CN105524211A - Preparation method of quadripolymer pour point depressant for diesel oil - Google Patents
Preparation method of quadripolymer pour point depressant for diesel oil Download PDFInfo
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- CN105524211A CN105524211A CN201610082252.2A CN201610082252A CN105524211A CN 105524211 A CN105524211 A CN 105524211A CN 201610082252 A CN201610082252 A CN 201610082252A CN 105524211 A CN105524211 A CN 105524211A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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Abstract
The invention discloses a preparation method of a quadripolymer pour point depressant for diesel oil. The preparation method at least comprises steps as follows: a, in the presence of a solvent, methacrylic acid higher alcohol ester is synthesized with methacrylic acid and higher alcohol used as raw materials; b, in the presence of a solvent, maleic anhydride higher alcohol ester is synthesized with maleic anhydride and higher alcohol used as raw materials; c, in the presence of a solvent, methacrylic acid higher alcohol ester, maleic anhydride higher alcohol ester, vinyl acetate and styrene are taken as monomers, an initiator is added, and the quadripolymer pour point depressant for diesel oil is prepared, wherein the molar ratio of methacrylic acid higher alcohol ester to maleic anhydride higher alcohol ester to vinyl acetate to styrene is 4:(1.8-2.2):(2.8-3.2):(0.8-1.2). The preparation method has the benefits as follows: the quadripolymer pour point depressant is adopted to replace an existing homopolymer pour point depressant, and the pour point depression effect of the quadripolymer pour point depressant is better than that of the single-component homopolymer pour point depressant obviously.
Description
Technical field
The present invention relates to the present invention and be specifically related to diesel pour inhibitor field, particularly a kind of preparation method of tetrapolymer diesel pour inhibitor.
Background technology
Cold flow improver is the crystallisation process that a class can improve wax in diesel oil, makes diesel oil at low temperatures can continuous flow, and add-on seldom but the larger oil dope of effect.Turbidity removal agent, pour point depressant and anti-wax sinking agent can be divided into by its function.Diesel pour inhibitor can reduce zero pour and the cold filter clogging temperature of diesel oil effectively, makes diesel oil meet the requirement of low temperature use properties, thus increasing output of diesel oil, improve oil refining enterprise's economic benefit.Because add-on is few, cost is low, easy to operate, the method has become the prefered method solving research of cold flow properties of diesel fuel.It is all of great significance diesel component source of improving the quality of products, expand, raising refinery economic benefit.
Existing diesel pour inhibitor component is too single, and cannot adapt to the petroleum products of different structure, therefore depression effeCt is undesirable.Growing along with waxy crude oil output, existing diesel pour inhibitor can not be satisfied the demand.
Therefore, a kind of petroleum products that not only can adapt to different structure containing various ingredients, the preparation method that can also be applicable to the tetrapolymer diesel pour inhibitor of waxy crude oil becomes the key of dealing with problems.
Summary of the invention
As the result of various extensive and careful research and experiment, the present inventor has been found that: using tetrapolymer as the homopolymer pour point depressant of the depression effeCt of pour point depressant significantly better than single composition.
One object of the present invention provides a kind of preparation method of tetrapolymer diesel pour inhibitor, by methylacrylic higher alcohols ester, maleic anhydride high-carbon alcohol ester, vinyl acetate and vinylbenzene are prepared into copolymerization pour point depressant, effectively can reduce the cold filter clogging temperature of oil product, make it be more applicable for the high crude oil of the content of wax.
A further object of the invention is the preparation method providing a kind of tetrapolymer diesel pour inhibitor, can also according to the difference of diesel fuel oil structure, with the alcohols synthesizing carboxylate of different carbon number, to be applicable to the oil product of different wax content.
