CN108863987A - It is a kind of to strengthen the epoxidised production method of grease using surfactant - Google Patents
It is a kind of to strengthen the epoxidised production method of grease using surfactant Download PDFInfo
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- CN108863987A CN108863987A CN201810826060.7A CN201810826060A CN108863987A CN 108863987 A CN108863987 A CN 108863987A CN 201810826060 A CN201810826060 A CN 201810826060A CN 108863987 A CN108863987 A CN 108863987A
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- grease
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Strengthen the epoxidised production method of grease using surfactant the invention discloses a kind of, it using consaturated oil and hydrogen peroxide as raw material, formic acid is catalyst, PEG-30 is grease dispersing agent, carries out epoxidation reaction, generates epoxidation environment-friendly plasticizer；Method of the invention can be widely applied to the epoxidation reaction of vegetable oil lipid, under conditions of not increasing mechanical stirring revolving speed, add the PEG-30 of denier, reaction efficiency can be improved, PVC product is used to prepare to the plasticizer of generation, the plasticising performance of plasticizer entirety can be improved in discovery when being tested for the property to PVC product, addition PEG-30.
Description
Technical field
The present invention relates to technical field of oil chemical industry, and in particular to a kind of epoxidised using surfactant reinforcing grease
Production method.
Background technique
Currently, the adjacent benzene class plasticizer from petroleum resources is still the most widely used in plastic processing industry
A kind of plasticizer.But due to such plasticizer to human health have it is potentially hazardous, various countries put into effect regulation in succession to limit this
The use of class plasticizer.Epoxidized vegetable oil and plasticizer are a kind of novel environmentally friendly class plasticizer, such plasticizer possesses raw material
The advantages that renewable, toxicity is minimum and biodegradable, has been allowed in many countries as food, medicine and toy for children
The plasticizer of equal plastic products.
It is heterogeneous that grease epoxidation reaction system belongs to liquid-liquid（Oily phase and water phase）Reaction system realizes that water-oil phase is good
Good mixing is the basis that reaction is gone on smoothly.Industrial grease epoxidation mostly uses mechanically stirred reactor at present（It is Chinese special
Sharp CN 201482479U, CN 101914219B CN102391210A, CN 101139328B, CN 101284821A, CN
100580025C, CN 100590188C, CN 101928267B, CN 102675254A）.Such reactor relies on agitating paddle
Realize the mixing of material, and the local partial circulating easy to form of whipping process liquid, lead to water-oil phase insufficient contact, thus instead
Answer efficiency lower.Under the conditions of identical material proportion, the reaction completed in 8 hours or so is only needed to stir in industry in laboratory
12-16 hour completion is generally required in reactor, this point has absolutely proved mixing for the importance of the reaction.
In grease epoxidation reaction in the prior art, water-oil phase often is realized by using mechanic whirl-nett reaction device
Mixing, to improve reaction efficiency.Mechanic whirl-nett reaction device is current industrial most widely used reactor, is stirred by increasing
The mixing of water-oil phase can be promoted by mixing paddle revolving speed, but energy consumption can be significantly greatly increased simultaneously, so that production cost is higher.
Summary of the invention
For above-mentioned technical problem of the existing technology, surfactant is utilized the purpose of the present invention is to provide a kind of
Strengthen the epoxidised production method of grease, Surfactant PEG is added under conditions of not increasing mechanical stirring revolving speed in the present invention
The interfacial tension of liquid-liquid two-phase is reduced, this can effectively reduce dispersion particle diameter of the dispersed phase in continuous phase, to increase unit bodies
Long-pending phase contact area improves reaction rate and product quality, greatly reduces production cost.
The is a kind of to strengthen the epoxidised production method of grease using surfactant, it is characterised in that with unsaturation
Grease and hydrogen peroxide are raw material, formic acid is catalyst, PEG-30 is grease dispersing agent, carry out epoxidation reaction, generate epoxidation
Environment-friendly plasticizer.
A kind of utilization surfactant strengthens the epoxidised production method of grease, it is characterised in that consaturated oil
Including polyunsaturated vegetable oil rouge or polyunsaturated vegetable oil rouge derivative.
A kind of utilization surfactant strengthens the epoxidised production method of grease, it is characterised in that unsaturated plant
Grease includes soybean oil；Polyunsaturated vegetable oil rouge derivative includes fatty acid methyl ester or fatty acid monooctyl ester.
A kind of utilization surfactant strengthens the epoxidised production method of grease, it is characterised in that the weight of PEG-30
Amount is the 0.005%-5%, preferably 0.01%-0.06% of consaturated oil weight.
