CN103193933B - Preparation method of macromolecule plasticizer based on recycled cooking oil - Google Patents
Preparation method of macromolecule plasticizer based on recycled cooking oil Download PDFInfo
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- CN103193933B CN103193933B CN201310107972.6A CN201310107972A CN103193933B CN 103193933 B CN103193933 B CN 103193933B CN 201310107972 A CN201310107972 A CN 201310107972A CN 103193933 B CN103193933 B CN 103193933B
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Abstract
The invention discloses a preparation method of macromolecule plasticizer based on recycled cooking oil, which is characterized in that the purified recycled cooking oil is copolymerized with monomers with polyvinyl chloride (PVC) and similar solubility parameters in a radical grafting way, the glass-transition temperature of a material is adjusted through the molecular design, so that the non-transference macromolecule plasticizer which is applicable to the PVC is obtained. Compared with the traditional plasticizer such as dioctyl phthalate (DOP), the macromolecule plasticizer has the advantages of no volatilization, no transference, low cost, durability and stability of plasticizing property and the like. The macromolecule plasticizer based on the recycled cooking oil can be widely used in the field of semi-hard or soft PVC composite materials such as an oil-resisting and heat-resisting PVC cable, a gasket, artificial leather and the like.
Description
Technical field
The present invention relates to the technical field of functional high molecule material preparation and modification, especially a kind of preparation method of the macromole softening agent based on sewer oil.
Background technology
China is edible fat production and consumes big country, annual edible oil consumption is up to 2,100 ten thousand tons, and in its use procedure, produce again the waste grease (mainly comprising kitchen hogwash fat and business frying oil) of nearly 8,000,000 tons every year, i.e. so-called " sewer oil ".At present, the existence of the astronomical number sewer oil like this living environment of people having been lived and healthyly cause tremendous influence.On the one hand, the necessary municipal sewage system system of our daily life is corroded in the random discharge of sewer oil just gradually, in turn increases the burden of municipal sewage treatment enterprise to people's life while making troubles; On the other hand, some lawless person under the ordering about of abundant economic interests by sewer oil through simply filtering, making again it openly and legally flow to dining table after purification process, thus serious threat is caused to the healthy diet of people.Because sewer oil mostly be edible oil through decocting, fried after the waste grease that formed, edible oil has lived through a series of comparatively complicated chemistry and biochemical reaction in first time use procedure, and forming the poisonous and harmful substances such as there is the aldehyde of complicated molecule structure, acid and benzene analog derivative (as flavacin) wherein, Long Term Contact or eat only certainly will constitute a threat to the life security of human body through the sewer oil of simply and easy treat.Therefore, if sewer oil recycling is improper, tremendous influence is caused by the daily production of people and life.On the contrary, if be used by sewer oil by certain practicable new technology, then can effectively avoid it again to flow to dining table, and can by these wide material sources and resource cheap and easy to get be again used, turn waste into wealth.The Appropriate application of sewer oil has important theory and practice meaning to the resource utilization of urban waste grease and the healthy diet that improves people.
At present, both at home and abroad trench oil treatment process is mainly contained following several:
1, hydrolysis method prepares low-grade industrial oleic acid and stearic acid, and then prepares industrial solid lubricant;
2, saponification method produces the emulsifying agent needed for cleaning product, as the daily chemicals such as sodium oleate, sodium stearate;
3, alcoholysis method prepares biofuel, and main component is fatty acid methyl ester or ethyl ester.
Wherein, the 1st and the 2nd kind for the treatment of process comparatively common at home, be also the main path of domestic current industrial process sewer oil.But its subject matter faced is that the purity of these two kinds of method products therefroms and grade are relatively low, and be separated, purification difficult, directly cause the added value of end product lower, had a strong impact on the enthusiasm for production of this series products, this is also the large reason that sewer oil flows to dining table again.And the 3rd kind of method is the method that the developed countries such as current Japan, the U.S. generally adopt.But regrettably, with regard to the price of current petroleum based diesel, the biodesel produced by sewer oil does not have obvious price advantage compared with petroleum based diesel, and the production of most enterprises related products is all just accomplished under the active support of the government.As can be seen here, in a short time, this type of biodesel is difficult in the world, particularly in China, replaces petroleum based diesel and is widely used in automobile or relevant supply of power equipment.Therefore, constantly explore and product innovation, the novel material of exploitation based on sewer oil, widen its Application Areas, be only the effective way avoiding sewer oil again to flow to dining table.