For achieving the above object, the invention provides a kind of preparation method of tetrapolymer diesel pour inhibitor, described method comprises:
A, under solvent condition, methacrylic acid and higher alcohols are heated to 60 ~ 70 DEG C, methacrylic acid and higher alcohols are fully dissolved in a solvent, add catalyzer tosic acid again, reacting by heating system is to occurring backflow, temperature of reaction is controlled at 110 ~ 130 DEG C, react 2 ~ 4 hours, obtained methylacrylic higher alcohols ester after dehydration;
B, under solvent condition, first maleic anhydride and higher alcohols are heated to 60 ~ 80 DEG C, maleic anhydride and higher alcohols are fully dissolved in a solvent, add catalyzer tosic acid again, reacting by heating system is to occurring backflow, temperature of reaction is controlled at 110 ~ 130 DEG C, react 2 ~ 4 hours, obtained maleic anhydride high-carbon alcohol ester after dehydration;
C, under solvent condition, with methylacrylic higher alcohols ester, maleic anhydride high-carbon alcohol ester, vinyl acetate and vinylbenzene for monomer, then add initiator, be prepared into tetrapolymer diesel pour inhibitor;
Wherein, methylacrylic higher alcohols ester described in step c: maleic anhydride high-carbon alcohol ester: vinyl acetate and cinnamic mol ratio are 4:1.8 ~ 2.2:2.8 ~ 3.2:0.8 ~ 1.2, the add-on of initiator accounts for 0.75% ~ 1.0% of total monomer total amount, temperature of reaction is 75-85 DEG C, and the reaction times is 5 ~ 7h.
Preferably, higher alcohols described in step a and step b is one or both in hexadecanol, stearyl alcohol.
Preferably, described solvent is toluene.
Preferably, in step a, methacrylic acid and higher alcohols are heated to 65 DEG C, methacrylic acid and higher alcohols are fully dissolved in a solvent, add catalyzer tosic acid again, reacting by heating system is to occurring backflow, temperature of reaction is controlled at 120 DEG C, react 3 hours, obtained methylacrylic higher alcohols ester.
Preferably, first maleic anhydride and higher alcohols are heated to 70 DEG C in step b, maleic anhydride and higher alcohols are fully dissolved in a solvent, add catalyzer tosic acid again, reacting by heating system is to occurring backflow, temperature of reaction is controlled at 120 DEG C, react 3 hours, obtained maleic anhydride high-carbon alcohol ester.
Preferably, also need to refine the methylacrylic higher alcohols ester of gained in step a and step b and maleic anhydride high-carbon alcohol ester respectively before step c.
Preferably, the process for purification of methylacrylic higher alcohols ester is: the methylacrylic higher alcohols ester of gained in step a is carried out underpressure distillation, to remove unreacted methacrylic acid and solvent; Be the NaOH solution cleaning of 5% again with massfraction, to remove unreacted catalyzer; Extremely neutral with deionized water wash again; After vacuum-drying, the methylacrylic higher alcohols ester after must refining.
Preferably, the process for purification of maleic anhydride high-carbon alcohol ester is: the maleic anhydride high-carbon alcohol ester of gained in step b is carried out underpressure distillation, to remove unreacted maleic anhydride and solvent; Be the NaOH solution cleaning of 5% again with massfraction, to remove unreacted catalyzer; Extremely neutral with deionized water wash again; After vacuum-drying, the maleic anhydride high-carbon alcohol ester after must refining.
Preferably, initiator described in step c is azo-bis-isobutyl cyanide.
Preferably, in steps d, methylacrylic higher alcohols ester, maleic anhydride high-carbon alcohol ester, vinyl acetate and cinnamic mol ratio are 4:2:3:1.
The invention has the beneficial effects as follows: 1, adopt tetrapolymer pour point depressant to substitute existing homopolymer pour point depressant, the depression effeCt of tetrapolymer pour point depressant is significantly better than the homopolymer pour point depressant of single composition; 2, tetrapolymer pour point depressant is adopted to be applicable to solve the existing homopolymer pour point depressant problem bad to paraffin molecule molecular weight inhomogenous oil product depression effeCt; 3, depression effeCt is good, is suitable for high-content wax oil product.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, can implement according to this with reference to specification sheets word to make those skilled in the art.
