JP2002517547A - Wax crystal modifier - Google Patents

Abstract

This invention relates to copolymer compositions useful as wax crystal modifiers and flow improvers. The composition comprises a C ₆ -C ₂₅₀ straight chain structure or a branched structure dialkyl fumarate, carbon monoxide, and C ₃ -C ₃₀ alpha-olefins, ethylene, at least one compound selected from the group consisting of styrene and vinyl acetate Consisting of a copolymer of

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a wax crystal (wax crystal) modifier which is effective for improving the flow characteristics of lubricating oil and crude oil.

BACKGROUND Many oils, particularly crude oils, contain alkanes of linear and branched structures that crystallize with decreasing temperature. Crystallization of alkanes (waxes) under these oils causes an increase in viscosity which causes problems such as difficulties in pipeline transport of crude oil.
The temperature at which wax begins to crystallize in oil is the wax appearance temperature of oil (WAT
)is called. Polymer and copolymer compounds can be combined with the oil to reduce the WAT of the oil. Such additives, known as wax crystal modifiers, can be used as flow improvers in lubricating oils.

[0003] Lubricating oils and crude oils have completely different compositions. For example, crude oil contains trace levels of inorganic substances, resins, and asphaltene that are not present in lubricating oils. In addition, crude oil contains hydrocarbons with a wide range of molecular weights. These factors make the WAT of crude oil higher than that of lubricating oil. Lubricating oils have a WAT of about -25 to about -5C, while crude oils have a WAT of about -15C to about 30C.

[0004] Dialkyl fumarate-vinyl acetate (DAF-VA) copolymers have been used as flow improvers in lubricating oils. These copolymers can be formed by free radical polymerization of vinyl acetate with a DAF ester containing an alkyl of about 10 to about 18 carbon atoms in size. Such copolymers may range from about -25 to about-
At a temperature of 5 ° C, it is an effective lube oil flow improver. However, these fluidity improvers are not effective for crude oil because the WAT of crude oil is usually out of the above temperature range.

[0005] There remains an ongoing need for polymers and copolymers that improve the flowability of oils, especially polymers and copolymers that allow for improved flowability and pipeline adaptability of crude oils.

[0006] Summary One aspect of the invention, the present invention is a copolymer of dialkyl fumarate linear structure or branched structure of carbon monoxide and C ₆ -C _250. Other aspects, the present invention is flowable for use in dialkyl fumarate and oily liquid consisting of one or more copolymers of carbon monoxide with alkyl of straight chain structure or branched structure C ₆ -C ₂₅₀ It is an enhancer. As yet another aspect, the present invention is dialkyl fumarate and C ₃ -C ₃₀ alpha olefin having a straight-chain alkyl structure or branched structure C ₆ -C _250, ethylene, styrene, carbon monoxide, and vinyl acetate A wax crystal modifier of crude oil comprising a copolymer with at least one compound selected from the group consisting of: Dialkyl further to another aspect, the invention provides with a method of improving the fluidity of the oil liquid, against a large amount of the oil liquid, a straight-chain alkyl structure or branched structure C ₆ -C ₂₅₀ fumarate and C ₃ -C ₃₀ alpha-olefins, ethylene, styrene, and carbon monoxide copolymers with a compound selected from the group consisting of adding a small amount of at least one, characterized. However, in this case, when the oily liquid is a lubricating oil or a distilled oil, the compound is carbon monoxide. In yet another aspect, the present invention relates to a process for producing a copolymer, comprising: forming a C ₆ -C solvent in a solvent selected from the group consisting of hexane, benzene, cyclohexane, chloroform, xylene, oil, and heptane. C ₂₅₀ dissolving the dialkyl fumarates of straight-chain structure, a dissolution dialkyl fumarate, t- butyl peroxypivalate, benzoyl peroxide, the group consisting of t-butyl perbenzoate and t-butyl peroxide Combining in the reactor with an initiator selected from the group consisting of: sealing the reactor, purging with purified nitrogen; and removing at least one compound selected from the group consisting of carbon monoxide and ethylene. Pressurizing the reactor to a pressure of about 100 to about 3000 psig, to form a copolymer, using: The reactor is heated to a temperature in the range of from about 1 hour to about 48 hours at about 40 to 200 ° C., and wherein. In yet another aspect, the invention is a method of making a copolymer, comprising: hexane, benzene, cyclohexane, hexane, benzene, cyclohexane, under free radical polymerization conditions, for a time, temperature, and pressure sufficient to form the copolymer. C ₆ -C ₂₅₀ linear dialkyl fumarate dissolved in a solvent selected from the group consisting of chloroform, xylene, oil, and heptane; selected from the group consisting of ethylene and carbon monoxide At least one compound selected from the group consisting of t-butyl peroxypivalate, benzoyl peroxide, t-butyl perbenzoate, and t-butyl peroxide. I do. In yet another aspect, a method for improving the flowability of an oily liquid containing at least one alkane species, comprising determining the molecular weight distribution of the alkane species in the oily liquid, , substantially dialkyl fumarates and C ₃ -C ₃₀ alpha olefin having a straight chain or branched structure alkyl having the same molecular weight distribution, ethylene, styrene, and at least one compound selected from the group consisting of carbon monoxide And adding a small amount of at least one of the copolymers with

