CA2008986A1 - Concentraded mixtures of graft copolymers of esters of unsaturated acids and ethylene/vinyl ester copolymers - Google Patents
Concentraded mixtures of graft copolymers of esters of unsaturated acids and ethylene/vinyl ester copolymersInfo
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- CA2008986A1 CA2008986A1 CA002008986A CA2008986A CA2008986A1 CA 2008986 A1 CA2008986 A1 CA 2008986A1 CA 002008986 A CA002008986 A CA 002008986A CA 2008986 A CA2008986 A CA 2008986A CA 2008986 A1 CA2008986 A1 CA 2008986A1
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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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
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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
-
- 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
-
- 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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
-
- 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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Graft Or Block Polymers (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
- 20 - O.Z. 0050/40595 Abstract of the Disclosure: Concentrated mixtures con-tain (i) an organic solvent, (ii) a low molecular weight graft copolymer of the general formula I and (iii) a relatively high molecular weight graft copolymer of the general formula I
A - E I
where A is a-segment of a polymer which consists of from 70 to 100% by weight of monomer units of the general formula II and from 0 to 30% by weight of monomer units of the general formula III
XHC=CR1Y II
CH2=CR1Z III
where R1 is H or CH3, X is H, COOH or COOR2, Y is COOH or COOR2 or X and Y are the anhydride radical CO-O-CO, Z is OCOR2, OR2, a heterocyclic 5-membered or 6-membered ring or a radical CO-B-D-R3, R2 is C1-C40-alkyl, B is O or NH, D is a C2-C10-hydrocarbon bridge and R3 is OH or N(R2)2 in which R2 has the abovementioned meaning, and E is a segment of a copolymer of ethylene with vinyl esters of aliphatic C1-C24-carboxylic acids, with or without (iv) a polymer which contains only the segments A.
A - E I
where A is a-segment of a polymer which consists of from 70 to 100% by weight of monomer units of the general formula II and from 0 to 30% by weight of monomer units of the general formula III
XHC=CR1Y II
CH2=CR1Z III
where R1 is H or CH3, X is H, COOH or COOR2, Y is COOH or COOR2 or X and Y are the anhydride radical CO-O-CO, Z is OCOR2, OR2, a heterocyclic 5-membered or 6-membered ring or a radical CO-B-D-R3, R2 is C1-C40-alkyl, B is O or NH, D is a C2-C10-hydrocarbon bridge and R3 is OH or N(R2)2 in which R2 has the abovementioned meaning, and E is a segment of a copolymer of ethylene with vinyl esters of aliphatic C1-C24-carboxylic acids, with or without (iv) a polymer which contains only the segments A.
Description
X008981~
O.Z. 0050/40595 Concentrated mixtures of qraft copolymers of esters of unsaturated acid~ and ethylene/vinyl ester copolymer~
The present invention relates to concentrated mixtures of graft copolymers of e~ters of unsaturated acids, such as (meth)acrylates and ethylene/vinyl ester copolymers and their use as flow improver~ and pour point depressants for crude oils, residues and middle distillates.
Depending on their origin, petroleum oils may contain substantial amounts of paraffins (which are also referred to as wax). At ~he temperatures prevailing in the ground, the paraffins are present in dissolved form.
When the petroleum oil c0015, for example during trans-port in a pipeline or storage in a tank, the dissolved paraffins may gradually separate out. They frequently form three-dimensional structures which are capable of binding large hmounts of petroleum oil. Thi~ results in an increase in the viscosity of the petroleum oil and, at sufficiently low temperatures, the oil may even completely solidify. This is particularly true for the residues obtained in refineries, al80 referred to as long residues, since their content of low-boiling components has been reduced by distillation and they therefore have a higher wax content.
This behavior is very disadvantageous particular-ly during transport of the petroleum oil through pipe-lines. Paraffin deposits may hinder flow, necescitating greater pumping power. This may lead to high tran~port costs, particularly in pipelines which extend over long distances. If the resistance is too high, the permis-sible maximum pressure may be reached, causing transport to be shut down.
Furthermore, when transport is interrupted due to crystallization of the paraffins on coolin~ of the petroleum oil, the viscosity may increase to such an extent that transpor~ cannot be restarted since either - 2 - O.Z. 0050/40595 the pumps can no longer provide the required start-u~
pressure, which is several times higher than the regular transport pressure, or the pipeline cannot withstand the start-up pressure.
5It is therefore very important to keep to a minimum the adverse effect of wax on the flow properties of the petroleum oil or of other paraffin-containing oils, such as residues or middle distillates. This can be achieved if low-boiling petroleum oil fractions, for 10example diesel or kerosine, are added to the oil so that, as a result of the dilution, the paraffins are kept in solution on cooling. Moreover, storage means may be de~igned to be heatable so that the paraffins are prevented from crystallizing out by the higher tempera-15ture. However, these procedures are highly energy-consumptive and therefore uneconomical in many cases. It i8 an ob~ect of the present invention to provide suitable additives which, when used in a very small amount, prevent cry~tsllization of the paraffin on cooling of the 20petroleum oil or of other oils or which modify the crystals being formed in such a way that the flow proper-ties of the oil are not adversely affected.
Additives which are liquid at about 25C and have a very high polymer content are increasingly being 25required for indu~trial use. To ensure simple metering of multiple component additive~, all components in a single additive should be present in macroscopically homogeneous form. This also ensures rapid mixing with, and dissolution in, the wax-containing oils, which is an 30important precondition for the efficiency of the additive.
In addition to others, two polymer classes in particular have been found to date to be ef~icient pour point depre3sants and flow improvers for petroleu~ oils.
35The first group comprises polymeric esters of unsaturated mono- or bifunctional carboxylic acids and long-chain alkanols, for example polyalkyl (meth)acrylates (cf. U.S.
~30898~
_ 3 _ o.Z. 0050/40595 Patents 3,669,189 and 3,729,296). The second group com-prises copolymers of ethylene and vinyl esters of Cl-C4-fatty acids with a vinyl ester content of about 10-40~ by weight (cf. U.S. Patents 3,567,639 and 3,669,189). These polymers are generally referred to as EVA polymers.
U.~. Patent 3,726,653 describes mixtures of poly-alkyl acrylates and EVA polymers which are distinguished by the synergistic effect of the two components. Japan-ese Preliminary Published Application 53593/84 (Chem.
~bstr. 101, 133833z) discloses graft copolymers of EVA
polymers and C3-C2l-alkyl acrylates and/or styrene or alkylated derivatives and their use as flow improvers for middle distillates and petroleum oils.
Solutions of relatively high molecular weight ethylene/vinyl acetate copolymers in aromatic solvents possess good flow properties at room temperature and can be handled only if they have polymer contents of not more than about 10-15% by weight. Polylmeth~acrylates of C16-C2a-fatty alcohols are likewise solid at temperatures slightly below room temperature.
As stated above, the combination of ethylene/
vinyl acetate copolymer~ and polyalkyl (meth)acrylates according to U.S. Patent 3,726,653 particularly effect-ively depresses the pour point of petroleum oils. How-ever, if the two polymer system~ are mixed in a solvent, phase separation occurs owing to the incompatibility of the two polymer ~y~tems, the EVA copolymer settling out in gelatinous form on the bottom of the vessels. Such a mixture cannot be used industrially.
German Laid-Open Application DOS 3,613,247 describes stable concentrated emulsions of ethylene/vinyl ester copolymers. They are obtained by dispersing EVA
polymers and~or polyalkyl (meth)acrylates in ~a carrier in which the polymer~ are insolubleO The dispersants used include block or graft copolymers of EVA polymers and alkyl (meth)acrylates. However, the known systems are unsatisfactory.
Xl~ 9~, _ 4 _ o.z 0050~40595 We have found that this object i8 achieved by an advantageous system for use a~ a flow improver and pour point depressant for wax-containing oils. The pre~ent invention relates to concentrated mixtures containing (i) an organic solvent, ~ii) a low molecular weight graft copolymer of the general formula I and (iii) a relatively high molecular weight graft copolymer of the general formula I
A - E
where A is a segment of a pol~mer which consists of from 70 to 100% by weight of monomer units of the general formula II and from O to 30~ by weight of monomer units of the general formula III
XHC=CR1Y II
CH2=C~1Z III
where R1 is H or CH3, X i8 H, COOH or COOR2, Y is COOH or COOR2 or X and Y are the anh~dride radical CO-O-CO, Z is OCOR2, OR2, a heterocyclic 5-membered or 6-membered ring or a radical CO-B-D-R3, R2 i~ Cl-C40-alkyl, B i.R O or NH, D is a C2-C1O-hydrocarbon bridge and R3 is OH or N(R2) 2 in which R2 has the abovementioned meaning, and E i3 a segment of a copolymer of ethylene with vinyl esters of aliphatic C1-C24-carboxylic acids, with or without ~iv) a polymer which contains only the ~egments A.