Embodiment 1
A, in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add hexadecanol, methacrylic acid and solvent toluene, reaction system is heated to 65 DEG C make it all dissolve after, then add catalyzer tosic acid.There is backflow in intensification reacting by heating system to 110 DEG C, maintains temperature of reaction 120 DEG C, reflux about 3h, obtains methacrylic acid hexadecanol ester; There is chemical reaction in the process as follows:
Wherein, R represents the alkyl of the carbon atom of 16
B, by maleic anhydride and hexadecanol, add successively in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add solvent toluene, be heated to 60 DEG C make it all dissolve after, add catalyzer tosic acid.Be heated to 110 DEG C and occur backflow, maintain temperature of reaction 120 DEG C, reflux about 3h, obtains maleic anhydride hexadecanol ester; There is chemical reaction in the process as follows:
Wherein, R represents the alkyl of the carbon atom of 16
C, the methacrylic acid hexadecanol ester of gained in step a is carried out underpressure distillation, to remove unreacted methacrylic acid and solvent; Then 5%NaOH aqueous cleaning is used, to remove unreacted catalyzer; Use deionized water wash again, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the methacrylic acid hexadecanol ester after refining.The maleic anhydride hexadecanol ester of gained in step b is carried out underpressure distillation, to remove unreacted maleic anhydride and solvent; Then use 5%NaOH aqueous cleaning, to remove catalyzer, then use deionized water wash, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the maleic anhydride hexadecanol ester after refining;
D, with the methacrylic acid hexadecanol ester after refining, maleic anhydride hexadecanol ester and vinyl acetate and vinylbenzene are monomer, added with electric mixer, reflux condensing tube, nitrogen ingress pipe, thermometer and dropping funnel four-hole boiling flask in, wherein methacrylic acid hexadecanol ester, maleic anhydride hexadecanol ester, vinyl acetate and cinnamic mol ratio are 4:2:3:1, add solvent toluene again, stir until monomer all dissolves at 60 DEG C, logical nitrogen protection, be warming up to 80 DEG C, add initiator dibenzoyl peroxide again, the add-on of initiator accounts for 0.85% of total monomer total amount, reaction 6h, i.e. obtained tetrapolymer diesel pour inhibitor of the present invention.There is following chemical reaction in the process:
Wherein, R represents the alkyl of the carbon atom of 16
Embodiment 2
A, in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add stearyl alcohol, methacrylic acid and solvent toluene, reaction system is heated to 60 DEG C make it all dissolve after, then add catalyzer tosic acid.There is backflow in intensification reacting by heating system to 110 DEG C, maintains temperature of reaction 130 DEG C, reflux about 2h, obtains methacrylic acid octadecyl;
B, by maleic anhydride and stearyl alcohol, add successively in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add solvent toluene, be heated to 60 DEG C make it all dissolve after, add catalyzer tosic acid.Be heated to 110 DEG C and occur backflow, maintain temperature of reaction 130 DEG C, reflux about 2h, obtains maleic anhydride octadecyl;
C, the methacrylic acid octadecyl of gained in step a is carried out underpressure distillation, to remove unreacted methacrylic acid and solvent; Then 5%NaOH aqueous cleaning is used, to remove unreacted catalyzer; Use deionized water wash again, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the methacrylic acid octadecyl after refining.The maleic anhydride octadecyl of gained in step b is carried out underpressure distillation, to remove unreacted maleic anhydride and solvent; Then use 5%NaOH aqueous cleaning, to remove catalyzer, then use deionized water wash, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the maleic anhydride octadecyl after refining;
D, with the methacrylic acid octadecyl after refining, maleic anhydride octadecyl and vinyl acetate and vinylbenzene are monomer, added with electric mixer, reflux condensing tube, nitrogen ingress pipe, thermometer and dropping funnel four-hole boiling flask in, wherein methacrylic acid octadecyl, maleic anhydride octadecyl, vinyl acetate and cinnamic mol ratio are 4:1.8:3.2:0.8, add solvent toluene again, stir until monomer all dissolves at 60 DEG C, logical nitrogen protection, be warming up to 75 DEG C, add initiator dibenzoyl peroxide again, the add-on of initiator accounts for 0.75% of total monomer total amount, reaction 7h, i.e. obtained tetrapolymer diesel pour inhibitor of the present invention.