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a dialkyl fumarate-containing copolymer having a linear or branched alkyl in the size range of about C ₆ to about C ₂₅₀ , which is used in oil-based liquids such as fuel oils, lubricating oils, and crude oils. It is based on the discovery that it is an effective fluidity improver. The present invention is further based on the discovery that dialkyl fumarate can be copolymerized with carbon monoxide.

The copolymer according to the present invention has the following chemical formula:

Embedded image In the above formula, B is carbon monoxide, vinyl acetate, styrene, ethylene, and
Formed from C ₃ -C ₃₀ compounds selected from the group consisting of alpha-olefins, R is alkyl having a branched or straight chain structure in the range of C ₆ -C _250.

This polymer is produced as follows. Dialkyl fumarate esters with alkyl ranging up to C ₂₅₀ are prepared by diesterification of fumaric acid with an aliphatic alcohol in the presence of a p-toluenesulfonic acid catalyst. This ester can also be prepared from fumaryl chloride and an alkyl alcohol using an amine catalyst.

[0010] comonomers B are vinyl acetate, styrene, C ₃ -C ₃₀ alpha-olefins, formed from at least one compound selected from the group consisting of ethylene and carbon monoxide. The term copolymer, as used herein, is used as described above according to the meaning of a polymer comprising two or more different monomers.

R represents a group selected from linear or branched alkyl groups each having about C ₆ to about C ₂₅₀ . Preferred alkyl are those in the range of from about C ₈ ~ about C _40.

[0012] The copolymer of the present invention can be synthesized by free radical polymerization. Dialkyl fumarate and rate, vinyl acetate, styrene, or in the case of copolymers of monomers such as C ₃ -C ₃₀ alpha-olefins, the polymerization is generally performed during the standard glass reactor, monomer Any interfering substances present in the column are removed through the interfering column. The purified monomer is then filled into a tube with the DAF ester monomer. The tube was sealed with an inner stopper, and the tube was
Flush with nitrogen for ~ 4 hours. The ratio of the monomers is about 5: 9 by mole%.
It can vary from 5 to about 95: 5.

The reaction is carried out in a solvent or without a solvent. When a solvent is used, it must be non-reactive or non-interfering in the free radical polymerization. These solvents include benzene, cyclohexane, hexane, heptane and the like. Solvents or oils such as xylene can also be used. The solvent can be added to the monomer after flushing with argon or nitrogen.

The polymerization reaction can be run at 40 to 100 ° C. based on the reactivity of the monomers, the half-life of the initiator used, or the boiling point of the solvent. The reaction can be performed in an inert atmosphere. The solvent is maintained at the reaction temperature and the initiator (dissolved in the appropriate solvent) is added to the solvent. Typical free radical initiators are dialkyl peroxides such as ditertiary butyl peroxide, 2,5-dimethyl-2,5-ditertiary-butylperoxyhexane, dicumyl peroxide; benzoyl peroxide Includes alkyl peroxides; peroxyesters such as tertiary-butylperoxypivalate, tertiary-butylperbenzoate; and compounds such as azobis-isobutyronitrile. Reaction temperature about 60 to about 1
Free radical initiators that have the proper half-life at 40 ° C. can be used. In order to terminate the reaction without any additives (solvent-free), both the monomer and the initiator are charged together, flushed with nitrogen and kept at the reaction temperature. The components are agitated for a time sufficient to form a homogeneous mixture.

[0015] The reaction time ranges from about 1 to about 48 hours. The obtained polymer is separated by precipitation in poor solubility (solvent in which the polymer is insoluble). Then, the product is dried in a vacuum oven.