The novel concentrated mixture which contain an organic solvent and both a low molecular weight and a relatively high molecular w~ight graft copolymer of e~ters of unsaturated acids, for example (meth)acrylates, and EVA polymers give ready-to-despatch forms which remain stable and retain their good flow properties even on prolonged storage at conventional ambient temperature~
and do not cause precipitation of polymer3. Furthermore, the polymers are present in a form ~uch tha~t, when the mixture is added to the wax-containing oils or when further ~olvent is added to the concentrated mixtures, the said polymers go into solution readily and rapidly.
At the same time, the use of the novel mixture of a low _ 5 _ o.z. 0050~40595 molecular weight graft polymer and a relatively high molecular weight graft polymer results in a ~ynergistic effect in terms of improvement of the flow properties and of the pour point depression of the wax-containing oilR, in that the combination of low molecular weight and relatively high molecular weight graft copolymerR has a greater effect than the sum of the individual effects of low molecular weight graft polymer and relatively high molecular weight graft copolymer.
The organic solvents u~ed for the novel concen-trated mixtures are in general aliphatic and, preferably, aromatic hydrocarbons. Suitable aliphatic hydrocarbons are, for example, gasoline fractions, such as light naphtha, naphtha, median gasoline, ligroin, kero3ine, diesel oil and gas oil. Examples of suitable aromatic hydrocarbons are benzene, toluene, xylene, alkylbenzenes and mixtures thereof. The organic solvents are used in general in amounts such that the total polymer content of the novel concentrated misture is from 20 to 70, prefer-ably from 20 to 65, in particular from 25 to 60, % by weight.
The novel concentrated mixtures contain, in addi-tion to the organic solvent, a low molecular weight graft copolymer and a relatively high molecular weight graft copolymer each of the general formula I
A - E
where A is a segment of a polymer (polymer A~ which con-8iSt8 of from 70 to 100, preferably from 80 to 100, ~ by weight of monomer units of the general formula II and from 0 to 30, preferably from 0 to 20, ~ by weight of monomer units of the general formula III
XHC=CR1Y II
CHz=CRlZ ~III
where R1 i8 H or CH3, X is H, COOH or COOR2, Y is COOH or COOR2 or X and Y are the anhydride radical CO-O-CO, Z is OCOR2, OR2, a heterocyclic 5-membered or ~-membered ring or a radical CO-B-D-R3, R2 is Cl-C40-alkyl, B is O or NH, Z~ ~9~
- 6 - O.Z. 0050/40595 D is a C2-C1O-hydrocarbon bridge and R3 i8 OH or N(R2)2 in which R2 has the abovementioned meanin~.
Suitable monomers of the general formula II are, for example, mono- and dialkyl maleates and mono- and di-alkylfumarates, maleic anhydride and alkyl (met~)-acrylates having in general a Cl-C40-, preferably C1-C34-, in particular Ca-C24-alkyl group. Ethers of (meth)acrylic acid with C1-C40-, preferably C1-C34-, preferably C8-C24-alcohols, from O to 20~ by weight of whose alkyl chains may be branched, are preferably used. In general, these alcohols are essentially primary alcohols, for example having a content of from 80 to 100~ by weight of primary alcohols, but may contain from O to 20% by weight of secondary alcohols.
The monomers of the general formula II are essen-tially esters of unsaturated acid~ and alcohols, which can be obtained by the known es~erification processes.
For example, the alkyl (meth)acrylates can be obtained by a method in which a solution of (meth)acrylic acid and an alkanol in an organic solvent, preferably in the solvent in which the polymerization to give the graft copolymers is subsequently carried out, is heated to the boil with the addition of a conventional polymerization inhibitor, for example a hydroquinone derivative, and an esterifica-tion cataly3t, such as sulfuric acid or p-toluenesulfonic acid, and the water of reaction formed is removed by azeotropic distillation. To purify ~he ester, in par-ticular to remove the added inhibitor and excess (meth)-acrylic acid, the ester solution can be washed with an alkaline agent, for example with dilute sodium hydroxide solution or sodium carbonate solution, and then with water.
Examples of suitable monomers of ~he general formula III are vinylalkyl esters, alkylamino~meth)-acrylates, alkylamino(meth)acrylamides and vlnylhetero-cycles, such as vinylpyridine, vinylpyrrolidone, vinyl-carbazole, vinylimidazole and their alkyl derivatives.
2~R986 - 7 - O.Z. OG50/40595 In the general formula I, E is a segment of a co-polymer of ethylene with vinyl e~ters o~ aliphatic, generally saturated C1-C24-carboxylic acids, preferably of aliphatic Cl-C4-carboxylic acids (EVA polymers). The EVA
polymers are known per se (cf. U.S. Patent 3,382,055).
In their preparation, it is also possible simultaneously to use vinyl esters which differ from one another. They can be prepared, for example, by mass, emulsion or solu-tion polymerization. Examples of comonomers are vinyl esters of acetic acid, propionic acid, butyric acid, 2-ethylhexanecarboxylic acid, pelargonic acid and stearic acid, in particular C2-C4-carboxylic acid~, vinyl acetate being particularly preferred. In general, the vinyl ester content is from 10 to 80, preferably from 15 to 45, % by weight, ie. the ethylene content is accordingly from 20 to 90, preferably from 55 to 85, % by weight. The melt flow index according to ASTM D 1238 is generally from 1 to 800, preferably from 10 to 400, in particular from 15 to 100, g/10 min.
The graft copolymer~ of the general formula I are generally obtained by conventional free radical graft polymexization, by graftinq the monomers of the general formula II and, if required, those of the general formula III onto EVA polymers. For example, an initiator and some of the monomer~ of the general formula II and, where relevant, III are added to a solution of the EVA polymer, such a~ the ethylene/vinyl acetate copolymer, in an organic solvent, for example in an aliphatic or, prefer-ably, aromatic hydrocarbon, such as benzene, toluene, xylene or another alkylbenzene or a mixture thereof, advantageou~ly under a blanketing agent, such as nitrogen or carbon dioxide, and the remainder of the monomers and further initiator are added in the course~of several hours, for example from 2 to 8 hours. The free radical polymerization may al~o be carried out by the batch method, in which the ethylene/vinyl acetate copolymer and the total amount of the monomer~ of the formulae II and, X0~ 3fi - 8 - O.Z- 0050/40595 where relevant, III are initially taken and the initiator is then metered in over several hours. The polymeriza-tion reaction is advantageously effected at from 50 to 200C, preferably from 60 to 130C. Depending on the polymerization temperature, peroxo or azo initiators, eg.
tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, cumyl hydroperodixide, tert-butyl hydroperoxide,2,2'-azobis-(2,4-dimethylvaleronitrile)or 2,2'-azobisisobutyronitrile, are generally used as initiators, advantageously in amount~ of from 0.05 to 5, preferably from 0.1 to 1, % by weight, based on the mono-mers used. Redox systems, for example benzoin, dimethyl-aniline, ascorbic acid and complexes of heavy metals, such as copper, cobalt, manganese, iron, nickel and chromium, which are soluble in organic solvents, are also suitable as initiators, or the reaction may be ac-celerated by the concomitant use of such redox systems as coinitiators. The amounts usually used are from 0.1 to 2,000, preferably from 0.1 to 1,000, ppm by weight. In choosing the initiator or the initiator system, it is advantageou~ to ensure that the half life of the in-itiator or of the initiator system is less than 3 hours at the ~elected polymerization temperature. At 150C, for example, the half life of tert-butyl hydroperoxide i3 less than 3 hours. On the other hand, the polymerization behavior of the initiator system comprising 1% by weight of tert-butyl hydroperoxide/S ppm by weight of copper(II) acetylacetonate at as low as 100C is comparable with that of 1% by weight of tert-butyl hydroperoxide at 150C. If, for example, prepolymerization is carried out at a low temperature and polymerization is completed at a higher temperature, two or more initiators are generally used.
To obtain low molecular weight graft copolymers, it is often advantageous to carry out the reaction in the presence of regulators. Example~ of -~uitable regulators are allyl compounds, such as allyl alcohol, but-1-en-3-ol 20~R986 _ g _ o.z. 0050/40595 and, preferably, organic mercapto compounds, ~uch as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and-tert-dodecyl mercaptan, which are generally used in amount~ of from 0.1 to 10~ by weight.
Apparatuses which are suitable for the polymeriz-ation are, for example, conventional stirred kettles having, for example, anchor stirrers, paddle stirrers, Lmpeller stirrers or multistage impulse countercurrent agitators, and apparatuses which are suitable for the continuous preparation are ~tirred kettle cascade~, tube reactors and static mixers.
In the graft copolymers of the general formula I, the ratio of segments A to segments E is in general from 20 to 95, preferably from 60 to 95, in particular from 70 to 90, % by w~ight of segment A and from S to 80, prefer-ably from 5 to 40, in particular from 10 to 30, % by weight of segment E.