Embodiment 3
A, in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add stearyl alcohol, methacrylic acid and solvent toluene, reaction system is heated to 70 DEG C make it all dissolve after, then add catalyzer tosic acid.There is backflow in intensification reacting by heating system to 110 DEG C, maintains temperature of reaction 110 DEG C, reflux about 4h, obtains methacrylic acid octadecyl;
B, by maleic anhydride and stearyl alcohol, add successively in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add solvent toluene, be heated to 80 DEG C make it all dissolve after, add catalyzer tosic acid.Be heated to 110 DEG C and occur backflow, maintain temperature of reaction 110 DEG C, reflux about 4h, obtains maleic anhydride octadecyl;
C, the methacrylic acid octadecyl of gained in step a is carried out underpressure distillation, to remove unreacted methacrylic acid and solvent; Then 5%NaOH aqueous cleaning is used, to remove unreacted catalyzer; Use deionized water wash again, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the methacrylic acid octadecyl after refining.The maleic anhydride octadecyl of gained in step b is carried out underpressure distillation, to remove unreacted maleic anhydride and solvent; Then use 5%NaOH aqueous cleaning, to remove catalyzer, then use deionized water wash, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the maleic anhydride octadecyl after refining;
D, with the methacrylic acid octadecyl after refining, maleic anhydride octadecyl and vinyl acetate and vinylbenzene are monomer, added with electric mixer, reflux condensing tube, nitrogen ingress pipe, thermometer and dropping funnel four-hole boiling flask in, wherein methacrylic acid octadecyl, maleic anhydride octadecyl, vinyl acetate and cinnamic mol ratio are 4:2.2:2.8:1.2, add solvent toluene again, stir until monomer all dissolves at 60 DEG C, logical nitrogen protection, be warming up to 85 DEG C, add initiator dibenzoyl peroxide again, the add-on of initiator accounts for 1% of total monomer total amount, reaction 5h, i.e. obtained tetrapolymer diesel pour inhibitor of the present invention.
Embodiment 4
A, in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add stearyl alcohol and hexadecanol, methacrylic acid and solvent toluene, reaction system is heated to 68 DEG C make it all dissolve after, then add catalyzer tosic acid.There is backflow in intensification reacting by heating system to 110 DEG C, maintains temperature of reaction 112 DEG C, reflux about 2.5h, obtains methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl);
B, by maleic anhydride, hexadecanol and stearyl alcohol, add successively in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add solvent toluene, be heated to 78 DEG C make it all dissolve after, add catalyzer tosic acid.Be heated to 110 DEG C and occur backflow, maintain temperature of reaction 112 DEG C, reflux about 4h, obtains maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl);
C, the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) of gained in step a is carried out underpressure distillation, to remove unreacted methacrylic acid and solvent; Then 5%NaOH aqueous cleaning is used, to remove unreacted catalyzer; Use deionized water wash again, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) after refining.The maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl) of gained in step b is carried out underpressure distillation, to remove unreacted maleic anhydride and solvent; Then use 5%NaOH aqueous cleaning, to remove catalyzer, then use deionized water wash, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl) after refining;
D, with the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) after refining, maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl) and vinyl acetate and vinylbenzene are monomer, added with electric mixer, reflux condensing tube, nitrogen ingress pipe, thermometer and dropping funnel four-hole boiling flask in, wherein methylacrylic higher alcohols ester, maleic anhydride high-carbon alcohol ester, vinyl acetate and cinnamic mol ratio are 4:1.9:3.1:0.9, add solvent toluene again, stir until monomer all dissolves at 60 DEG C, logical nitrogen protection, be warming up to 78 DEG C, add initiator dibenzoyl peroxide again, the add-on of initiator accounts for 0.8% of total monomer total amount, reaction 5.5h, i.e. obtained tetrapolymer diesel pour inhibitor of the present invention.