When producing the compounds of the present invention from monomers which are gaseous at normal temperature and pressure, such as ethylene and carbon monoxide, the reaction is generally carried out in a high pressure reactor such as an autoclave reactor. Will be In such copolymerization, a reactor is first charged with a monomer such as a dialkyl fumarate dissolved in a solvent such as hexane, and an initiator is added. Typical initiators include t-butyl peroxypivalate, benzoyl peroxide, t-butyl perbenzoate, t-butyl peroxide. The reactor is capped and purged with purified nitrogen. The reactor is then pressurized with carbon monoxide and / or ethylene monomer until the appropriate pressure is reached. The pressure ranges from about 100 to about 3000 psig. Preferred polymerization pressures are from about 500 to about 1200 psig. The reaction temperature is about 40-200 <0> C based on the half-life of the solvent and the initiator. The pressure of the reaction is maintained from about 1 hour to about 48 hours based on the reactivity of the monomers, the half-life of the initiator. The reactor is then cooled to room temperature and depressurized. A rotary evaporator is used to remove the solvent and obtain the product.

The product is usually characterized by standard techniques such as FTIR, NMR, GPC.

According to the invention, the wax crystal modifier is present in an amount of from about 10 to about
It is added to oily liquids such as oil at a concentration of 50,000 ppm. The recommended concentration is about 500ppm
It is. Specific examples of oily liquids containing paraffin (alkane) species that benefit from the addition of the compounds of the present invention include crude oils (ie, mining oils before being distilled or separated), fuel oils such as middle distillate fuel oils, and the like. Oils of lubricating viscosity (lubricating oils) are included.

It is believed that the copolymer flow improvers of the present invention, when present in an effective amount, are capable of preventing nucleation and growth of wax crystals in oily liquids such as oils. Although we do not want to be associated with any theory,
It is believed that the presence of an effective amount of the copolymer lowers the WAT of the oil because the copolymer molecules closely approximate the paraffinic species in the oil that coalesce into the growing wax crystals. Once coalesced, the polymeric nature of the flow improver (ie, branching and high molecular weight) prevents further addition of paraffins in oil to the crystals. It is believed that the presence of the copolymer in the growing wax crystals also alters the crystal morphology by preventing growth into undesirably large flat platelets. It is believed that such platelets result from the interconnection, mutual growth, and agglomeration of the nucleated wax crystals. Such a change in crystal morphology as a result of incorporation of the copolymer greatly reduces the ability of the wax crystals to interconnect, grow and agglomerate.

In the practice of this invention, it is desirable to first determine the molecular weight distribution of the paraffinic species present in the oil. The molecular weight distribution of the alkyls present in the fumaric acid species of the copolymer will be approximately the same as that of the paraffinic species in the oil. When the same is true, it is believed that the compounds of this invention are most effective.

While the compounds of the present invention are effective against oily liquids containing all paraffinic species, the compounds recommended will depend on the type of liquid used.

For example, lubricating oils require improved fluidity at temperatures even lower than those normally required for crude oils. In other words, the fumarate species contains
Having an alkyl ranging from C ₁₂ ~ about C _14, and about 2000 to about 100,000 copolymer molecular weight is desirable. In crude oil, is required reduced solubility of the compound, the preferred compounds have an alkyl ranging from about C ₁₅ ~ about C _40, and those having a molecular weight of about 2000 to about 50,000 range. For distilled oil, it recommended copolymer having an alkyl ranging from about C ₁₀ ~ about C _22, and those having a molecular weight of from about 2000 to about 20000 range.

Experimental Examples The present invention will be described in more detail with reference to experimental examples, but the present invention is not limited to these experimental examples.

I.Synthesis of dialkyl fumarate ester monomer  Experimental Example 1. Monomer synthesis from fumaric acid and 1-eicosanol Reaction flask (Dean-Stark trap equipment to remove generated reaction water and
2.8 g (FW116.07, 0.01875 mol) of fumaric acid, and 1
-11.2 g of eicosanol (FW298.56, 0.0375 mol), p-toluenesulfonic acid 1 water
0.3567 g (0.00188 mol) of the hydrate and 50 ml of toluene were added. The mixture
Heated at 130 ° C. under nitrogen for 18 hours. The reaction was then cooled to room temperature,
Filtration and removal of the toluene solvent by rotary evaporator, the product (mp. 71-73)
° C). That C₂₀The fumarate ester product is analyzed by IR and NMR spectroscopy.
Characterized. Its IR spectrum was obtained by dissolving a solid film in a NaCl plate.
Recorded. According to the spectrum, the peak of the ester is 1728 cm.^-1, Double tie
Absorption peak is 1647cm^-1Met. Product¹³In CNMR, the absorption peak of the double bond is
Is 134.0 ppm (trans-HC = CH-, carbon) and the peak of carbonyl ester is 165 ppm
Was seen in The NMR spectrum also shows the methylene (-C (O) O-CH _Two The absorption peak due to-) was shown at 66 ppm.