An essential feature of the present invention i~
that the concentrated mixtureY contain a low molecular weight and a relatively high molecular weight graft copolymer of the general formula I. The low molecular weight and relatively high molecular weight graft copoly-mers are ob~ained a~ a low molecular weight or relatively high molecular weight graft copolymer depending on the choice of the initiators, coinitiators, regulators, polymerization temperatures and molecular weight of the EVA polymer used. Thus, for the preparation of the low molecular weight graft copolymers, regulators are advan-tageously added. The weight ratio of the low molecular weight graft copolymer to the relatively high molecular weight graft copolymer in the novel concentra~ed mixtures is in general from 1 : 10 to 100 : 1, preferably from 2 : 1 to 40 : 1, in particular from 5 : 1 to 30 : 1. The segments A and E in the low molecular weight and relatively high molecular weight graft copolymers may be Z0C~898~
- 10 - O.Z. OG50/40595 identical or different. By appropriate combination of segment~ A and E in the low molecular weight and rela-tively high molecular weight graft polymers, it i~
possible to adapt and optimize the efficiency of the novel concentrated mixtures with regard to improvement of the flow behavior and depression of the pour point, to meet the requirements of the particular oil pre~ent.
The concentrated mixtures used are in general those where the low molecular weight graft copolymers present in the mixture are graft copolymer~ as obtained by grafting the monomers of the general formulae II and III onto E~A polymers under reaction conditions which, when only the EVA polymers are omitted and under other-wise identical reaction conditions, give polymers of the monomer~ of the general formulae II and, where relevant, III which have R values (according to H. Fikentscher, Cellulosechemie, 13 (1932~, 58-64 and 71-74) of from 7 to 20, preferably from 10 to 18, and in which the relatively high molecular weight graft copolymer~ present in the mixture are graft copolymers as obtained by grafting the monomers of the general formulae II and, where relevant, III onto EVA polymers under reaction conditions which, when only the EVA polymer~ are omitted and under other-wise identical reaction condition~, give polymers of the monomers of the general formulae II and, where relevant, III which have R values of from 20 to 70, preferably from 25 to 50.
- The novel concentrated mixtures are obtained, for example, by mixing the corresponding amounts of low molecular weight and relatively high molecular weight graft copolymers at, adYantageously, from 60 to 180C, preferably from 80 to 150C, in the organic solvent. The temperature and order of addition are ad~antageously chosen so that the low molecular weight graft copolymer is first dissolved in the organic solvent to give a homogeneous solution. The high molecular weight polymer i8 then added. In another possible method, the 2~8986 - 11 - O.Z. 0050t40595 polymerization reaction for the preparation of the graft copolymers is controlled in such a way that the low molecular weight and relatively high molecular weight graft copolymers are formed in one reaction vessel. For example, this can be achieved in the batch proces~ by first carrying out prepolymerization with a small amount of initiator at a low temperature with formation of the high molecular weight graft copolymer and then, after the addition of regulator and further initiator, completing the polymerization at a higher temperature with formation of the low molecular weight graft copolymer. In another possible method for the preparation of concentrated mixtures, the relatively high molecular weight graft copolymer is initially taken in a reaction vessel and the low molecular weight graft copolymer i~ prepared in the reaction vessel in the pre ence of the relatively high molecular weight graft copolymer.
The novel concentrated mixtures may additionally contain a polymer A corresponding to tho segments A, for example in amounts of from 0 to 50% by weight, based on the total polymer content of the concentrated mixtures.
This may be effected by adding to the concentrated mix-tures polymer A which ha~ baen prepared separately in a similar manner to the graft copclymers by free radical polymerization from the monomers of the general formulae II and, where relevant, III.
However, the concentrated mixtures containing polymer A may also be obtained by converting some of the monomers II and~ where relevant, III to the polymer A in the preparation of the novel graft copolymers, and in general in the preparation of the low molecular weight graft copolymers, the said polymer A remaining ungrafted.
The Example~ which follow illustrate the invention.
EXAMPLE~
A) Preparation of the esters - 12 - O.Z. 0050/40595 Preparation of a Cl6-C22-alkyl acrylate (e~ter 1~
25% by weight, based on the starting materials alkanol mixture and acrylic acicl, of toluene were added to 1 mole of a fatty alcohol mixture con~isting of about 20~ by weight of n-C16-alkanol, 40% by weight of n-C18-alkanol, 10% by weight of n-C20-alkanol and 30% by weight of n-C22-alkanol, 1 mole of acrylic acid, 4 millimoles of hydroquinone monomethyl ether and 5 millimoles of p-toluenesulfonic acid, and the mixture was heated under a water separator until no further water was separated off.
Preparation of a Cla-C22-alkyl acrylate (ester 1) The preparation was carried out similarly to lS Example 1, except that a fatty alcohol mixture consisting of about 45% by weight of n-Cl8-alkanol, 10% by weight of n-C20-alkanol and 45% by weight of n-C22-alkanol was used.
B) Preparation of the relatively high molecular weight graft copolymers Preparation of polymer 1 (P1) 200 g of ester 1 (80% strength by weight in toluene), 80 g of an ethylene/vinyl ace~ate copolymer (28% by weight of vinyl acetate, melt flow index accord-ing to ASTM D 1238 (MFI) = 40 g/10 min) and 20 g of toluene were heated to 100C and stirred for 30 minutes, a clear solution being formed. Thereafter, a solution of 0.6 g of tert-butyl perethylhexanoate in 43 g of toluene was metared in at 85C in the course of 4 hours under a nitrogen atmosphere, polymerization was continued for one hour and the mixture was diluted with 137 g of toluene.
A highly viscous, about 50% strength by weight solution of relatively high molecular weight graft copoly~er whose segment ratio A : E was 2 : 1 was obtained.
Determination of the equivalent R value for the graft copolymer obtained according to Example 3 To characterize the resulting graft copolymer 2~)089~36 - 13 - O.Z. 0050/40595 with regard to its molecular weight, Example 3 was repeated with the single modification that no ethyl~ne/
vinyl acetate copolymer was added, so that only polymer-ization of ester 1 to the polyacrylate occurred. The K
S value of the resulting polyacrylate was determined according to H. Fikentscher, Cellulosechemie, 13 (1932), 58-64 and 71-74, the measurement~ being carried out using 2% strength by weight solutions in xylene at 25C. The K
value of the polyacrylate was 28. This K value served a~
the equivalent K value for characterizing the relatively high molecular weight graft copolymer obtained in Example 3 with the addition of the ethylene/vinyl acetate copoly-mer, ie. the equivalent K value of the relatively high molecular weight graft copolymer was 28.
Preparation of polymer 2 (P2) 300 g of ester 1 (80% strength by weight in toluene), 60 g of an ethylene/vinyl acetate copolymer (28% of vinyl acetate, MFI - 40 g/10 min) and 16 g of toluene were heated to 100C and ~tirred for 30 minute~, after which a clear solution was formedO Thereafter, a solution of 0.72 g of tert-butyl perethylhexanoate in 54 g of toluene was metered in at an internal temperature of 85C under a nitrogen atmosphere in the course of 4 hours, polymerization was continued for two hours and the mixture was diluted with 168 g of toluene. A viscous, about 50% strength by weight solution of a relatively high molecular weight graft copolymer whose segment ratio A : R was 4 : 1 was obtained. An equivalent K value of 31 was determined for the resulting graft copolymer by the method described in the second paragraph of Example 3.
Preparation of polymer 3 (P3) The procedure described in Example 4 was fol-lowed, except that ester 2 was used instead of ester 1.
A viscous, about 50% strength by weight ~olution of a ;~008986 - 14 - O.Z. 0050/40595 relatively high molecular weight graft copolymer whose segment ratio A : E wa~ 4 : 1 was obtained. The equivalent R value was 33.
C) Preparation of the low molecular weight graft copolymers Preparation of polymer 4 (P4) 140 g of ester 1, 56 g of an ethyleneJvinyl acetate copolymer (28% of vinyl acetate, MFI = 40 g/10 min), 85 g of toluene and 0.5 g of mercaptoethanol were heated to 110C and stirred for 30 minutes. Thereafter, a solution of 0.5 g of tert-butyl perethylhexanoate in 55 g of toluene was metered in over three hours under a nitrogen atmosphere and polymerization W8~ then continued for one hour. An about 50% strength by weight polymer solution which was homogeneous at 110C but separated into two phase~ on cooling wa~ obtained. Dilution with toluene to a 10~ strength by weight polymer ~olution gaYe a clear solution. The segment ratio A : E of the result-ing graft copolymer was 2 : 1. The equivalent R value was 13.
Preparation of polymer 5 (P5) 150 g of ester 1, 30 g of an ethylene/vinyl acetate copolymer (28% of vinyl acetate, MFI = 40 g/10 min), 70 g of toluene and 0.6 g of mercaptoethanol were heated to 110C and stirred for 30 minutes. Thereafter, a solution of 0.5 g of tert-butyl perethylhexanoate in 50 g of toluene was metered in over three hours under a nitrogen atmosphere and polymerization was then continued for one hour. An about 50% strength by weight polymer solution which was homogeneous a~ 110C but separated into two phases on cooling wa~ obtained. Dilution with toluene to a 10% strength by weight polymer solution gave a clear solution. The segment ratio A : E of the result-ing graft copolymer wa~ 4 : 1. Its equivalent R value was 14.
