myrcenyl ester compound as lubricating oil, and it has excellent low-temperature fluidity and the advantage of environmental protection as lubricating oil.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is:
Myrcenyl ester compound is as an application for lubricating oil, and the general formula of myrcenyl ester compound is:
Wherein, R represents C
8~ C
22alkyl.
The preparation method of described myrcenyl ester compound is as follows:
Step one, Diels-Alder react
（1）
Step 2, esterification
（2）
Wherein, R represents C
8~ C
22alkyl; Described catalyzer is protonic acid or Lewis acid.Concrete, described catalyzer is that the metal oxide of routine is (as ZnO, SnO or TiO
2), molecular sieve (as ZSM-5 zeolite), heteropolyacid be (as H
3pW
12o
40), solid super-strong acid, resin (as storng-acid cation exchange resin) and organometallic compound (as organo-tin compound, butyl (tetra) titanate), one or several mixture in organic acid, inorganic salt.
Preferably, in step one, the temperature of Diels-Alder reaction is 30 ~ 80 DEG C.
Alcohol used in esterification in step 2 is C
8~ C
22alcohol in any one, Heating temperature is the reflux temperature of alcohol used.
Preferably,
for
β-firpene isomery gained.
βthe content of-firpene in rosin have up to more than 30%, rich in natural resources reduces the cost of lubricating oil.
In order to obtain better effect, in step 2, esterification also adds water entrainer, and described water entrainer is any one in toluene, dimethylbenzene, hexanaphthene or benzene.
The consumption of described water entrainer is 5 ~ 25% of all raw material total masses.
The beneficial effect adopting technique scheme to produce is: (1) applies myrcene lubricating oil in esters prepared by method of the present invention, containing "-C=C-" group and branched structure in molecule, makes it have good low-temperature fluidity; (2) adopt myrcene biomass resource to be basic raw material, instead of with oil is branched acids and the odd number carbonic acid of basic raw material, expands the added value of biomass material, decreases the utilization of fossil resources, environmental friendliness; (3) current, synthesis class branched acids and the main dependence on import of odd number carbonic acid, adopt syntheti c route ester oil of the present invention, can reduce the dependence to imported product, reduces the use cost of lubricating oil; (4) in the preparation process from basic material to the finished product, the gentle and environmental friendliness of operational path preparation condition.
Embodiment
Myrcenyl ester compound is as the application of lubricating oil, and the general formula of myrcenyl ester compound is:
Wherein, R represents C
8~ C
22alkyl, as octane base, dodecyl, hexadecyl, eicosyl etc."-C=C-" group and branched structure in above-mentioned myrcenyl ester compound, make it have good low-temperature fluidity.Its preparation method is as follows:
Step one: 30 ~ 80 DEG C, under the condition of catalyst-free, the myrcene of equimolar amount and toxilic acid (acid anhydride) are carried out Diels-Alder and reacts 3 ~ 7 hours, obtain intermediate product, called after 4-(4-methyl-3-pentenyl)-4-tetrahydrobenzene-1,2-acid (acid anhydride) (referred to as MYM); Step 2: make catalyzer with protonic acid or Lewis acid, consumption is 0.5% ~ 3% of MYM molar weight, adds water entrainer, and MYM and alcohol, keeping carrying out esterification at the temperature refluxed 3 ~ 15 hours, obtain target product ester oil.Described protonic acid or Lewis acid can be specifically that the metal oxide of routine is (as ZnO, SnO or TiO
2), molecular sieve (as ZSM-5 zeolite), heteropolyacid be (as H
3pW
12o
40), solid super-strong acid, resin (as storng-acid cation exchange resin) and organometallic compound (as organo-tin compound, butyl (tetra) titanate), organic acid (thionamic acid), one or several mixture in inorganic salt.Described water entrainer is any one in toluene, dimethylbenzene, hexanaphthene or benzene, and its consumption is 5 ~ 25% of all raw material total masses.
Be described in detail below by specific embodiment.
Embodiment 1
(1) Diels-Alder reaction
(prolong meets built-in CaCl being equipped with heating jacket, whipping appts, thermometer, dropping funnel and reflux condensing tube
2drying tube) 500mL four-hole boiling flask in, add 0.8mol maleic anhydride and heating make it melt.Start agitator, temperature maintains 50 DEG C ~ 60 DEG C, and from dropping funnel, dropping waits mole myrcene, controls to dropwise in 0.5h, is warming up to 70 DEG C of reaction 4h after dropwising.Reaction terminates, and adopts underpressure distillation, and cut under collection 180 DEG C/1.05kPa (absolute pressure), is intermediate product 4-(4-methyl-3-pentenyl)-4-tetrahydrobenzene-1,2-acid (acid anhydride) (referred to as MYM).