Polyvinyl chloride (PVC) is one of four large commodity polymer materials.At present, the global output of PVC has broken through 4,000 ten thousand tons/year, and this wherein has close to 30% and is used to semi-rigid or flexible PVC material respectively more than 50%.This just means in the preparation process of semi-rigid or flexible PVC material, every year by use 4,000,000 tons ~ 6,000,000 tons softening agent.But in current used softening agent, having more than 80% is poisonous, harmful phthalic ester plasticizer (as dioctyl phthalate (DOP), O-phthalic dibutylester etc.).Though this type of conventional plasticizers has excellent plasticising performance, its health and security also more and more receive the concern of people, and particularly its potential carcinogenic risk causes the great attention of people especially.In the recent period, Europe and America majority state have put into effect corresponding policy, and completely forbid in PVC field, particularly pack with the food and medicine that the mankind directly contact, in the material such as toy for children, raincoat, use phthalic ester plasticizer.
For the above-mentioned defect of sewer oil and conventional plasticizers, the consistency of sewer oil (main component is Unsaturatcd fatty acid glycerides) and PVC macromolecular chain is significantly increased if can manage, simultaneously not obvious increase material cost again, then can be used as PVC softening agent by purifying sewer oil that is cheap, that be easy to get in a large number.
Summary of the invention
Technical problem to be solved by this invention is for the above-mentioned state of the art, and a kind of preparation method of the macromole softening agent based on sewer oil is provided, be characterized in the sewer oil after by purification process and there is high polymerization activity and have the monomer of close solubility parameter to carry out radical graft copolymerization with PVC, and the second-order transition temperature of material is regulated by molecular designing, obtain the non-migratory macromole softening agent being applicable to PVC.
The present invention solves the problems of the technologies described above adopted technical scheme:
Based on a preparation method for the macromole softening agent of sewer oil, wherein, comprise the following steps:
Step one, sewer oil carried out wash, decolour, filter, adsorb, sterilization, obtain the purifying sewer oil that main chemical compositions is Unsaturatcd fatty acid glycerides;
Step 2, the purifying sewer oil and high polymerization activity monomer, the second-order transition temperature that step one are obtained regulate monomer and close solubility parameter monomer 5 ~ 100:5 in mass ratio ~ 20:0 ~ 100:0 ~ 50 of PVC to mix obtained mixed solution, filling in mixed solution with mixed solution mass ratio is the initiator of 0% ~ 15%, temperature of reaction is within the scope of 0 DEG C ~ 150 DEG C, through conventional free radical or living free radical polymerization 1 little of 10 hours, must based on the macromole softening agent of sewer oil.
For optimizing technique scheme, the measure taked also comprises:
Above-mentioned initiator is at least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate and ammonium persulphate.
Above-mentioned high polymerization activity monomer is at least one in vinylbenzene, Vinylstyrene, sodium methacrylate, glycidyl methacrylate, vinylformic acid, acrylamide, maleic anhydride and vinyl pyridine.
Above-mentioned second-order transition temperature adjustment monomer is at least one in ethylpropylene, butyl acrylate, n-octyl, Hydroxyethyl acrylate, Propylene glycol monoacrylate and vinylformic acid ethylhexyl.
The close solubility parameter monomer of above-mentioned PVC is at least one in methyl acrylate, ethyl propenoate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, vinylchlorid, Ethylene Dichloride, vinylidene chloride and vinyl acetate.
Above-mentioned conventional radical polymerization method is at least one in solution polymerization, letex polymerization, suspension polymerization.
Above-mentioned active free radical polymerization is at least one in anionoid polymerization, cationoid polymerisation, atom transfer radical polymerization and reversible addition fracture radical polymerization.
Gained macromole softening agent of the present invention and conventional plasticizers, as dioctyl phthalate (DOP) DOP compares, there is the advantages such as non-volatile, non-migratory, cheap, plasticising performance lasting stability, this type of trench oil base macromole softening agent can be widely used in semi-rigid or flexible PVC field of compound material, as oil resistant, heat-resistant PVC cable, gasket, leatheroid etc.
The present invention also has the following advantages:
1, the prepared macromole softening agent based on sewer oil have non-volatility, nonmigratory, with the feature of PVC excellent compatibility.
2, part conventional plasticizers DOP (o-phthalic acid dibutyl ester) can be replaced even completely, remarkable in economical benefits.
3, can consume sewer oil in a large number, can effectively avoid sewer oil again to flow to dining table, social benefit be good.
Accompanying drawing explanation
Fig. 1 is the macromole softening agent chemical structure schematic diagram based on sewer oil of the present invention;
Fig. 2 is the Mechanics Performance Testing figure of the PVC matrix material using the macromole softening agent based on sewer oil of the present invention.
Embodiment
Below embodiments of the invention are described in further detail.