2 0~8 9~6 - 15 - O.Z. 0050/40595 EXAMPLE a Preparation of polymer 6 ( P6 ) The procedure described in Example 7 was fol-lowed, except that ester 2 was used instead of ester 1.S The segment ratio A : E of the resulting graft copolymer was 4 : 1. The equivalent K value was 1~.
D) Preparation of the novel concentrated mixtures Preparation of concentrated mixture 1 (M1) 10 parts of polymer 4 and 1 part of polymer 1 (each 50% strength by weight in toluene) were heated at 100C for 30 minutes and cooled to room temperature with vigorous stirring. A viscous, slightly cloudy mixture which did not settle out on standing was obtained.
Preparation of concentrated mixture 2 (M2) 10 parts of polymer 5 and 1 part of polymer 1 (each 50% strength by weight in toluene) were heated at 100C for 30 minutes and cooled to room temperature with vigorous stirring. A slightly cloudy mixture which was of medium viscosity and did not settle out on standing was obtained~
Preparation of concentrated mixture 3 tM3) 10 parts of polymer 6 and 1 part of polymer 1 (each 50% strength by weight in toluene) were heated at 100C for 30 minutes and cooled to room temperature with vigorous stirring. A slightly cloudy mixture which was of medium viscosity and did not settle out on standing was obtained.
Preparation of comparative mixture 1 10 parts of polymer 5 (low molecular waight graft copolymer, 50% strength by weight in toluene), 0.8 part of the polyacrylate obtained as described in the second paragraph of Example 3, 0.1 part of an ethylene/vinyl Z0089~36 - 16 - O.Z. 0050/40595 acetate copolymer (28% of vinyl acetate, MFI = 40 g/10 min) and 0.1 part of toluene were heated at 100C for 30 minutes and cooled with vigorou~ stirring. The mixture had a low viscosity and po sessed two pha~eR at room temperature. It contained coarse gel particle~ which settled out within a few hourc.
Preparation of comparative mixture 2 10 parts of polymer 5 (low molecular weight graft copolymer, 50% strength by weight in toluene) and 1 part of the polyacrylate obtained as de cribed in the second paragraph of Example 3 were heated at 100C for 30 minute~
and cooled with vigorous stirring. The mixture had a low viscosity and posse3sed two phases at room temperature.
It contained coar~e gel particles which settled out within a few hours. Visually, there was no difference with respect to comparative mixture 2.
Comparative mixture 1 corre3ponded in its net composition (polyacrylate, ethyleneJvinyl acetate copoly-mer, toluene) to mixture 2 but did not contain any relatively high molecular weight graft copolymer but only the purely physical mixture of the component~.
Comparative mixture 2 shows that the pure poly-acrylate has no solubilizing and dispersing properties.
Mixtures 1 to 3 illustrate the outstanding suit-ability of the relatively high molecular weight graft copolymers a stabilizers of the low molecular weight graft copolymers.
E) Pour point determinations The pour point was determined according to ASTM
D 97-66. The particular additive was added by stirring it in at 50C in the course of 30 minute~. The results are summarized in Table 1.
X00~986 - 17 - O.Z. 0050/40595 Pour point determinations Oil Without Amount Pl P2 P3 P4 P5 P6 M1 M2 grade addi- added . tive (ppm) No. 1 39 1500 33 30 27 27 27 24 24 21 No. 2 42 1000 - 24 27 - 21 18 - 18 ~
No. 3 30 500 - 21 18 - 18 18 - 15 12 Oil No. 1 was a residue originating from Pakistan, oil No. 2 was a residue originating from Xorea and oil No. 3 was a German crude oil having an API
gravity of 36. The column headed ~without additive~
indicates the pour point of the particular oil grade without an additive.
Since the mixtures Ml to M3 have the following compositions:
M1 = P1 + P4 M2 = P2 + P5 M3 = P3 + P6 the efficiency of M1 i~ comparable with that of P1 (relatively high molecular weight graft copolymer) and P4 (low molecular weight graft copolymer) and similarly that of M2 with that of P2 and P5 and that of M3 with that of P3 and P6, for one oil grade. Table 1 shows that the low molecular weight polymer# P4, P5 and P6 generally have better efficiency ~han the relatively high molecular weight polymers Pl, P2 and P3. ~he best efficiencie~ in each ca~e were found for the novel mixtures Ml, M2 and M3.
O.Z. 0050/40595 Concentrated mixtures of qraft copolymers of esters of unsaturated acid~ and ethylene/vinyl ester copolymer~
The present invention relates to concentrated mixtures of graft copolymers of e~ters of unsaturated acids, such as (meth)acrylates and ethylene/vinyl ester copolymers and their use as flow improver~ and pour point depressants for crude oils, residues and middle distillates.
Depending on their origin, petroleum oils may contain substantial amounts of paraffins (which are also referred to as wax). At ~he temperatures prevailing in the ground, the paraffins are present in dissolved form.
When the petroleum oil c0015, for example during trans-port in a pipeline or storage in a tank, the dissolved paraffins may gradually separate out. They frequently form three-dimensional structures which are capable of binding large hmounts of petroleum oil. Thi~ results in an increase in the viscosity of the petroleum oil and, at sufficiently low temperatures, the oil may even completely solidify. This is particularly true for the residues obtained in refineries, al80 referred to as long residues, since their content of low-boiling components has been reduced by distillation and they therefore have a higher wax content.
This behavior is very disadvantageous particular-ly during transport of the petroleum oil through pipe-lines. Paraffin deposits may hinder flow, necescitating greater pumping power. This may lead to high tran~port costs, particularly in pipelines which extend over long distances. If the resistance is too high, the permis-sible maximum pressure may be reached, causing transport to be shut down.
Furthermore, when transport is interrupted due to crystallization of the paraffins on coolin~ of the petroleum oil, the viscosity may increase to such an extent that transpor~ cannot be restarted since either - 2 - O.Z. 0050/40595 the pumps can no longer provide the required start-u~
pressure, which is several times higher than the regular transport pressure, or the pipeline cannot withstand the start-up pressure.
5It is therefore very important to keep to a minimum the adverse effect of wax on the flow properties of the petroleum oil or of other paraffin-containing oils, such as residues or middle distillates. This can be achieved if low-boiling petroleum oil fractions, for 10example diesel or kerosine, are added to the oil so that, as a result of the dilution, the paraffins are kept in solution on cooling. Moreover, storage means may be de~igned to be heatable so that the paraffins are prevented from crystallizing out by the higher tempera-15ture. However, these procedures are highly energy-consumptive and therefore uneconomical in many cases. It i8 an ob~ect of the present invention to provide suitable additives which, when used in a very small amount, prevent cry~tsllization of the paraffin on cooling of the 20petroleum oil or of other oils or which modify the crystals being formed in such a way that the flow proper-ties of the oil are not adversely affected.
Additives which are liquid at about 25C and have a very high polymer content are increasingly being 25required for indu~trial use. To ensure simple metering of multiple component additive~, all components in a single additive should be present in macroscopically homogeneous form. This also ensures rapid mixing with, and dissolution in, the wax-containing oils, which is an 30important precondition for the efficiency of the additive.
In addition to others, two polymer classes in particular have been found to date to be ef~icient pour point depre3sants and flow improvers for petroleu~ oils.
35The first group comprises polymeric esters of unsaturated mono- or bifunctional carboxylic acids and long-chain alkanols, for example polyalkyl (meth)acrylates (cf. U.S.
~30898~
_ 3 _ o.Z. 0050/40595 Patents 3,669,189 and 3,729,296). The second group com-prises copolymers of ethylene and vinyl esters of Cl-C4-fatty acids with a vinyl ester content of about 10-40~ by weight (cf. U.S. Patents 3,567,639 and 3,669,189). These polymers are generally referred to as EVA polymers.
U.~. Patent 3,726,653 describes mixtures of poly-alkyl acrylates and EVA polymers which are distinguished by the synergistic effect of the two components. Japan-ese Preliminary Published Application 53593/84 (Chem.
~bstr. 101, 133833z) discloses graft copolymers of EVA
polymers and C3-C2l-alkyl acrylates and/or styrene or alkylated derivatives and their use as flow improvers for middle distillates and petroleum oils.
Solutions of relatively high molecular weight ethylene/vinyl acetate copolymers in aromatic solvents possess good flow properties at room temperature and can be handled only if they have polymer contents of not more than about 10-15% by weight. Polylmeth~acrylates of C16-C2a-fatty alcohols are likewise solid at temperatures slightly below room temperature.
As stated above, the combination of ethylene/
vinyl acetate copolymer~ and polyalkyl (meth)acrylates according to U.S. Patent 3,726,653 particularly effect-ively depresses the pour point of petroleum oils. How-ever, if the two polymer system~ are mixed in a solvent, phase separation occurs owing to the incompatibility of the two polymer ~y~tems, the EVA copolymer settling out in gelatinous form on the bottom of the vessels. Such a mixture cannot be used industrially.