Embodiment 5
A, in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add stearyl alcohol and hexadecanol, methacrylic acid and solvent toluene, reaction system is heated to 62 DEG C make it all dissolve after, then add catalyzer tosic acid.There is backflow in intensification reacting by heating system to 110 DEG C, maintains temperature of reaction 128 DEG C, reflux about 3.5h, obtains methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl);
B, by maleic anhydride, hexadecanol and stearyl alcohol, add successively in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add solvent toluene, be heated to 72 DEG C make it all dissolve after, add catalyzer tosic acid.Be heated to 110 DEG C and occur backflow, maintain temperature of reaction 115 DEG C, reflux about 3.2h, obtains maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl);
C, the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) of gained in step a is carried out underpressure distillation, to remove unreacted methacrylic acid and solvent; Then 5%NaOH aqueous cleaning is used, to remove unreacted catalyzer; Use deionized water wash again, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) after refining.The maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl) of gained in step b is carried out underpressure distillation, to remove unreacted maleic anhydride and solvent; Then use 5%NaOH aqueous cleaning, to remove catalyzer, then use deionized water wash, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl) after refining;
D, with the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) after refining, maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl) and vinyl acetate and vinylbenzene are monomer, added with electric mixer, reflux condensing tube, nitrogen ingress pipe, thermometer and dropping funnel four-hole boiling flask in, wherein methylacrylic higher alcohols ester, maleic anhydride high-carbon alcohol ester, vinyl acetate and cinnamic mol ratio are 4:2.1:2.9:1.1, add solvent toluene again, stir until monomer all dissolves at 60 DEG C, logical nitrogen protection, be warming up to 82 DEG C, add initiator dibenzoyl peroxide again, the add-on of initiator accounts for 0.9% of total monomer total amount, reaction 6.5h, i.e. obtained tetrapolymer diesel pour inhibitor of the present invention.
Embodiment 6
A, in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add stearyl alcohol and hexadecanol, methacrylic acid and solvent toluene, reaction system is heated to 66 DEG C make it all dissolve after, then add catalyzer tosic acid.There is backflow in intensification reacting by heating system to 110 DEG C, maintains temperature of reaction 125 DEG C, reflux about 3.3h, obtains methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl);
B, by maleic anhydride, hexadecanol and stearyl alcohol, add successively in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add solvent toluene, be heated to 63 DEG C make it all dissolve after, add catalyzer tosic acid.Be heated to 110 DEG C and occur backflow, maintain temperature of reaction 118 DEG C, reflux about 3.8h, obtains maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl);
C, the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) of gained in step a is carried out underpressure distillation, to remove unreacted methacrylic acid and solvent; Then 5%NaOH aqueous cleaning is used, to remove unreacted catalyzer; Use deionized water wash again, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) after refining.The maleic anhydride high-carbon alcohol ester (comprising maleic anhydride octadecyl and maleic anhydride hexadecanol ester) of gained in step b is carried out underpressure distillation, to remove unreacted maleic anhydride and solvent; Then use 5%NaOH aqueous cleaning, to remove catalyzer, then use deionized water wash, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl) after refining;
D, with the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) after refining, maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl) and vinyl acetate and vinylbenzene are monomer, added with electric mixer, reflux condensing tube, nitrogen ingress pipe, thermometer and dropping funnel four-hole boiling flask in, wherein methylacrylic higher alcohols ester, maleic anhydride high-carbon alcohol ester, vinyl acetate and cinnamic mol ratio are 4:1.9:2.9:1, add solvent toluene again, stir until monomer all dissolves at 60 DEG C, logical nitrogen protection, be warming up to 76 DEG C, add initiator dibenzoyl peroxide again, the add-on of initiator accounts for 0.8% of total monomer total amount, reaction 6.8h, i.e. obtained tetrapolymer diesel pour inhibitor of the present invention.