Experimental Example 2 Using the procedure of Monomer Synthesis Example 1 from fumaric acid and 1-docosanol, was obtained C ₂₂ fumarate ester product. In the ¹³ CNMR spectrum of the product, the double bond absorption peak was found at 134.0 ppm (trans-HC = CH—, carbon), and the carbonyl ester peak was found at 165 ppm. Methylene next to the ester group (-C (O) O-CH 2 -) absorption peak due were also seen 66 ppm.

Experimental Example 3 Monomer Formation from Fumaryl Chloride and Polyethylene Monoalcohol A round bottom flask was charged with 22.6 g (0.032 mol) of polyethylene monoalcohol (mw700) available from Aldrich, Milwaukee, Wis. Along with 300 ml of toluene. The mixture was heated to 80 ° C. under nitrogen and 30 ml of triethylamine was added. Then 2.6 g of fumaryl chloride diluted with 25 ml of toluene (0.0 g
17 mol) was added slowly over 1 hour. After the addition, the mixture was heated at 80 ° C. under nitrogen for 4 hours. The reaction mixture was then poured into 1500 ml of methanol containing 90 ml of hydrochloric acid. The resulting precipitate was then filtered, washed with methanol, and dried in vacuum at 75 ° C. for 12 hours to obtain 23.1 g of a fumarate ester product.

The IR spectrum of the product is 1724 cm^-1Absorption peak due to ester carbonyl at room temperature
And 1647cm^-1Showed a small double bond peak. Its spectrum is 729 and 719cm ^-1 Shows two sharp peaks similar to the polyethylene spectrum
Was.¹³In CNMR, the double bond absorption peak was 134.0 ppm (-HC = CH-, carbon)
The peak for the nil ester was found at 165 ppm. Also, the methyl group next to the ester group
(-C (O) O-CH_TwoThe absorption peak due to-) was found at 66 ppm. This peak is PE-OH
In the methylene next to -OH (HO-CH_Two-) Shifted to 63 ppm, relative to the peak
Was.

Experimental Example 4 Monomer formation from fumaric acid and polyethylene butylene monoalcohol 0.15 g (0.00125 mol) of fumaric acid and polyethylene butylene monoalcohol (Mn = 3
317) 8.3 g (0.00125 mol) and p-toluenesulfonic acid monohydrate 0.0238 g (0.0
Was charged to a reaction flask and heated at 100 ° C. under nitrogen for 20 hours. Then, the reaction product was poured into water, separated, and washed with acetone. The residue was dried under vacuum.

[0029] In the IR spectrum of the fumarate ester product, the absorption peaks for the ester carbonyl at 1724 cm ^-1, a small double bond peak at 1647cm ^-1 were observed. In the proton NMR spectrum, a double bond absorption (= CH, proton) was observed at 6.9 ppm, and a -C (O) OCH ₂ -absorption peak was observed at 4.2 ppm. Raw material alcohol (EB-OH
) I am, showed the -CH ₂ OH peak at 3.7ppm. -CH ₂ from - - -CH ₂ from EB-OH - and -C (O) OCH ₂ According to by the integral of the absorption peak, is in the product to be present 34% of the EB-OH confirmed.

II.Synthesis of dialkyl fumarate-containing copolymer by free radical polymerization  Hydroquinone inhibitor is converted to vinyl acetate through an inhibitor removal column.
Removed from Tate. This purified vinyl acetate is combined with DAF ester monomer
Installed in a tube. The tube was capped with a septum and flushed with nitrogen for 1 hour.
The solvent was flushed with nitrogen and added into the tube containing the monomer. The solution
And add the initiator (dissolved in the appropriate solvent) to each monomer solution.
Was. In order to perform without the addition of special additives (no solvent), the monomers and
The initiator was added, flushed with nitrogen and kept at the reaction temperature. The mixture overnight
Stirred. After 24 hours, the polymer solution is precipitated in methanol and dried in vacuo.
, NMR and GPC. The results are summarized in Table 1.
In the table, the monomer feed ratio is a molar ratio in weight%, and the product molar ratio is
Molar ratio.

[0031]

[Table 1]

III.Dialkyl fumarate-alpha olefin and dialkyl fumarate
Synthesis of styrene copolymer  The polymerization procedures shown in Experimental Examples 5 to 8 were carried out using dialkyl fumarate, styrene and alpha.
Used for the synthesis of olefin copolymers. The reaction status and analysis results are
Shown in 2. The notation of the molar ratio is the same as in Table 1.