(2) Kaolinite Preparation of Catalyst
Get 10gSnCl
2in 150mL beaker, add 45g distilled water, ultra-sonic oscillation are to SnCl
2dissolve, in beaker, then drip ammoniacal liquor to pH=7, leave standstill 60min, layering, takes off layer SnO for subsequent use.
(3) in the 250mL there-necked flask that heating jacket, whipping appts, thermometer, water trap (water trap takes back flow condenser) are housed, add 0.1molMYM, 0.2mol n-Octanol and 0.2mol isooctyl alcohol, add the freshly prepd SnO catalyzer of toluene 45g and 0.18g simultaneously, MYM and n-Octanol are keeping carrying out esterification at the temperature refluxed 3 hours, after reaction terminates, Filtration of catalyst, extract unreacted raw material under 180 DEG C/1.05kPa (absolute pressure) and water entrainer again out and reclaim, in flask, remaining liq is final product.
This final product called after MYM-8, it can be used as refrigerator oil base oil allotment refrigerator oil proportioning as follows:
Title mass ratio
MYM-899.4%
Oxidation inhibitor T5310.15%
Oxidation inhibitor T5010.3%
Metal passivator T5510.05%
Friction improver T4510.1%
By above-mentioned formula modulation processed oil, its performance is as shown in table 1:
The processed oil performance test that table 1 is allocated
Above result shows: based on the MYM-8 utilizing the present embodiment to prepare, the refrigerator oil of oil allotment meets the requirement of the performance index of refrigerator oil, and it can use as lubricating oil.
Embodiment 2
(1) (prolong meets built-in CaCl being equipped with heating jacket, whipping appts, thermometer, dropping funnel and reflux condensing tube
2drying tube) 500mL four-hole boiling flask in, add 0.8mol toxilic acid.Start agitator, from dropping funnel, dropping waits mole myrcene, controls to dropwise in 0.5h, is warming up to 70 DEG C of reaction 4h after dropwising.Reaction terminates, and adopts underpressure distillation, and under collecting 180 DEG C/1.05kPa (absolute pressure), cut is intermediate product MYM.
(2) in the 250mL there-necked flask that heating jacket, whipping appts, thermometer, water trap (water trap takes back flow condenser) are housed, add 0.1molMYM and 0.4mol lauryl alcohol, add toluene 45g and 0.2g composite catalyst SnO-ZnO simultaneously, MYM and lauryl alcohol are keeping carrying out esterification at the temperature refluxed 3 hours, after reaction terminates, Filtration of catalyst, extract unreacted raw material under 200 DEG C/1.05kPa (absolute pressure) and water entrainer again out and reclaim, in flask, remaining liq is final product.
This final product called after MYM-12, it can be used as base oil to be deployed into processed oil according to the proportioning of embodiment 1, and carries out performance test according to the test event of table 1.Result shows: myrcenyl ester compound prepared by the present embodiment can use as lubricating oil, meets the correlated performance requirement of refrigerator oil.
Embodiment 3
(1) (prolong meets built-in CaCl being equipped with heating jacket, whipping appts, thermometer, dropping funnel and reflux condensing tube
2drying tube) 500mL four-hole boiling flask in, add 0.8mol maleic anhydride.Start agitator, from dropping funnel, dropping waits mole myrcene, controls to dropwise in 0.5h, is warming up to 70 DEG C of reaction 4h after dropwising.Reaction terminates, and adopts underpressure distillation, and under collecting 180 DEG C/1.05kPa (absolute pressure), cut is intermediate product MYM.
(2) in the 250mL there-necked flask that heating jacket, whipping appts, thermometer, water trap (water trap takes back flow condenser) are housed, add 0.1molMYM and 0.35mol hexadecanol, add benzene 45g and 2.0g molecular sieve ZSM-5 catalyzer simultaneously, MYM and hexadecanol are keeping carrying out esterification at the temperature refluxed 3.5 hours, after reaction terminates, Filtration of catalyst, extract unreacted raw material under 240 DEG C/1.05kPa (absolute pressure) and water entrainer again out and reclaim, in flask, remaining liq is final product.
This final product called after MYM-16, it can be used as base oil to be deployed into processed oil according to the proportioning of embodiment 1, and carries out performance test according to the test event of table 1.Result shows: myrcenyl ester compound prepared by the present embodiment can use as lubricating oil, meets the correlated performance requirement of refrigerator oil.