Embodiment 7
A, in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add stearyl alcohol and hexadecanol, methacrylic acid and solvent toluene, reaction system is heated to 66 DEG C make it all dissolve after, then add catalyzer tosic acid.There is backflow in intensification reacting by heating system to 110 DEG C, maintain temperature of reaction 125 DEG C, reflux about 3.3h, obtains methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester, methacrylic acid octadecyl and methacrylic acid hexadecanol ester);
B, by maleic anhydride, hexadecanol and stearyl alcohol, add successively in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add solvent toluene, be heated to 63 DEG C make it all dissolve after, add catalyzer tosic acid.Be heated to 110 DEG C and occur backflow, maintain temperature of reaction 118 DEG C, reflux about 3.8h, obtains maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl);
C, the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) of gained in step a is carried out underpressure distillation, to remove unreacted methacrylic acid and solvent; Then 5%NaOH aqueous cleaning is used, to remove unreacted catalyzer; Use deionized water wash again, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) after refining.The maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl) of gained in step b is carried out underpressure distillation, to remove unreacted maleic anhydride and solvent; Then use 5%NaOH aqueous cleaning, to remove catalyzer, then use deionized water wash, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl) after refining;
D, with the methylacrylic higher alcohols ester (comprising methacrylic acid hexadecanol ester and methacrylic acid octadecyl) after refining, maleic anhydride high-carbon alcohol ester (comprising maleic anhydride hexadecanol ester and maleic anhydride octadecyl) and vinyl acetate and vinylbenzene are monomer, added with electric mixer, reflux condensing tube, nitrogen ingress pipe, thermometer and dropping funnel four-hole boiling flask in, wherein methylacrylic higher alcohols ester, maleic anhydride high-carbon alcohol ester, vinyl acetate and cinnamic mol ratio are 4:1.9:3.1:1, add solvent toluene again, stir until monomer all dissolves at 60 DEG C, logical nitrogen protection, be warming up to 76 DEG C, add initiator dibenzoyl peroxide again, the add-on of initiator accounts for 0.95% of total monomer total amount, reaction 6.8h, i.e. obtained tetrapolymer diesel pour inhibitor of the present invention.
Comparative example 1
A, in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add hexadecanol, methacrylic acid and solvent toluene, reaction system is heated to 80 DEG C make it all dissolve after, then add catalyzer tosic acid.There is backflow in intensification reacting by heating system to 110 DEG C, maintains temperature of reaction 140 DEG C, reflux about 1.5h, obtains methacrylic acid hexadecanol ester;
B, by maleic anhydride and hexadecanol, add successively in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add solvent toluene, be heated to 80 DEG C make it all dissolve after, add catalyzer tosic acid.Be heated to 110 DEG C and occur backflow, maintain temperature of reaction 140 DEG C, reflux about 1.5h, obtains maleic anhydride hexadecanol ester;
C, the methacrylic acid hexadecanol ester of gained in step a is carried out underpressure distillation, to remove unreacted methacrylic acid and solvent; Then 5%NaOH aqueous cleaning is used, to remove unreacted catalyzer; Use deionized water wash again, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the methacrylic acid hexadecanol ester after refining.The maleic anhydride hexadecanol ester of gained in step b is carried out underpressure distillation, to remove unreacted maleic anhydride and solvent; Then use 5%NaOH aqueous cleaning, to remove catalyzer, then use deionized water wash, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the maleic anhydride hexadecanol ester after refining;
D, with the methacrylic acid hexadecanol ester after refining, maleic anhydride hexadecanol ester and vinyl acetate and vinylbenzene are monomer, added with electric mixer, reflux condensing tube, nitrogen ingress pipe, thermometer and dropping funnel four-hole boiling flask in, wherein methacrylic acid hexadecanol ester, maleic anhydride hexadecanol ester, vinyl acetate and cinnamic mol ratio are 4:2:2:1, add solvent toluene again, stir until monomer all dissolves at 60 DEG C, logical nitrogen protection, be warming up to 90 DEG C, add initiator dibenzoyl peroxide again, the add-on of initiator accounts for 0.6% of total monomer total amount, reaction 4h, i.e. tetrapolymer diesel pour inhibitor processed.