[0033]

[Table 2]

IV.Synthesis of dialkyl fumarate ethylene copolymer  Experimental Example 11. In a 300 ml autoclave engineer reactor, dialkyl fumarate [alkyl
Has an average carbon atom count of about 13 (C₁₃DAF)] 10g, 150ml genuine n-hexane, 0.5g
02 g of a 75% solution of t-butyl peroxypivalate in mineral oil was charged. T- in this case
Butyl peroxypivalate can be obtained in a 0.2 molar benzene solution at 55 ° C for 10 hours.
Half-life (Swern, Organic Peroxide, John Wiley and sons, 1970, Vo
l. 1, pp. 82,87). The mixture was dissolved with stirring. Sealed reactor
And purged with purified nitrogen. The reactor was then pressurized to 700 psig with ethylene,
The temperature was increased to 66 ° C with stirring and the pressure was maintained for 24 hours. Then, put the reactor in the chamber
Cool to warm, depressurize, remove hexane on rotary evaporator and remove 20 g of product
Obtained.

The IR spectrum of the product indicated that there was no unreacted DAF monomer. In its IR spectrum of the product, the presence of carbonyl at 1738 cm ^-1, the peak of the two characteristics of polyethylene was observed at 729 and 719cm ^-1. The ¹³ C NMR of this product is:
Recorded in CDCl ₃ using chromium (III) acetylacetonate (Cr (acac) ₃ ). In ¹³ CNMR of this product, only ester carbonyl absorption was observed at 172 ppm. Integration of the carbonyl peak indicated the presence of 2.6% carbonyl carbon.

VI.Dialkyl fumarate-carbon monoxide copolymer and dialkyl fumarate-
Synthesis of carbon oxide-ethylene terpolymer  Example 12 Dialkyl Fumarate-Carbon Monoxide Copolymer In a 300 ml autoclave engineer reactor, the average number of carbon atoms in the alkyl was about 1
3 dialkyl fumarate (C₁₃DAF) 5 g, 150 ml n-hexane, and 0.507 g t-
Filled with 75% mineral oil of butyl peroxypivalate. The reactor is sealed and purified nitrogen
Purged with hydrogen. The reactor was then pressurized to 700 psig with carbon monoxide. Don't stir
The temperature was raised to 66 ° C. and the pressure was maintained for 24 hours. The reactor is then cooled to room temperature
Palm, depressurized. The hexane was removed on a rotary evaporator to give 4.5 g of product.

[0037] In the IR spectrum of the product, the peak of the ester carbonyl was observed at 1738 cm ^-1, disappearance of the peak of the double bonds of DAF monomers in 1649 cm ^-1 was observed. The ¹³ C NMR of this product was recorded in CDCl ₃ using Cr (acac) ₃ as a moderator to quantify the spectrum. The ¹³ C NMR of this product showed complete disappearance of the double bond peak at 134 ppm and a monomeric carbonyl peak at 165 ppm. The product showed two carbonyl peaks (206 ppm and 172 peaks).
multiple peaks with ppm). The relative integration of the carbonyl in the product indicated that the coalescence of carbon monoxide into the copolymer was 10% CO.

The GPC of this product was recorded in THF utilizing polystyrene standards. GPC of the product showed that the polymer had Mn = 1547 and Mw = 2228.

Experimental Example 13. In a 300 ml autoclave reactor, 2.5 g of didocosanyl fumarate (C ₂₂ fumarate ester) and 0.502 g of t-butyl peroxypivalate dissolved in 150 ml of n-hexane were added. A 75% mineral oil solution was charged. Seal reactor and 700p with carbon monoxide
Pressurized to sig. The temperature was raised to 66 ° C. with stirring and the pressure was maintained for 24 hours.
The reactor was then cooled to room temperature and depressurized. The hexane was removed on a rotary evaporator to give 4.5 g of product. The IR spectrum of the product, show a peak of the ester carbonyl at 1740 cm ^-1, disappearance of the peak of the double bonds of DAF monomers in 1649 cm ^-1 was observed. The ¹³ C NMR of this product was recorded in CDCl ₃ with Cr (acac) ₃ used as a moderator, with spectral limitations, and the spectra quantified. In ¹³ CNMR of this product, complete disappearance of the double bond peak at 134 ppm and a monomer carbonyl peak at 165 ppm were observed. The product is
There were two carbonyl peaks around 206 ppm and 172 ppm. G of this product
PC was recorded in THF using polystyrene standards. In GPC of this product,
The polymer was found to have Mw = 2840.