Compared with the existing technology, what the present invention obtained has the beneficial effect that：It, can be significantly by adding Surfactant PEG -30
The interfacial tension between water-oil phase is reduced, so that the phase contact area of unit volume in reaction system be significantly greatly increased, fortification substance exists
Two alternate mass transfers shorten the reaction time, reduce the energy consumption of production, improve product quality.The present invention, which demonstrates, is not increasing machine
Under conditions of tool speed of agitator, the PEG-30 of denier is added, that is, reaction efficiency can be improved, the plasticizer of generation is used to prepare
The plasticising performance of plasticizer entirety can be improved in PVC product, discovery when being tested for the property to PVC product, addition PEG-30, this
The method of invention can be widely applied to the epoxidation reaction of vegetable oil lipid, have a good application prospect.
Detailed description of the invention
Fig. 1 is the PVC sample hot weight curve for adding various concentration PEG-30 plasticizer；
Fig. 2 is the anti-extracting of PVC sample and the weightless figure of migration for adding various concentration PEG-30 plasticizer.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1 ~ 2：
Embodiment 1：The raw oil material for being 125 in iodine number（Fatty acid methyl ester）In PEG-30 is not added, with mass fraction be 50% it is double
It with mol ratio is 1 that oxygen water, mass fraction, which are the formic acid of 95 %,:1.5:0.25（Carbon-carbon double bond in raw oil material:Hydrogen peroxide:First
Acid）It is reacted, control reaction temperature is 65 DEG C, and speed of agitator is 150 rpm, is reacted 8 hours, sample detection, as a result such as table 1
It is shown；
Embodiment 2：The raw oil material for being 125 in iodine number（Fatty acid methyl ester）It is middle that the PEG-30 that mass fraction is 0.035 % is added,
It with mol ratio is 1 with the hydrogen peroxide that mass fraction is 50 %, formic acid that mass fraction is 95 %:1.5:0.25（Raw oil material
Middle carbon-carbon double bond:Hydrogen peroxide:Formic acid）It is reacted, control reaction temperature is 65 DEG C, and speed of agitator is 150 rpm, and reaction 8 is small
When, sample detection, the results are shown in Table 1；
1. surfactant of table is on the epoxidised influence of grease
It is as shown in table 1 that the comparison of obtained product quality is reacted by embodiment 1 and embodiment 2, it can be seen that：After adding PEG-30, ring
The residual iodine number of oxygen methyl esters product is substantially reduced, and epoxide number improves, and product stability is more preferable.
Embodiment 3 ~ 4：
Embodiment 3：The raw oil material for being 125 in iodine number（Soybean oil）In PEG-30 is not added, with mass fraction be 50 % dioxygen
It with mol ratio is 1 that water, mass fraction, which are the formic acid of 95 %,:1.5:0.25（Carbon-carbon double bond in raw oil material:Hydrogen peroxide:Formic acid）
It is reacted, control reaction temperature is 75 DEG C, and speed of agitator is 150 rpm, is reacted 6 hours, sample detection, as a result such as 2 institute of table
Show；
Embodiment 4：The raw oil material for being 125 in iodine number（Soybean oil）It is middle that the PEG-30 that mass fraction is 0.035 % is added, with matter
The amount formic acid that score is the hydrogen peroxide of 50 %, mass fraction is 95 % is 1 with mol ratio:1.5:0.25（Carbon in raw oil material
Carbon double bond:Hydrogen peroxide:Formic acid）It is reacted, control reaction temperature is 75 DEG C, and speed of agitator is 150 rpm, reacts 6 hours, takes
Sample detection, the results are shown in Table 2；
2. surfactant of table is on the epoxidised influence of grease
It is as shown in table 2 that the comparison of obtained product quality is reacted by embodiment 3 and embodiment 4, it can be seen that：After adding PEG-30, ring
The residual iodine number of oxygen soybean oil product is substantially reduced, and epoxide number improves, and product stability is more preferable.
Embodiment 5 ~ 7：
Epoxy methyl esters is prepared, adds the PEG-30 of 0ppm, 100ppm and 350ppm respectively, other conditions react 8h with embodiment 2
Afterwards, epoxy methyl esters is made.
Epoxy methyl esters prepared by embodiment 5 ~ 7, is respectively used to preparation PVC film, and preparation method is as follows：By PVC powder,
Heat stabilizer and plasticizer（The heat stabilizer is calcium stearate and zinc stearate, and the plasticizer is that phthalic acid two is pungent
Rouge（DOP）With epoxy methyl esters）It weighs and is uniformly mixed, be then sufficiently mixed the mixture 8 at 180 DEG C using double roller mixing mill
Minute, mixed sample is then cut into the square small pieces of about 2 centimeter lengths and using solidification press at 180 DEG C with scissors,
By the compression forming of PVC sample small pieces the film with a thickness of 1 millimeter is made under the pressure of 10MPa.It is final to suppress 6 minutes and cool down 3
Minute obtains PVC sample, and the component and content of gained PVC sample are as shown in table 3；
3 PVC sample component list of table
For 5 ~ 7 gained epoxy methyl esters of embodiment, the carry out performance comparison of prepared PVC film, test its sample mechanical performance,
Sample heat resistance and anti-extracting and the weightless performance of migration, test result is respectively as shown in table 4, Fig. 1 and Fig. 2；
The mechanical performance of table 4.PVC sample
In table 4, the examination criteria of sample mechanical performance is：ASTM D638-2003；As seen from Table 4, a small amount of PEG-30 is added
Afterwards, obtained epoxy methyl esters plasticizer is used to prepare PVC film, and the tensile strength of gained PVC sample slightly enhances.