Based on a preparation method for the macromole softening agent of sewer oil, wherein, comprise the following steps:
Step one, sewer oil carried out wash, decolour, filter, adsorb, sterilization, obtain the purifying sewer oil that main chemical compositions is Unsaturatcd fatty acid glycerides;
Step 2, the purifying sewer oil and high polymerization activity monomer, the second-order transition temperature that step one are obtained regulate monomer and close solubility parameter monomer 5 ~ 100:5 in mass ratio ~ 20:0 ~ 100:0 ~ 50 of PVC to mix obtained mixed solution, filling in mixed solution with mixed solution mass ratio is the initiator of 0% ~ 15%, temperature of reaction is within the scope of 0 DEG C ~ 150 DEG C, through conventional free radical or living free radical polymerization 1 little of 10 hours, must based on the macromole softening agent of sewer oil.
In embodiment, initiator is at least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate and ammonium persulphate.
In embodiment, high polymerization activity monomer is at least one in vinylbenzene, Vinylstyrene, sodium methacrylate, glycidyl methacrylate, vinylformic acid, acrylamide, maleic anhydride and vinyl pyridine.
In embodiment, second-order transition temperature adjustment monomer is at least one in ethylpropylene, butyl acrylate, n-octyl, Hydroxyethyl acrylate, Propylene glycol monoacrylate and vinylformic acid ethylhexyl.
In embodiment, the close solubility parameter monomer of PVC is at least one in methyl acrylate, ethyl propenoate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, vinylchlorid, Ethylene Dichloride, vinylidene chloride and vinyl acetate.
In embodiment, conventional radical polymerization method is at least one in solution polymerization, letex polymerization, suspension polymerization.
In embodiment, active free radical polymerization is at least one in anionoid polymerization, cationoid polymerisation, atom transfer radical polymerization and reversible addition fracture radical polymerization.
This invention exploits a kind of macromole softening agent based on sewer oil, be mainly used in semi-rigid or flexible PVC field of compound material.
The present invention has the following advantages:
1, the prepared macromole softening agent based on sewer oil have non-volatility, nonmigratory, with the feature of PVC excellent compatibility.
2, part conventional plasticizers DOP can be replaced even completely, remarkable in economical benefits.
3, can consume sewer oil in a large number, can effectively avoid sewer oil again to flow to dining table, social benefit be good.
Set forth below by way of specific embodiment:
Embodiment 1
100 g ethyl acetate, 100 g purifying sewer oils, 10 g vinylbenzene, 50 g butyl acrylates, 25 g methyl methacrylates and 10 g dibenzoyl peroxide are added successively in the there-necked flask carrying heating and whipping appts, system temperature is made to be increased to 70 DEG C after mixing gradually, insulation reaction is after 7 hours, system temperature is increased to 78 DEG C, continue insulation reaction, after 2 hours, system temperature is cooled to 40 DEG C, obtain the solution polymerization type macromole softening agent based on sewer oil.
Embodiment 2
80 g dehydrated alcohols, 20 g pure water, 100 g purifying sewer oils, 25 g vinylbenzene, 100 g n-octyl, 50 g methyl acrylates and 20 g ammonium persulphates are added successively in the there-necked flask carrying heating and whipping appts, system temperature is made to be increased to 75 DEG C after mixing gradually, insulation reaction is after 8 hours, system temperature is increased to 80 DEG C, continue insulation reaction, after 2 hours, system temperature is cooled to 40 DEG C, obtain the precipitation polymerization type macromole softening agent based on sewer oil.
Embodiment 3
In the stainless steel pressure reactor of jacketed and whipping appts, add 1000 g successively remove pure water, 450 g purifying sewer oils, 50 g vinylbenzene, 300 g vinylformic acid ethylhexyls, 200 g vinylchlorid, 20 g peroxy dicarbonates and 30 g Potassium Persulphates, a small amount of emulsifying agent, dispersion agent and still release agent, system temperature is made to be increased to 52 DEG C after mixing under normal temperature gradually, after heat-insulation pressure keeping reaction obviously occurs Pressure Drop to system, continue reaction 30 minutes.System temperature is cooled to normal temperature, obtains the letex polymerization type macromole softening agent based on sewer oil.
Embodiment 4
In the stainless steel pressure reactor of jacketed and whipping appts, add 1000 g successively remove pure water, 600 g purifying sewer oils, 40 g butyl acrylates, 30 g vinylchlorid, 20 g peroxy dicarbonates and a small amount of dispersion agent and still release agent, make system temperature be increased to 52 DEG C after mixing under normal temperature gradually, heat-insulation pressure keeping reacts 30 minutes.360 g butyl acrylates, 270 g vinylchlorid and 80 g peroxy dicarbonates are added successively in stainless steel pressure holding bottle, mix rear peristaltic meatering pump and the mixed solution in holding bottle is evenly pumped into reactor, be controlled in 1 hour and mixed solution is all pumped into reactor.After heat-insulation pressure keeping reaction obviously occurs Pressure Drop to system, continue reaction 30 minutes.System temperature is cooled to normal temperature, obtains the suspension polymerization type macromole softening agent based on sewer oil.