Experimental Example 14. Dialkyl fumarate / carbon monoxide / ethylene terpolymer In a 300 ml autoclave engineer reactor, dialkyl fumarate (C) having an average alkyl number of about 13 carbon atoms in alkyl dissolved in 150 ml of n-hexane was used. ₁₃ DAF) 5g and 0.
507 g of a 75% solution of t-butyl peroxypivalate in mineral oil was charged. The reactor was sealed and purged with purified nitrogen. Then, a mixed gas of ethylene / carbon monoxide (90:10
) To 700 psig. The temperature was raised to 66 ° C. with stirring and the pressure was maintained for 24 hours. Next, the reactor was cooled to room temperature and depressurized. The hexane was removed on a rotary evaporator to give 13.9 g of product.

[0041] In the IR spectrum of the product, the peak of the carbonyl ester in 1724 cm ^-1, polyethylene peaks in 723cm ^-1 was observed. The IR spectrum of the product also showed the absence of a double bond peak in the unreacted DAF monomer. The ¹³ C NMR of this product was recorded in CDCl ₃ using Cr (acac) ₃ as moderator and the spectra were quantified. The ¹³ C NMR of this product indicated the presence of two types of carbonyls, an ester and a ketone in the terpolymer. The measured value is
This indicated the presence of multiple peaks coming from the ketone and an absorption peak coming from the ester at 173 ppm. The NMR spectrum of the product also shows unreacted DAF
The absence of an absorption peak due to the monomer ester (165 ppm) and an absorption peak due to unreacted double bonds (134 ppm) were indicated. The GPC of this product was recorded in THF using polystyrene standards. The GPC of this product is 661184, 15599
And multiple peaks consisting of 1375 g / mol. This product contains hexane and T
It was soluble in HF. From this observation, we concluded that this product could not be either a high molecular weight PE or ECO polymer because both PE and ECO polymers were insoluble in hexane. By changing the amount of ethylene monomer in this reaction, the molecular weight, crystallinity and solubility of the polymer can be controlled.

VII.Dialkyl fumarate-containing copolymer as crude wax crystal modifier
Performance as  The results are summarized in Table 3.

The performance of the products from Examples 5, 7, 10, 11, 12, 13 and 14 was evaluated using a differential scanning calorimeter (DSC) with liquid nitrogen cooling. Measurements were taken at temperatures ranging from about -140 to about 100 ° C by heating and cooling at a rate of 10 ° C / min. Nitrogen was used as a purge gas at 50 cm ³ / min. Prior to sampling, all solutions were warmed to about 60 ° C. and care was taken to ensure that the added compounds were dissolved in the oil. A sealed aluminum pan was used for all measurements to avoid loss of low volatile compounds.

The wax appearance temperature (WAT) is an indicator of a thermodynamic hindrance to the generation of stable nuclei that promote further crystal growth. That is, WAT is the temperature at which stable wax crystals begin to appear first. The occurrence of wax crystallization requires supercooling to overcome free energy barriers to nucleation. Low WAT is preferred for oils because WAT is a major thermodynamic obstacle to further crystal growth. Additive compounds that prevent nucleation of wax crystals increase free energy impairment and lower WAT. The WAT of Alaskan North Slope crude was determined by cooling the crude at 10 ° C./min with or without experimental additives. The untreated Alaskan North Slope crude had a WAT of 14.35 ° C. Experimental example 5
The WAT was 13.71 ° C. at a concentration of 500 ppm of the additive, and the WAT was 11.00 ° C. at a concentration of 500 ppm of the additive in Experimental Example 11. The effect of changing the additive concentration in Experimental Example 5 was
It was studied using DSC. The results are shown in Tables 3 and 4.

The additive of Experimental Example 5 was also evaluated by the poor point test. 0.5% by weight
At concentrations, the poor point of Alaskan North Slope crude was reduced by 7 ° C. These results indicate that these additives are active as wax crystal modifiers.

[0046]

[Table 3]

[Table 4]

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] June 26, 2000 (2000.6.26)

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[0004] Dialkyl fumarate-vinyl acetate (DAF-VA) copolymers have been used as flow improvers in lubricating oils. These copolymers can be formed by free radical polymerization of vinyl acetate with a DAF ester containing an alkyl of about 10 to about 18 carbon atoms in size. Such copolymers may range from about -25 to about-
At a temperature of 5 ° C., it is an effective lubricating oil flow improver (U.S. Pat.
, 182 and 4,670,130) . However, these fluidity improvers are not effective for crude oil because the WAT of crude oil is usually out of the above temperature range.