German Laid-Open Application DOS 3,613,247 describes stable concentrated emulsions of ethylene/vinyl ester copolymers. They are obtained by dispersing EVA
polymers and~or polyalkyl (meth)acrylates in ~a carrier in which the polymer~ are insolubleO The dispersants used include block or graft copolymers of EVA polymers and alkyl (meth)acrylates. However, the known systems are unsatisfactory.
Xl~ 9~, _ 4 _ o.z 0050~40595 We have found that this object i8 achieved by an advantageous system for use a~ a flow improver and pour point depressant for wax-containing oils. The pre~ent invention relates to concentrated mixtures containing (i) an organic solvent, ~ii) a low molecular weight graft copolymer of the general formula I and (iii) a relatively high molecular weight graft copolymer of the general formula I
A - E
where A is a segment of a pol~mer which consists of from 70 to 100% by weight of monomer units of the general formula II and from O to 30~ by weight of monomer units of the general formula III
XHC=CR1Y II
CH2=C~1Z III
where R1 is H or CH3, X i8 H, COOH or COOR2, Y is COOH or COOR2 or X and Y are the anh~dride radical CO-O-CO, Z is OCOR2, OR2, a heterocyclic 5-membered or 6-membered ring or a radical CO-B-D-R3, R2 i~ Cl-C40-alkyl, B i.R O or NH, D is a C2-C1O-hydrocarbon bridge and R3 is OH or N(R2) 2 in which R2 has the abovementioned meaning, and E i3 a segment of a copolymer of ethylene with vinyl esters of aliphatic C1-C24-carboxylic acids, with or without ~iv) a polymer which contains only the ~egments A.
The novel concentrated mixture which contain an organic solvent and both a low molecular weight and a relatively high molecular w~ight graft copolymer of e~ters of unsaturated acids, for example (meth)acrylates, and EVA polymers give ready-to-despatch forms which remain stable and retain their good flow properties even on prolonged storage at conventional ambient temperature~
and do not cause precipitation of polymer3. Furthermore, the polymers are present in a form ~uch tha~t, when the mixture is added to the wax-containing oils or when further ~olvent is added to the concentrated mixtures, the said polymers go into solution readily and rapidly.
At the same time, the use of the novel mixture of a low _ 5 _ o.z. 0050~40595 molecular weight graft polymer and a relatively high molecular weight graft polymer results in a ~ynergistic effect in terms of improvement of the flow properties and of the pour point depression of the wax-containing oilR, in that the combination of low molecular weight and relatively high molecular weight graft copolymerR has a greater effect than the sum of the individual effects of low molecular weight graft polymer and relatively high molecular weight graft copolymer.
The organic solvents u~ed for the novel concen-trated mixtures are in general aliphatic and, preferably, aromatic hydrocarbons. Suitable aliphatic hydrocarbons are, for example, gasoline fractions, such as light naphtha, naphtha, median gasoline, ligroin, kero3ine, diesel oil and gas oil. Examples of suitable aromatic hydrocarbons are benzene, toluene, xylene, alkylbenzenes and mixtures thereof. The organic solvents are used in general in amounts such that the total polymer content of the novel concentrated misture is from 20 to 70, prefer-ably from 20 to 65, in particular from 25 to 60, % by weight.
The novel concentrated mixtures contain, in addi-tion to the organic solvent, a low molecular weight graft copolymer and a relatively high molecular weight graft copolymer each of the general formula I
A - E
where A is a segment of a polymer (polymer A~ which con-8iSt8 of from 70 to 100, preferably from 80 to 100, ~ by weight of monomer units of the general formula II and from 0 to 30, preferably from 0 to 20, ~ by weight of monomer units of the general formula III
XHC=CR1Y II
CHz=CRlZ ~III
where R1 i8 H or CH3, X is H, COOH or COOR2, Y is COOH or COOR2 or X and Y are the anhydride radical CO-O-CO, Z is OCOR2, OR2, a heterocyclic 5-membered or ~-membered ring or a radical CO-B-D-R3, R2 is Cl-C40-alkyl, B is O or NH, Z~ ~9~
- 6 - O.Z. 0050/40595 D is a C2-C1O-hydrocarbon bridge and R3 i8 OH or N(R2)2 in which R2 has the abovementioned meanin~.
Suitable monomers of the general formula II are, for example, mono- and dialkyl maleates and mono- and di-alkylfumarates, maleic anhydride and alkyl (met~)-acrylates having in general a Cl-C40-, preferably C1-C34-, in particular Ca-C24-alkyl group. Ethers of (meth)acrylic acid with C1-C40-, preferably C1-C34-, preferably C8-C24-alcohols, from O to 20~ by weight of whose alkyl chains may be branched, are preferably used. In general, these alcohols are essentially primary alcohols, for example having a content of from 80 to 100~ by weight of primary alcohols, but may contain from O to 20% by weight of secondary alcohols.
The monomers of the general formula II are essen-tially esters of unsaturated acid~ and alcohols, which can be obtained by the known es~erification processes.
For example, the alkyl (meth)acrylates can be obtained by a method in which a solution of (meth)acrylic acid and an alkanol in an organic solvent, preferably in the solvent in which the polymerization to give the graft copolymers is subsequently carried out, is heated to the boil with the addition of a conventional polymerization inhibitor, for example a hydroquinone derivative, and an esterifica-tion cataly3t, such as sulfuric acid or p-toluenesulfonic acid, and the water of reaction formed is removed by azeotropic distillation. To purify ~he ester, in par-ticular to remove the added inhibitor and excess (meth)-acrylic acid, the ester solution can be washed with an alkaline agent, for example with dilute sodium hydroxide solution or sodium carbonate solution, and then with water.
Examples of suitable monomers of ~he general formula III are vinylalkyl esters, alkylamino~meth)-acrylates, alkylamino(meth)acrylamides and vlnylhetero-cycles, such as vinylpyridine, vinylpyrrolidone, vinyl-carbazole, vinylimidazole and their alkyl derivatives.
2~R986 - 7 - O.Z. OG50/40595 In the general formula I, E is a segment of a co-polymer of ethylene with vinyl e~ters o~ aliphatic, generally saturated C1-C24-carboxylic acids, preferably of aliphatic Cl-C4-carboxylic acids (EVA polymers). The EVA
polymers are known per se (cf. U.S. Patent 3,382,055).
In their preparation, it is also possible simultaneously to use vinyl esters which differ from one another. They can be prepared, for example, by mass, emulsion or solu-tion polymerization. Examples of comonomers are vinyl esters of acetic acid, propionic acid, butyric acid, 2-ethylhexanecarboxylic acid, pelargonic acid and stearic acid, in particular C2-C4-carboxylic acid~, vinyl acetate being particularly preferred. In general, the vinyl ester content is from 10 to 80, preferably from 15 to 45, % by weight, ie. the ethylene content is accordingly from 20 to 90, preferably from 55 to 85, % by weight. The melt flow index according to ASTM D 1238 is generally from 1 to 800, preferably from 10 to 400, in particular from 15 to 100, g/10 min.
The graft copolymer~ of the general formula I are generally obtained by conventional free radical graft polymexization, by graftinq the monomers of the general formula II and, if required, those of the general formula III onto EVA polymers. For example, an initiator and some of the monomer~ of the general formula II and, where relevant, III are added to a solution of the EVA polymer, such a~ the ethylene/vinyl acetate copolymer, in an organic solvent, for example in an aliphatic or, prefer-ably, aromatic hydrocarbon, such as benzene, toluene, xylene or another alkylbenzene or a mixture thereof, advantageou~ly under a blanketing agent, such as nitrogen or carbon dioxide, and the remainder of the monomers and further initiator are added in the course~of several hours, for example from 2 to 8 hours. The free radical polymerization may al~o be carried out by the batch method, in which the ethylene/vinyl acetate copolymer and the total amount of the monomer~ of the formulae II and, X0~ 3fi - 8 - O.Z- 0050/40595 where relevant, III are initially taken and the initiator is then metered in over several hours. The polymeriza-tion reaction is advantageously effected at from 50 to 200C, preferably from 60 to 130C. Depending on the polymerization temperature, peroxo or azo initiators, eg.
tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, cumyl hydroperodixide, tert-butyl hydroperoxide,2,2'-azobis-(2,4-dimethylvaleronitrile)or 2,2'-azobisisobutyronitrile, are generally used as initiators, advantageously in amount~ of from 0.05 to 5, preferably from 0.1 to 1, % by weight, based on the mono-mers used. Redox systems, for example benzoin, dimethyl-aniline, ascorbic acid and complexes of heavy metals, such as copper, cobalt, manganese, iron, nickel and chromium, which are soluble in organic solvents, are also suitable as initiators, or the reaction may be ac-celerated by the concomitant use of such redox systems as coinitiators. The amounts usually used are from 0.1 to 2,000, preferably from 0.1 to 1,000, ppm by weight. In choosing the initiator or the initiator system, it is advantageou~ to ensure that the half life of the in-itiator or of the initiator system is less than 3 hours at the ~elected polymerization temperature. At 150C, for example, the half life of tert-butyl hydroperoxide i3 less than 3 hours. On the other hand, the polymerization behavior of the initiator system comprising 1% by weight of tert-butyl hydroperoxide/S ppm by weight of copper(II) acetylacetonate at as low as 100C is comparable with that of 1% by weight of tert-butyl hydroperoxide at 150C. If, for example, prepolymerization is carried out at a low temperature and polymerization is completed at a higher temperature, two or more initiators are generally used.