Claims (4)
1., based on a preparation method for the macromole softening agent of sewer oil, it is characterized in that: comprise the following steps:
Step one, sewer oil carried out wash, decolour, filter, adsorb, sterilization, obtain the purifying sewer oil that main chemical compositions is Unsaturatcd fatty acid glycerides;
Step 2, the purifying sewer oil and high polymerization activity monomer, the second-order transition temperature that step one are obtained regulate monomer and the close solubility parameter monomer 5 ~ 100:5 in mass ratio ~ 20:100:50 of PVC to mix obtained mixed solution, filling in mixed solution with mixed solution mass ratio is the initiator of 15%, temperature of reaction is within the scope of 52 DEG C ~ 80 DEG C, through conventional free radical or living free radical polymerization 1 little of 10 hours, must based on the macromole softening agent of sewer oil;
Described initiator is at least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate and ammonium persulphate;
Described high polymerization activity monomer is at least one in vinylbenzene, Vinylstyrene, sodium methacrylate, glycidyl methacrylate, vinylformic acid, acrylamide, maleic anhydride and vinyl pyridine;
Described second-order transition temperature adjustment monomer is at least one in butyl acrylate, n-octyl, Hydroxyethyl acrylate, Propylene glycol monoacrylate and vinylformic acid ethylhexyl.
2. the preparation method of a kind of macromole softening agent based on sewer oil according to claim 1, is characterized in that: the close solubility parameter monomer of described PVC is at least one in methyl acrylate, ethyl propenoate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, vinylchlorid, Ethylene Dichloride, vinylidene chloride and vinyl acetate.
3. the preparation method of a kind of macromole softening agent based on sewer oil according to claim 1, is characterized in that: described conventional radical polymerization method is at least one in solution polymerization, letex polymerization, suspension polymerization.
4. the preparation method of a kind of macromole softening agent based on sewer oil according to claim 1, is characterized in that: described active free radical polymerization is at least one in anionoid polymerization, cationoid polymerisation, atom transfer radical polymerization and reversible addition fracture radical polymerization.
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| CN103642120B (en) * | 2013-11-01 | 2016-04-20 | 安徽冠泓塑业有限公司 | A kind of polypropylene expanded Wood plastic boards |
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| CN103773609A (en) * | 2013-10-29 | 2014-05-07 | 尚诚德 | Method for preparing plastic plasticizer by using illegally recycled waste cooking oil |
| CN103642122B (en) * | 2013-11-01 | 2016-04-20 | 安徽冠泓塑业有限公司 | The wood plastic composite that a kind of basalt fibre strengthens |
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| CN106350216A (en) * | 2016-08-25 | 2017-01-25 | 林群祥 | Chlorinated waste edible oil |
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| CN116041872B (en) * | 2021-10-28 | 2024-02-13 | 中国石油化工股份有限公司 | Migration-precipitation-resistant and aging-resistant PVC cable material composition |
| CN114736462B (en) * | 2022-05-19 | 2023-12-05 | 温州市金田塑业有限公司 | Ultralow-temperature heat sealing material for polypropylene and preparation method and application thereof |
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| JPS60161474A (en) * | 1984-01-31 | 1985-08-23 | Human Ind Corp | Production of solidified waste oil |
| JP3967173B2 (en) * | 2001-05-09 | 2007-08-29 | 株式会社クレハ | Polyvinylidene chloride resin composition and method for producing the same |
| CN100580025C (en) * | 2007-02-27 | 2010-01-13 | 张伟明 | Method for producing epoxy plasticizer from dirty oil and vegetable and animal waste oil |
| CN101519578B (en) * | 2008-03-01 | 2012-05-30 | 中国石油化工股份有限公司 | Special material for automotive seal strip and preparation method thereof |
| CN102161938B (en) * | 2011-03-25 | 2013-01-02 | 河北金谷油脂科技有限公司 | Method for producing epoxy fatty acid methyl ester by using illegal cooking oil |
| CN102295718B (en) * | 2011-05-26 | 2014-01-01 | 北京化工大学 | Bio-based high-branched polyester and preparation method thereof |
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| CN103642120B (en) * | 2013-11-01 | 2016-04-20 | 安徽冠泓塑业有限公司 | A kind of polypropylene expanded Wood plastic boards |
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