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[0006] Summary One aspect of the invention, the present invention is a copolymer of dialkyl fumarate linear structure or branched structure of carbon monoxide and C ₆ -C _250. Other aspects, the present invention is flowable for use in dialkyl fumarate and oily liquid consisting of one or more copolymers of carbon monoxide with alkyl of straight chain structure or branched structure C ₆ -C ₂₅₀ It is an enhancer. As yet another aspect, the present invention is dialkyl fumarate and C ₃ -C ₃₀ alpha olefin having a straight-chain alkyl structure or branched structure C ₆ -C _250, ethylene, styrene, carbon monoxide, and vinyl acetate A wax crystal modifier of crude oil comprising a copolymer with at least one compound selected from the group consisting of: Dialkyl further to another aspect, the invention provides with a method of improving the fluidity of the oil liquid, against a large amount of the oil liquid, a straight-chain alkyl structure or branched structure C ₆ -C ₂₅₀ fumarate and C ₃ -C ₃₀ alpha-olefins, ethylene, styrene, and carbon monoxide copolymers with a compound selected from the group consisting of adding a small amount of at least one, characterized. However, in this case, when the oily liquid is a lubricating oil or a distilled oil, the compound is carbon monoxide. In yet another aspect, the present invention relates to a process for producing a copolymer, comprising: forming a C ₆ -C solvent in a solvent selected from the group consisting of hexane, benzene, cyclohexane, chloroform, xylene, oil, and heptane. C ₂₅₀ dissolving the dialkyl fumarates of straight-chain structure, a dissolution dialkyl fumarate, t- butyl peroxypivalate, benzoyl peroxide, the group consisting of t-butyl perbenzoate and t-butyl peroxide Combining in the reactor with an initiator selected from the group consisting of: sealing the reactor, purging with purified nitrogen; and removing at least one compound selected from the group consisting of carbon monoxide and ethylene. used, be pressurized to a pressure of about 100 to about 3000psig the reactor (689.5 to about 20685KPa), the copolymer To formed, the reactor, about 1 hour to about
Heating to a temperature in the range of about 40 to 200 ° C. for 48 hours. In yet another aspect, the invention is a method of making a copolymer, comprising: hexane, benzene, cyclohexane, hexane, benzene, cyclohexane, under free radical polymerization conditions, for a time, temperature, and pressure sufficient to form the copolymer. C ₆ -C ₂₅₀ linear dialkyl fumarate dissolved in a solvent selected from the group consisting of chloroform, xylene, oil, and heptane; selected from the group consisting of ethylene and carbon monoxide At least one compound selected from the group consisting of t-butyl peroxypivalate, benzoyl peroxide, t-butyl perbenzoate, and t-butyl peroxide. I do. In yet another aspect, a method for improving the flowability of an oily liquid containing at least one alkane species, comprising determining the molecular weight distribution of the alkane species in the oily liquid, , substantially dialkyl fumarates and C ₃ -C ₃₀ alpha olefin having a straight chain or branched structure alkyl having the same molecular weight distribution, ethylene, styrene, and at least one compound selected from the group consisting of carbon monoxide And adding a small amount of at least one of the copolymers with

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When producing the compounds of the present invention from monomers which are gaseous at normal temperature and pressure, such as ethylene and carbon monoxide, the reaction is generally carried out in a high pressure reactor such as an autoclave reactor. Will be In such copolymerization, a reactor is first charged with a monomer such as a dialkyl fumarate dissolved in a solvent such as hexane, and an initiator is added. Typical initiators include t-butyl peroxypivalate, benzoyl peroxide, t-butyl perbenzoate, t-butyl peroxide. The reactor is capped and purged with purified nitrogen. The reactor is then pressurized with carbon monoxide and / or ethylene monomer until the appropriate pressure is reached. The pressure is about 100 to about 3000 psig (689.5 to about 20685 kP
a) . Preferred polymerization pressures are from about 500 to about 1200 psig (3447.5 to about 8274 k
Pa) . The reaction temperature is about 40-200C based on the half-life of the solvent and the initiator. The pressure of the reaction ranges from about 1 hour to about 4 hours, based on the monomer reactivity, initiator half-life.
Maintained for 8 hours. The reactor is then cooled to room temperature and depressurized. A rotary evaporator is used to remove the solvent and obtain the product.

[Procedure amendment 5]

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[Correction target item name] 0034

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IV.Synthesis of dialkyl fumarate ethylene copolymer  Experimental Example 11. In a 300 ml autoclave engineer reactor, dialkyl fumarate [alkyl
Has an average carbon atom count of about 13 (C₁₃DAF)] 10g, 150ml genuine n-hexane, 0.5g
02 g of a 75% solution of t-butyl peroxypivalate in mineral oil was charged. T- in this case
Butyl peroxypivalate can be obtained in a 0.2 molar benzene solution at 55 ° C for 10 hours.
Half-life (Swern, Organic Peroxide, John Wiley and sons, 1970, Vo
l. 1, pp. 82,87). The mixture was dissolved with stirring. Sealed reactor
And purged with purified nitrogen. The reactor was then 700 psig with ethylene(4826.5kPa)
The temperature was increased to 66 ° C. while stirring and the pressure was maintained for 24 hours. Then
The reactor was cooled to room temperature, depressurized, and the hexane was removed on a rotary evaporator.
g of product was obtained.