To obtain low molecular weight graft copolymers, it is often advantageous to carry out the reaction in the presence of regulators. Example~ of -~uitable regulators are allyl compounds, such as allyl alcohol, but-1-en-3-ol 20~R986 _ g _ o.z. 0050/40595 and, preferably, organic mercapto compounds, ~uch as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and-tert-dodecyl mercaptan, which are generally used in amount~ of from 0.1 to 10~ by weight.
Apparatuses which are suitable for the polymeriz-ation are, for example, conventional stirred kettles having, for example, anchor stirrers, paddle stirrers, Lmpeller stirrers or multistage impulse countercurrent agitators, and apparatuses which are suitable for the continuous preparation are ~tirred kettle cascade~, tube reactors and static mixers.
In the graft copolymers of the general formula I, the ratio of segments A to segments E is in general from 20 to 95, preferably from 60 to 95, in particular from 70 to 90, % by w~ight of segment A and from S to 80, prefer-ably from 5 to 40, in particular from 10 to 30, % by weight of segment E.
An essential feature of the present invention i~
that the concentrated mixtureY contain a low molecular weight and a relatively high molecular weight graft copolymer of the general formula I. The low molecular weight and relatively high molecular weight graft copoly-mers are ob~ained a~ a low molecular weight or relatively high molecular weight graft copolymer depending on the choice of the initiators, coinitiators, regulators, polymerization temperatures and molecular weight of the EVA polymer used. Thus, for the preparation of the low molecular weight graft copolymers, regulators are advan-tageously added. The weight ratio of the low molecular weight graft copolymer to the relatively high molecular weight graft copolymer in the novel concentra~ed mixtures is in general from 1 : 10 to 100 : 1, preferably from 2 : 1 to 40 : 1, in particular from 5 : 1 to 30 : 1. The segments A and E in the low molecular weight and relatively high molecular weight graft copolymers may be Z0C~898~
- 10 - O.Z. OG50/40595 identical or different. By appropriate combination of segment~ A and E in the low molecular weight and rela-tively high molecular weight graft polymers, it i~
possible to adapt and optimize the efficiency of the novel concentrated mixtures with regard to improvement of the flow behavior and depression of the pour point, to meet the requirements of the particular oil pre~ent.
The concentrated mixtures used are in general those where the low molecular weight graft copolymers present in the mixture are graft copolymer~ as obtained by grafting the monomers of the general formulae II and III onto E~A polymers under reaction conditions which, when only the EVA polymers are omitted and under other-wise identical reaction conditions, give polymers of the monomer~ of the general formulae II and, where relevant, III which have R values (according to H. Fikentscher, Cellulosechemie, 13 (1932~, 58-64 and 71-74) of from 7 to 20, preferably from 10 to 18, and in which the relatively high molecular weight graft copolymer~ present in the mixture are graft copolymers as obtained by grafting the monomers of the general formulae II and, where relevant, III onto EVA polymers under reaction conditions which, when only the EVA polymer~ are omitted and under other-wise identical reaction condition~, give polymers of the monomers of the general formulae II and, where relevant, III which have R values of from 20 to 70, preferably from 25 to 50.
- The novel concentrated mixtures are obtained, for example, by mixing the corresponding amounts of low molecular weight and relatively high molecular weight graft copolymers at, adYantageously, from 60 to 180C, preferably from 80 to 150C, in the organic solvent. The temperature and order of addition are ad~antageously chosen so that the low molecular weight graft copolymer is first dissolved in the organic solvent to give a homogeneous solution. The high molecular weight polymer i8 then added. In another possible method, the 2~8986 - 11 - O.Z. 0050t40595 polymerization reaction for the preparation of the graft copolymers is controlled in such a way that the low molecular weight and relatively high molecular weight graft copolymers are formed in one reaction vessel. For example, this can be achieved in the batch proces~ by first carrying out prepolymerization with a small amount of initiator at a low temperature with formation of the high molecular weight graft copolymer and then, after the addition of regulator and further initiator, completing the polymerization at a higher temperature with formation of the low molecular weight graft copolymer. In another possible method for the preparation of concentrated mixtures, the relatively high molecular weight graft copolymer is initially taken in a reaction vessel and the low molecular weight graft copolymer i~ prepared in the reaction vessel in the pre ence of the relatively high molecular weight graft copolymer.
The novel concentrated mixtures may additionally contain a polymer A corresponding to tho segments A, for example in amounts of from 0 to 50% by weight, based on the total polymer content of the concentrated mixtures.
This may be effected by adding to the concentrated mix-tures polymer A which ha~ baen prepared separately in a similar manner to the graft copclymers by free radical polymerization from the monomers of the general formulae II and, where relevant, III.
However, the concentrated mixtures containing polymer A may also be obtained by converting some of the monomers II and~ where relevant, III to the polymer A in the preparation of the novel graft copolymers, and in general in the preparation of the low molecular weight graft copolymers, the said polymer A remaining ungrafted.
The Example~ which follow illustrate the invention.
EXAMPLE~
A) Preparation of the esters - 12 - O.Z. 0050/40595 Preparation of a Cl6-C22-alkyl acrylate (e~ter 1~
25% by weight, based on the starting materials alkanol mixture and acrylic acicl, of toluene were added to 1 mole of a fatty alcohol mixture con~isting of about 20~ by weight of n-C16-alkanol, 40% by weight of n-C18-alkanol, 10% by weight of n-C20-alkanol and 30% by weight of n-C22-alkanol, 1 mole of acrylic acid, 4 millimoles of hydroquinone monomethyl ether and 5 millimoles of p-toluenesulfonic acid, and the mixture was heated under a water separator until no further water was separated off.
Preparation of a Cla-C22-alkyl acrylate (ester 1) The preparation was carried out similarly to lS Example 1, except that a fatty alcohol mixture consisting of about 45% by weight of n-Cl8-alkanol, 10% by weight of n-C20-alkanol and 45% by weight of n-C22-alkanol was used.
B) Preparation of the relatively high molecular weight graft copolymers Preparation of polymer 1 (P1) 200 g of ester 1 (80% strength by weight in toluene), 80 g of an ethylene/vinyl ace~ate copolymer (28% by weight of vinyl acetate, melt flow index accord-ing to ASTM D 1238 (MFI) = 40 g/10 min) and 20 g of toluene were heated to 100C and stirred for 30 minutes, a clear solution being formed. Thereafter, a solution of 0.6 g of tert-butyl perethylhexanoate in 43 g of toluene was metared in at 85C in the course of 4 hours under a nitrogen atmosphere, polymerization was continued for one hour and the mixture was diluted with 137 g of toluene.
A highly viscous, about 50% strength by weight solution of relatively high molecular weight graft copoly~er whose segment ratio A : E was 2 : 1 was obtained.
Determination of the equivalent R value for the graft copolymer obtained according to Example 3 To characterize the resulting graft copolymer 2~)089~36 - 13 - O.Z. 0050/40595 with regard to its molecular weight, Example 3 was repeated with the single modification that no ethyl~ne/
vinyl acetate copolymer was added, so that only polymer-ization of ester 1 to the polyacrylate occurred. The K
S value of the resulting polyacrylate was determined according to H. Fikentscher, Cellulosechemie, 13 (1932), 58-64 and 71-74, the measurement~ being carried out using 2% strength by weight solutions in xylene at 25C. The K
value of the polyacrylate was 28. This K value served a~
the equivalent K value for characterizing the relatively high molecular weight graft copolymer obtained in Example 3 with the addition of the ethylene/vinyl acetate copoly-mer, ie. the equivalent K value of the relatively high molecular weight graft copolymer was 28.
Preparation of polymer 2 (P2) 300 g of ester 1 (80% strength by weight in toluene), 60 g of an ethylene/vinyl acetate copolymer (28% of vinyl acetate, MFI - 40 g/10 min) and 16 g of toluene were heated to 100C and ~tirred for 30 minute~, after which a clear solution was formedO Thereafter, a solution of 0.72 g of tert-butyl perethylhexanoate in 54 g of toluene was metered in at an internal temperature of 85C under a nitrogen atmosphere in the course of 4 hours, polymerization was continued for two hours and the mixture was diluted with 168 g of toluene. A viscous, about 50% strength by weight solution of a relatively high molecular weight graft copolymer whose segment ratio A : R was 4 : 1 was obtained. An equivalent K value of 31 was determined for the resulting graft copolymer by the method described in the second paragraph of Example 3.
Preparation of polymer 3 (P3) The procedure described in Example 4 was fol-lowed, except that ester 2 was used instead of ester 1.