Comparative example 2
A, in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add stearyl alcohol, methacrylic acid and solvent toluene, reaction system is heated to 55 DEG C make it all dissolve after, then add catalyzer tosic acid.There is backflow in intensification reacting by heating system to 110 DEG C, maintains temperature of reaction 110 DEG C, reflux about 4.5h, obtains methacrylic acid octadecyl;
B, by maleic anhydride and stearyl alcohol, add successively in the there-necked flask that thermometer, agitator, reflux exchanger, water trap are housed, add solvent toluene, be heated to 55 DEG C make it all dissolve after, add catalyzer tosic acid.Be heated to 110 DEG C and occur backflow, maintain temperature of reaction 110 DEG C, reflux about 4.5h, obtains maleic anhydride octadecyl;
C, the methacrylic acid octadecyl of gained in step a is carried out underpressure distillation, to remove unreacted methacrylic acid and solvent; Then 5%NaOH aqueous cleaning is used, to remove unreacted catalyzer; Use deionized water wash again, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the methacrylic acid octadecyl after refining.The maleic anhydride octadecyl of gained in step b is carried out underpressure distillation, to remove unreacted maleic anhydride and solvent; Then use 5%NaOH aqueous cleaning, to remove catalyzer, then use deionized water wash, until neutral; Under vacuum, temperature 40 DEG C, namely dry 24h obtains the maleic anhydride octadecyl after refining;
D, with the methacrylic acid octadecyl after refining, maleic anhydride octadecyl and vinyl acetate and vinylbenzene are monomer, added with electric mixer, reflux condensing tube, nitrogen ingress pipe, thermometer and dropping funnel four-hole boiling flask in, wherein methacrylic acid octadecyl, maleic anhydride octadecyl, vinyl acetate and cinnamic mol ratio are 4:2:4:1, add solvent toluene again, stir until monomer all dissolves at 60 DEG C, logical nitrogen protection, be warming up to 70 DEG C, add initiator dibenzoyl peroxide again, the add-on of initiator accounts for 1.2% of total monomer total amount, reaction 7h, i.e. tetrapolymer diesel pour inhibitor processed.
Testing data
By by diesel pour inhibitor obtained in embodiment 1-7 and comparative example 1-2 according to 0.08% the dosage that adds join the test carrying out cold filter clogging temperature in diesel oil, the data obtained is in table 1.Wherein the zero pour of diesel oil is 1 DEG C, cold filter clogging temperature-1 DEG C.
Table 1
| Project | Cold filter clogging temperature DEG C |
| Embodiment 1 | -8.5 |
| Embodiment 2 | -8.0 |
| Embodiment 3 | -7.9 |
| Embodiment 4 | -8.2 |
| Embodiment 5 | -8.3 |
| Embodiment 6 | -8.3 |
| Embodiment 7 | -8.4 |
| Comparative example 1 | -4.5 |
| Comparative example 2 | -6.2 |
As can be seen from table one, the pour point depressant prepared according to the inventive method has good depression effeCt, obviously can reduce cold filter clogging temperature.
By according to the obtained pour point depressant of embodiment 1 according to 0.065%, 0.075%, 0.080%, 0.09%, 0.10% the dosage that adds join in diesel oil, and carry out the test of cold filter clogging temperature respectively, test result is in table 2.
Table 2
| Add dosage % | Cold filter clogging temperature DEG C |
| 0.065 | -7.0 |
| 0.075 | -8.5 |
| 0.080 | -8.7 |
| 0.090 | -8.5 |
| 0.100 | -7.5 |
This shows, when adding dosage in 0.075% ~ 0.09% scope, good depression effeCt can be obtained.
As mentioned above, the preparation method of a kind of tetrapolymer diesel pour inhibitor of the present invention, adopts tetrapolymer pour point depressant to substitute existing homopolymer pour point depressant, and the depression effeCt of tetrapolymer pour point depressant is significantly better than the homopolymer pour point depressant of single composition; Tetrapolymer pour point depressant is adopted to be applicable to solve the existing homopolymer pour point depressant problem bad to paraffin molecule molecular weight inhomogenous oil product depression effeCt; Depression effeCt is good, is suitable for high-content wax oil product.
Although embodiment of the present invention are open as above, but it is not restricted to listed in bright book and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details.