Embodiment 4
(1) (prolong meets built-in CaCl being equipped with heating jacket, whipping appts, thermometer, dropping funnel and reflux condensing tube
2drying tube) 500mL four-hole boiling flask in, add 0.8mol maleic anhydride.Start agitator, from dropping funnel, dropping waits mole myrcene, controls to dropwise in 0.5h, is warming up to 70 DEG C of reaction 4h after dropwising.Reaction terminates, and adopts underpressure distillation, and under collecting 180 DEG C/1.05kPa (absolute pressure), cut is intermediate product MYM.
(2) in the 250mL there-necked flask that heating jacket, whipping appts, thermometer, water trap (water trap takes back flow condenser) are housed, add 0.1molMYM and 0.4mol eicosanol, add hexanaphthene 45g and 2.5g strong acid cation exchange resin catalyst simultaneously, MYM and eicosanol are keeping carrying out esterification at the temperature refluxed 4 hours, after reaction terminates, Filtration of catalyst, extract unreacted raw material under 250 DEG C/1.05kPa (absolute pressure) and water entrainer again out and reclaim, in flask, remaining liq is final product.
This final product called after MYM-20, it can be used as base oil to be deployed into processed oil according to the proportioning of embodiment 1, and carries out performance test according to the test event of table 1.Result shows: myrcenyl ester compound prepared by the present embodiment can use as lubricating oil, meets the correlated performance requirement of refrigerator oil.
Myrcenyl ester compound both can do lubricant base and use, and also can cook lubricating oil additive and use.
Claims (8)
1. myrcenyl ester compound is as an application for lubricating oil, it is characterized in that the general formula of myrcenyl ester compound is:
Wherein, R represents C
8~ C
22alkyl.
2. myrcenyl ester compound according to claim 1 is as the application of lubricating oil, it is characterized in that the preparation method of described myrcenyl ester compound is as follows:
Step one, Diels-Alder react
（1）
Step 2, esterification
（2）
Wherein, R represents C
8~ C
22alkyl; Described catalyzer is protonic acid or Lewis acid.
3. myrcenyl ester compound according to claim 2 is as the application of lubricating oil, it is characterized in that the temperature of Diels-Alder reaction in step one is 30 ~ 80 DEG C.
4. myrcenyl ester compound according to claim 2 is as the application of lubricating oil, it is characterized in that alcohol used in esterification in step 2 is C
8~ C
22alcohol in any one, Heating temperature is the reflux temperature of alcohol used.
5. myrcenyl ester compound according to claim 2 is as the application of lubricating oil, it is characterized in that
for
β-firpene isomery gained.
6. myrcenyl ester compound according to claim 2 is as the application of lubricating oil, and the catalyzer that it is characterized in that in step 2 is one or several the mixture in metal oxide, molecular sieve, heteropolyacid, solid super-strong acid, resin, organometallic compound, organic acid, inorganic salt.
7. myrcenyl ester compound according to claim 2 is as the application of lubricating oil, it is characterized in that in step 2, esterification also adds water entrainer, and described water entrainer is any one in toluene, dimethylbenzene, hexanaphthene or benzene.
8. myrcenyl ester compound according to claim 7 is as the application of lubricating oil, it is characterized in that the consumption of described water entrainer is 5 ~ 25% of all raw material total masses.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102787001A (en) * | 2012-06-07 | 2012-11-21 | 中国科学院微生物研究所 | Dibasic acid diester type base oil for lubricating oil, and preparation method and application thereof |
| WO2013028307A1 (en) * | 2011-08-24 | 2013-02-28 | Amyris, Inc. | Derivatives of hydrocarbon terpenes |
| CN104845699A (en) * | 2013-06-05 | 2015-08-19 | 山东瀚霖生物技术有限公司 | Diester lubricant base oil and preparation method thereof |
-
2015
- 2015-11-20 CN CN201510807456.3A patent/CN105296059B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013028307A1 (en) * | 2011-08-24 | 2013-02-28 | Amyris, Inc. | Derivatives of hydrocarbon terpenes |
| CN102787001A (en) * | 2012-06-07 | 2012-11-21 | 中国科学院微生物研究所 | Dibasic acid diester type base oil for lubricating oil, and preparation method and application thereof |
| CN104845699A (en) * | 2013-06-05 | 2015-08-19 | 山东瀚霖生物技术有限公司 | Diester lubricant base oil and preparation method thereof |
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