A viscous, about 50% strength by weight ~olution of a ;~008986 - 14 - O.Z. 0050/40595 relatively high molecular weight graft copolymer whose segment ratio A : E wa~ 4 : 1 was obtained. The equivalent R value was 33.
C) Preparation of the low molecular weight graft copolymers Preparation of polymer 4 (P4) 140 g of ester 1, 56 g of an ethyleneJvinyl acetate copolymer (28% of vinyl acetate, MFI = 40 g/10 min), 85 g of toluene and 0.5 g of mercaptoethanol were heated to 110C and stirred for 30 minutes. Thereafter, a solution of 0.5 g of tert-butyl perethylhexanoate in 55 g of toluene was metered in over three hours under a nitrogen atmosphere and polymerization W8~ then continued for one hour. An about 50% strength by weight polymer solution which was homogeneous at 110C but separated into two phase~ on cooling wa~ obtained. Dilution with toluene to a 10~ strength by weight polymer ~olution gaYe a clear solution. The segment ratio A : E of the result-ing graft copolymer was 2 : 1. The equivalent R value was 13.
Preparation of polymer 5 (P5) 150 g of ester 1, 30 g of an ethylene/vinyl acetate copolymer (28% of vinyl acetate, MFI = 40 g/10 min), 70 g of toluene and 0.6 g of mercaptoethanol were heated to 110C and stirred for 30 minutes. Thereafter, a solution of 0.5 g of tert-butyl perethylhexanoate in 50 g of toluene was metered in over three hours under a nitrogen atmosphere and polymerization was then continued for one hour. An about 50% strength by weight polymer solution which was homogeneous a~ 110C but separated into two phases on cooling wa~ obtained. Dilution with toluene to a 10% strength by weight polymer solution gave a clear solution. The segment ratio A : E of the result-ing graft copolymer wa~ 4 : 1. Its equivalent R value was 14.
2 0~8 9~6 - 15 - O.Z. 0050/40595 EXAMPLE a Preparation of polymer 6 ( P6 ) The procedure described in Example 7 was fol-lowed, except that ester 2 was used instead of ester 1.S The segment ratio A : E of the resulting graft copolymer was 4 : 1. The equivalent K value was 1~.
D) Preparation of the novel concentrated mixtures Preparation of concentrated mixture 1 (M1) 10 parts of polymer 4 and 1 part of polymer 1 (each 50% strength by weight in toluene) were heated at 100C for 30 minutes and cooled to room temperature with vigorous stirring. A viscous, slightly cloudy mixture which did not settle out on standing was obtained.
Preparation of concentrated mixture 2 (M2) 10 parts of polymer 5 and 1 part of polymer 1 (each 50% strength by weight in toluene) were heated at 100C for 30 minutes and cooled to room temperature with vigorous stirring. A slightly cloudy mixture which was of medium viscosity and did not settle out on standing was obtained~
Preparation of concentrated mixture 3 tM3) 10 parts of polymer 6 and 1 part of polymer 1 (each 50% strength by weight in toluene) were heated at 100C for 30 minutes and cooled to room temperature with vigorous stirring. A slightly cloudy mixture which was of medium viscosity and did not settle out on standing was obtained.
Preparation of comparative mixture 1 10 parts of polymer 5 (low molecular waight graft copolymer, 50% strength by weight in toluene), 0.8 part of the polyacrylate obtained as described in the second paragraph of Example 3, 0.1 part of an ethylene/vinyl Z0089~36 - 16 - O.Z. 0050/40595 acetate copolymer (28% of vinyl acetate, MFI = 40 g/10 min) and 0.1 part of toluene were heated at 100C for 30 minutes and cooled with vigorou~ stirring. The mixture had a low viscosity and po sessed two pha~eR at room temperature. It contained coarse gel particle~ which settled out within a few hourc.
Preparation of comparative mixture 2 10 parts of polymer 5 (low molecular weight graft copolymer, 50% strength by weight in toluene) and 1 part of the polyacrylate obtained as de cribed in the second paragraph of Example 3 were heated at 100C for 30 minute~
and cooled with vigorous stirring. The mixture had a low viscosity and posse3sed two phases at room temperature.
It contained coar~e gel particles which settled out within a few hours. Visually, there was no difference with respect to comparative mixture 2.
Comparative mixture 1 corre3ponded in its net composition (polyacrylate, ethyleneJvinyl acetate copoly-mer, toluene) to mixture 2 but did not contain any relatively high molecular weight graft copolymer but only the purely physical mixture of the component~.
Comparative mixture 2 shows that the pure poly-acrylate has no solubilizing and dispersing properties.
Mixtures 1 to 3 illustrate the outstanding suit-ability of the relatively high molecular weight graft copolymers a stabilizers of the low molecular weight graft copolymers.
E) Pour point determinations The pour point was determined according to ASTM
D 97-66. The particular additive was added by stirring it in at 50C in the course of 30 minute~. The results are summarized in Table 1.
X00~986 - 17 - O.Z. 0050/40595 Pour point determinations Oil Without Amount Pl P2 P3 P4 P5 P6 M1 M2 grade addi- added . tive (ppm) No. 1 39 1500 33 30 27 27 27 24 24 21 No. 2 42 1000 - 24 27 - 21 18 - 18 ~
No. 3 30 500 - 21 18 - 18 18 - 15 12 Oil No. 1 was a residue originating from Pakistan, oil No. 2 was a residue originating from Xorea and oil No. 3 was a German crude oil having an API
gravity of 36. The column headed ~without additive~
indicates the pour point of the particular oil grade without an additive.
Since the mixtures Ml to M3 have the following compositions:
M1 = P1 + P4 M2 = P2 + P5 M3 = P3 + P6 the efficiency of M1 i~ comparable with that of P1 (relatively high molecular weight graft copolymer) and P4 (low molecular weight graft copolymer) and similarly that of M2 with that of P2 and P5 and that of M3 with that of P3 and P6, for one oil grade. Table 1 shows that the low molecular weight polymer# P4, P5 and P6 generally have better efficiency ~han the relatively high molecular weight polymers Pl, P2 and P3. ~he best efficiencie~ in each ca~e were found for the novel mixtures Ml, M2 and M3.
Claims (8)
1. A concentrated mixture containing (i) an organic solvent, (ii) a low molecular weight graft copolymer of the formula I and (iii) a relatively high molecular weight graft copolymer of the formula I
A - E I
where A is a segment of a polymer which consists of from 70 to 100% by weight of monomer units of the general formula II and from 0 to 30% by weight of monomer units of the general formula III
XHC=CR1Y II
CH2=CR1Z III
where R1 is H or CH3, X is H, COOH or COOR2, Y is COOH or COOR2 or X and Y are the anhydride radical CO-O-CO, Z is OCOR2, OR2, a heterocyclic 5-membered or 6-membered ring or a radical CO-B-D-R3, R2 is C1-C40-alkyl, B is O or NH, D is a C2-C10-hydrocarbon bridge and R3 is OH or N(R2)2 in which R2 has the abovementioned meaning, and E is a segment of a copolymer of ethylene with vinyl esters of aliphatic C1-C24-carboxylic acids, with or without (iv) a polymer which corresponds only to the segments A.
A - E I
where A is a segment of a polymer which consists of from 70 to 100% by weight of monomer units of the general formula II and from 0 to 30% by weight of monomer units of the general formula III
XHC=CR1Y II
CH2=CR1Z III
where R1 is H or CH3, X is H, COOH or COOR2, Y is COOH or COOR2 or X and Y are the anhydride radical CO-O-CO, Z is OCOR2, OR2, a heterocyclic 5-membered or 6-membered ring or a radical CO-B-D-R3, R2 is C1-C40-alkyl, B is O or NH, D is a C2-C10-hydrocarbon bridge and R3 is OH or N(R2)2 in which R2 has the abovementioned meaning, and E is a segment of a copolymer of ethylene with vinyl esters of aliphatic C1-C24-carboxylic acids, with or without (iv) a polymer which corresponds only to the segments A.
2. A concentrated mixture as claimed in claim 1, wherein, in the graft copolymers of the formula I, the ratio of segments A : E is from 20 to 95% by weight of segment A and from 5 to 80% by weight of segment E.
3. A concentrated mixture as claimed in claims 1 and 2, wherein the weight ratio of the low molecular weight graft copolymer to the relatively high molecular weight graft copolymer is from 1 : 10 to 100 : 1.
4. A concentrated mixture as claimed in claim 1 or 2 or 3, wherein the graft copolymers of the formula I are prepared by grafting the monomers of the formula II and, where relevant, III onto a copolymer of ethylene with a vinyl ester of a C1-C24-carboxylic acid (EVA polymer).
5. A concentrated mixture as claimed in claim 1 or 2 or 3 or 4, wherein the low molecular weight graft copolymer present in the mixture is a graft copolymer as - 19 - O.Z. 0050/40595 obtained by grafting the monomers of formula II and, where relevant, III onto EVA polymers under reaction conditions which, when only the EVA polymers are omitted and under otherwise identical reaction conditions, give polymers of the monomers of the formulae II and, where relevant, III which have R values (according to H.