It can be seen from figure 1 that the thermal stability of PVC sample slightly enhances after adding a small amount of PEG-30；
In Fig. 2, the examination criteria of the anti-extracting of sample and the weightless performance of migration is respectively ISO 177:1998（E）And ASTMD
1239-2007；It can be seen in fig. 2 that the anti-extracting property enhancing of the heat of PVC sample, migration stability is after adding a small amount of PEG-30
Enhancing.
By examples detailed above as it can be seen that addition PEG-30 can strengthen the mass transport process of reaction, shorten the reaction time；And institute
The plasticising performance of plasticizer entirety can be improved in the presence of PEG-30.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated, protection scope of the present invention is also only in those skilled in the art's root
According to present inventive concept it is conceivable that equivalent technologies mean.
Claims (4)
1. a kind of strengthen the epoxidised production method of grease using surfactant, it is characterised in that with consaturated oil and dioxygen
Water is raw material, formic acid is catalyst, PEG-30 is grease dispersing agent, carries out epoxidation reaction, generates epoxidation environment-friendly plasticizer.
2. according to claim 1 a kind of using the surfactant reinforcing epoxidised production method of grease, feature exists
In consaturated oil include polyunsaturated vegetable oil rouge or polyunsaturated vegetable oil rouge derivative.
3. according to claim 2 a kind of using the surfactant reinforcing epoxidised production method of grease, feature exists
In polyunsaturated vegetable oil rouge include soybean oil；Polyunsaturated vegetable oil rouge derivative includes fatty acid methyl ester or fatty acid monooctyl ester.
4. according to claim 1 a kind of using the surfactant reinforcing epoxidised production method of grease, feature exists
In 0.005%-5%, preferably 0.01%-0.06% that the weight of PEG-30 is consaturated oil weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810826060.7A CN108863987B (en) | 2018-07-25 | 2018-07-25 | Production method for enhancing grease epoxidation by using surfactant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810826060.7A CN108863987B (en) | 2018-07-25 | 2018-07-25 | Production method for enhancing grease epoxidation by using surfactant |
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| Publication Number | Publication Date |
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| CN108863987A true CN108863987A (en) | 2018-11-23 |
| CN108863987B CN108863987B (en) | 2020-10-30 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265341A (en) * | 2008-03-24 | 2008-09-17 | 广州大学 | Method for preparing epoxy type plasticizing agent |
| US20090149586A1 (en) * | 2007-12-10 | 2009-06-11 | Nexoleum Bioderivados Ltda. | Primary pvc plasticizers derived from vegetable oils, process for obtaining primary pvc plasticizers derived from vegetable oils and plasticized pvc composition |
| CN101921248A (en) * | 2010-08-04 | 2010-12-22 | 湖北巨源油业有限公司 | Preparation method of epoxidation biodiesel plasticizer |
| CN102675254A (en) * | 2012-04-24 | 2012-09-19 | 上海众明化工科技发展有限公司 | Preparation method of epoxy fatty acid methyl ester serving as environment-friendly plasticizing agent |
-
2018
- 2018-07-25 CN CN201810826060.7A patent/CN108863987B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090149586A1 (en) * | 2007-12-10 | 2009-06-11 | Nexoleum Bioderivados Ltda. | Primary pvc plasticizers derived from vegetable oils, process for obtaining primary pvc plasticizers derived from vegetable oils and plasticized pvc composition |
| CN101265341A (en) * | 2008-03-24 | 2008-09-17 | 广州大学 | Method for preparing epoxy type plasticizing agent |
| CN101921248A (en) * | 2010-08-04 | 2010-12-22 | 湖北巨源油业有限公司 | Preparation method of epoxidation biodiesel plasticizer |
| CN102675254A (en) * | 2012-04-24 | 2012-09-19 | 上海众明化工科技发展有限公司 | Preparation method of epoxy fatty acid methyl ester serving as environment-friendly plasticizing agent |
Non-Patent Citations (5)
| Title |
|---|
| A.H. NOOR ARMYLISAS 等: "Modification of olefinic double bonds of unsaturated fatty acids and other vegetable oil derivatives via epoxidation: A review", 《GRASAS Y ACEITES》 * |
| 冯树波 等: "不同催化体系中脂肪酸甲酯环氧化反应研究", 《中国油脂》 * |
| 哈丽丹·买买提: "乳化体系中无溶剂合成环氧棉籽油", 《化工进展》 * |
| 程威威 等: "相转移催化制备环氧大豆油的工艺研究", 《华南理工大学学报( 自然科学版)》 * |
| 钟静芬 等: "《表面活性剂在药学中的应用》", 29 February 1996, 人民卫生出版社 * |
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