Claims (10)
1. a preparation method for tetrapolymer diesel pour inhibitor, is characterized in that, described method comprises:
A, under solvent condition, methacrylic acid and higher alcohols are heated to 60 ~ 70 DEG C, methacrylic acid and higher alcohols are fully dissolved in a solvent, add catalyzer tosic acid again, reacting by heating system is to occurring backflow, temperature of reaction is controlled at 110 ~ 130 DEG C, react 2 ~ 4 hours, obtained methylacrylic higher alcohols ester after dehydration;
B, under solvent condition, first maleic anhydride and higher alcohols are heated to 60 ~ 80 DEG C, maleic anhydride and higher alcohols are fully dissolved in a solvent, add catalyzer tosic acid again, reacting by heating system is to occurring backflow, temperature of reaction is controlled at 110 ~ 130 DEG C, react 2 ~ 4 hours, obtained maleic anhydride high-carbon alcohol ester after dehydration;
C, under solvent condition, with methylacrylic higher alcohols ester, maleic anhydride high-carbon alcohol ester, vinyl acetate and vinylbenzene for monomer, then add initiator, be prepared into tetrapolymer diesel pour inhibitor;
Wherein, methylacrylic higher alcohols ester described in step c: maleic anhydride high-carbon alcohol ester: vinyl acetate and cinnamic mol ratio are 4:1.8 ~ 2.2:2.8 ~ 3.2:0.8 ~ 1.2, the add-on of initiator accounts for 0.75% ~ 1.0% of total monomer total amount, temperature of reaction is 75-85 DEG C, and the reaction times is 5 ~ 7h.
2. the preparation method of tetrapolymer diesel pour inhibitor as claimed in claim 1, is characterized in that: higher alcohols described in step a and step b is one or both in hexadecanol, stearyl alcohol.
3. the preparation method of tetrapolymer diesel pour inhibitor as claimed in claim 1 or 2, is characterized in that: described solvent is toluene.
4. the preparation method of tetrapolymer diesel pour inhibitor as claimed in claim 1, it is characterized in that: in step a, methacrylic acid and higher alcohols are heated to 65 DEG C, methacrylic acid and higher alcohols are fully dissolved in a solvent, add catalyzer tosic acid again, reacting by heating system is to occurring backflow, temperature of reaction is controlled at 120 DEG C, react 3 hours, obtained methylacrylic higher alcohols ester.
5. the preparation method of tetrapolymer diesel pour inhibitor as claimed in claim 1, it is characterized in that: in step b, first maleic anhydride and higher alcohols are heated to 70 DEG C, maleic anhydride and higher alcohols are fully dissolved in a solvent, add catalyzer tosic acid again, reacting by heating system is to occurring backflow, temperature of reaction is controlled at 120 DEG C, react 3 hours, obtained maleic anhydride high-carbon alcohol ester.
6. the preparation method of tetrapolymer diesel pour inhibitor as claimed in claim 1 or 2, is characterized in that: also need to refine the methylacrylic higher alcohols ester of gained in step a and step b and maleic anhydride high-carbon alcohol ester respectively before step c.
7. the preparation method of tetrapolymer diesel pour inhibitor as claimed in claim 6, it is characterized in that, the process for purification of methylacrylic higher alcohols ester is: the methylacrylic higher alcohols ester of gained in step a is carried out underpressure distillation, to remove unreacted methacrylic acid and solvent; Be the NaOH solution cleaning of 5% again with massfraction, to remove unreacted catalyzer; Extremely neutral with deionized water wash again; After vacuum-drying, the methylacrylic higher alcohols ester after must refining.
8. the preparation method of tetrapolymer diesel pour inhibitor as claimed in claim 6, it is characterized in that, the process for purification of maleic anhydride high-carbon alcohol ester is: the maleic anhydride high-carbon alcohol ester of gained in step b is carried out underpressure distillation, to remove unreacted maleic anhydride and solvent; Be the NaOH solution cleaning of 5% again with massfraction, to remove unreacted catalyzer; Extremely neutral with deionized water wash again; After vacuum-drying, the maleic anhydride high-carbon alcohol ester after must refining.
9. the preparation method of tetrapolymer diesel pour inhibitor as claimed in claim 1, is characterized in that: initiator described in step c is azo-bis-isobutyl cyanide.
10. the preparation method of tetrapolymer diesel pour inhibitor as claimed in claim 1, is characterized in that: in steps d, methylacrylic higher alcohols ester, maleic anhydride high-carbon alcohol ester, vinyl acetate and cinnamic mol ratio are 4:2:3:1.
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| CN114989373A (en) * | 2022-05-11 | 2022-09-02 | 滨州学院 | Copolymer pour point depressant based on halloysite nanotube and preparation method thereof |
| CN114989373B (en) * | 2022-05-11 | 2023-05-05 | 滨州学院 | Copolymer pour point depressant based on halloysite nanotubes and preparation method thereof |
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