Fikentscher, Cellulosechemie, 13 (1932), 58-64 and 71-74) of from 7 to 20.
Fikentscher, Cellulosechemie, 13 (1932), 58-64 and 71-74) of from 7 to 20.
6. A concentrated mixture as claimed in claim 1 or 2 or 3 or 4 or 5, wherein the relatively high molecular weight graft copolymer present in the mixture is a graft copolymer as obtained by grafting the monomers of formula II and, where relevant, III onto EVA polymers under reaction conditions which, when only the EVA polymers are omitted and under otherwise identical reaction condi-tions, give polymers of the monomers of the formulae II
and, where relevant, III which have R values (according to H. Fikentscher, Cellulosechemie, 13 (1932), 58-64 and 71-74) of from 20 to 70.
and, where relevant, III which have R values (according to H. Fikentscher, Cellulosechemie, 13 (1932), 58-64 and 71-74) of from 20 to 70.
7. A concentrated mixture as claimed in claim 1 or 2 or 3 or 4 or 5 or 6, wherein the total polymer content of the mixture is from 20 to 70% by weight.
8. Use of a mixture as claimed in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 as a flow improver or pour point depressant for crude oils, residues and medium distillates.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3905681.3 | 1989-02-24 | ||
| DE3905681A DE3905681A1 (en) | 1989-02-24 | 1989-02-24 | CONCENTRATED MIXTURES OF GAPPOPOLYMERISATS FROM ESTERS OF UNSATURATED ACIDS AND ETHYLENE-VINYLESTER COPOLYMERISATS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2008986A1 true CA2008986A1 (en) | 1990-08-24 |
Family
ID=6374801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002008986A Abandoned CA2008986A1 (en) | 1989-02-24 | 1990-01-31 | Concentraded mixtures of graft copolymers of esters of unsaturated acids and ethylene/vinyl ester copolymers |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0384367A3 (en) |
| JP (1) | JPH03755A (en) |
| CA (1) | CA2008986A1 (en) |
| DE (1) | DE3905681A1 (en) |
| NO (1) | NO900866L (en) |
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| US7476264B2 (en) | 2003-10-25 | 2009-01-13 | Lariant Produkte (Deutshland) Gmbh | Cold flow improvers for fuel oils of vegetable or animal origin |
| US7500996B2 (en) | 2003-10-25 | 2009-03-10 | Clariant International Ltd. | Cold flow improvers for fuel oils of vegetable or animal origin |
| US7815697B2 (en) | 2003-12-11 | 2010-10-19 | Clariant Finance (Bvi) Limited | Fuel oils composed of middle distillates and oils of vegetable or animal origin and having improved cold flow properties |
| CN102020982B (en) * | 2009-09-17 | 2012-04-18 | 成都川大金钟科技有限公司 | Multiple-effect viscosity depressant for exploiting thickened oil |
| US20120174474A1 (en) * | 2009-09-25 | 2012-07-12 | Evonik Rohmax Additives Gmbh | Composition to improve cold flow properties of fuel oils |
| CN104837872A (en) * | 2012-12-18 | 2015-08-12 | 巴斯夫欧洲公司 | Polymer compositions of ethylene-vinyl ester copolymers and alkyl(meth)acrylates, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products |
| US9574146B2 (en) | 2012-12-18 | 2017-02-21 | Basf Se | Polymeric compositions composed of ethylene-vinyl ester copolymers alkyl (meth)acrylates, processes for production thereof and use thereof as pour point depressants for crude oils, mineral oils or mineral oil products |
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|---|---|---|---|---|
| US5278250A (en) * | 1989-11-04 | 1994-01-11 | Del-Ichi Ceramo Co., Limited | Process for preparing organic binder |
| DE4036225A1 (en) * | 1990-11-14 | 1992-05-21 | Basf Ag | Petroleum distillates with improved cold flow - contg. ethylene-based flow improver and copolymer of alkyl acrylate] and unsatd. di:carboxylic acid in amide form |
| DE4036227A1 (en) * | 1990-11-14 | 1992-05-21 | Basf Ag | PETROLEUM DISTILLATES WITH IMPROVED FLOW PROPERTIES IN THE COLD |
| DE4426003A1 (en) * | 1994-07-22 | 1996-01-25 | Basf Ag | Reaction products of polyolefins with vinyl esters and their use as fuel and lubricant additives |
| WO2005040315A1 (en) * | 2003-10-22 | 2005-05-06 | Leuna Polymer Gmbh | Additive mixture as component of a mineral oil composition |
| EP1674554A1 (en) * | 2004-12-24 | 2006-06-28 | Clariant Produkte (Deutschland) GmbH | Additives for low-sulfur mineral oil distillates, comprising graft copolymer based on ethylene-vinyl acetate copolymers. |
| DE102006001381A1 (en) * | 2006-01-11 | 2007-07-12 | Clariant International Limited | Low-sulfur mineral oil distillate additives comprising graft copolymers based on ethylene-vinyl ester copolymers |
| MX368295B (en) | 2012-06-05 | 2019-09-27 | Dow Global Technologies Llc | Films containing functional ethylene-based polymer compositions. |
| RU2656213C2 (en) * | 2013-02-04 | 2018-06-01 | Эвоник Ойль Эддитифс Гмбх | Cold flow improver with broad applicability in mineral diesel, biodiesel and blends thereof |
| EP3798261A1 (en) | 2019-09-26 | 2021-03-31 | Clariant International Ltd | Polymer compositions and their use as pour point depressant in paraffin-containing hydrocarbon oils |
| WO2023083941A1 (en) | 2021-11-15 | 2023-05-19 | Evonik Operations Gmbh | Ethylene vinyl acetate-based dispersions suitable as pour point depressants with improved performance and stability |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2905954C2 (en) * | 1979-02-16 | 1982-10-28 | Röhm GmbH, 6100 Darmstadt | Concentrated polymer emulsions as viscosity index improvers for mineral oils |
| DE3207291A1 (en) * | 1982-03-01 | 1983-09-08 | Röhm GmbH, 6100 Darmstadt | CONCENTRATED EMULSIONS OF OLEFIN COPOLYMERS |
| JPS6017476B2 (en) * | 1982-09-20 | 1985-05-02 | 日本合成化学工業株式会社 | Cold fluidity improver for petroleum products |
| DE3339103A1 (en) * | 1983-10-28 | 1985-05-09 | Röhm GmbH, 6100 Darmstadt | ADDITIVES FOR LUBRICANTS |
| FR2572410B1 (en) * | 1984-10-25 | 1987-09-04 | Elf Aquitaine | ETHYLENE GRAFT COPOLYMERS USED IN PARTICULAR AS ADDITIVES FOR THE INHIBITION OF PARAFFIN DEPOSITION IN CRUDE OILS AND COMPOSITIONS CONTAINING THE OILS AND ADDITIVES |
| DE3613247C2 (en) * | 1986-04-19 | 1995-04-27 | Roehm Gmbh | Concentrated emulsions of ethylene-vinyl acetate copolymers, processes for their preparation and their use as pour point improvers |
| DE3725059A1 (en) * | 1987-07-29 | 1989-02-09 | Roehm Gmbh | POLYMER FLOW IMPROVERS FOR MEDIUM DISTILLATES |
-
1989
- 1989-02-24 DE DE3905681A patent/DE3905681A1/en not_active Withdrawn
-
1990
- 1990-01-31 CA CA002008986A patent/CA2008986A1/en not_active Abandoned
- 1990-02-20 EP EP19900103178 patent/EP0384367A3/en not_active Withdrawn
- 1990-02-23 NO NO90900866A patent/NO900866L/en unknown
- 1990-02-23 JP JP2041399A patent/JPH03755A/en active Pending
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| KR20120090993A (en) * | 2009-09-25 | 2012-08-17 | 에보니크 로막스 아디티페스 게엠베하 | A composition to improve cold flow properties of fuel oils |
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| US10131776B2 (en) | 2009-09-25 | 2018-11-20 | Evonik Oil Additives Gmbh | Composition to improve cold flow properties of fuel oils |
| CN104837872A (en) * | 2012-12-18 | 2015-08-12 | 巴斯夫欧洲公司 | Polymer compositions of ethylene-vinyl ester copolymers and alkyl(meth)acrylates, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products |
| US9574146B2 (en) | 2012-12-18 | 2017-02-21 | Basf Se | Polymeric compositions composed of ethylene-vinyl ester copolymers alkyl (meth)acrylates, processes for production thereof and use thereof as pour point depressants for crude oils, mineral oils or mineral oil products |
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Also Published As
| Publication number | Publication date |
|---|---|
| NO900866D0 (en) | 1990-02-23 |
| NO900866L (en) | 1990-08-27 |
| EP0384367A2 (en) | 1990-08-29 |
| JPH03755A (en) | 1991-01-07 |
| DE3905681A1 (en) | 1990-08-30 |
| EP0384367A3 (en) | 1990-10-17 |
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| FZDE | Discontinued |