[Procedure amendment 6]

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[Correction target item name] 0036

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VI.Dialkyl fumarate-carbon monoxide copolymer and dialkyl fumarate-
Synthesis of carbon oxide-ethylene terpolymer  Example 12 Dialkyl Fumarate-Carbon Monoxide Copolymer In a 300 ml autoclave engineer reactor, the average number of carbon atoms in the alkyl was about 1
3 dialkyl fumarate (C₁₃DAF) 5 g, 150 ml n-hexane, and 0.507 g t-
Filled with 75% mineral oil of butyl peroxypivalate. The reactor is sealed and purified nitrogen
Purged with hydrogen. The reactor was then purged with carbon monoxide at 700 psig(4826.5kPa)Pressurized
. The temperature was raised to 66 ° C. with stirring and the pressure was maintained for 24 hours. Then the reactor
Was cooled to room temperature and depressurized. The hexane was removed on a rotary evaporator and 4.5 g of raw
A product was obtained.

[Procedure amendment 7]

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[Correction target item name] 0039

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Experimental Example 13. 2.5 g of zide dissolved in 150 ml of n-hexane was placed in a 300 ml autoclave reactor.
Kosanil fumarate (C_{twenty two}Fumarate ester) and 0.502 g of t-butylperoxide
A 75% mineral oil solution of xipivalate was charged. Seal reactor and 700p with carbon monoxide
sig(4826.5kPa)Pressurized. Raise the temperature to 66 ° C while stirring and increase the pressure to 24 hours
For a while. The reactor was then cooled to room temperature and depressurized. On a rotary evaporator
The hexane was removed to give 4.5 g of product. In the IR spectrum of the product, 1
740cm^-1The peak of ester carbonyl is seen at 1649 cm^-1In DAF mode
The disappearance of the peak of the double bond of the nomer was observed. Of this product¹³CNMR is Cr (acac) _Three Use as a moderator, limit the spectrum and use CDCl_ThreeRecorded in and spectated
Was quantified. Of this product¹³In CNMR, the double bond peak at 134 ppm
Was completely disappeared, and a monomer carbonyl peak at 165 ppm was observed. That raw
The product showed two carbonyl peaks around 206 ppm and 172 ppm. this
The GPC of the product was recorded in THF utilizing polystyrene standards. Of this product
GPC showed that the polymer had Mw = 2840.

[Procedure amendment 8]

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[Correction target item name] 0040

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Experimental Example 14. Dialkyl fumarate / carbon monoxide / ethylene terpolymer In a 300 ml autoclave engineer reactor, dialkyl fumarate (C) having an average alkyl number of about 13 carbon atoms in alkyl dissolved in 150 ml of n-hexane was used. ₁₃ DAF) 5g and 0.
507 g of a 75% solution of t-butyl peroxypivalate in mineral oil was charged. The reactor was sealed and purged with purified nitrogen. Then, a mixed gas of ethylene / carbon monoxide (90:10
) To 700 psig (4826.5 kPa) . The temperature was raised to 66 ° C. with stirring and the pressure was maintained for 24 hours. Next, the reactor was cooled to room temperature and depressurized. The hexane was removed on a rotary evaporator to give 13.9 g of product.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 159/06 C10M 159/06 C10N 30:02 C10N 30:02 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, (KG, KZ, MD, RU, TJ, TM), AL, AU, BA, BB, BG, BR, CA, CN, CU, CZ, EE, GE, HR, HU, ID, IL IN, IS, JP, KP, KR, LC, LK, LR, LT, LV, MG, MK, MN, MX, NO, NZ, PL, RO, SG, SI, SK, SL, TR, TT, UA , UZ, VN, YU, ZA (72) Inventor Zushima Stefan 08809 Clinton Main Street, New Jersey USA 30 (72) Inventor Beruce Enoch United States of America New Jersey 08865 Phillipsburg Pedlars Lane 55 (72) Inventor Balman-Nair Manica USA New Jersey State 07059 Warren Sycamore Way 28 F-term (reference) 4H013 CC01 4H104 CB09C CB11C LA01 4J005 AB01 4J100 AA00Q AA01Q AA02Q AA15Q AB02Q AG04Q AL34P CA04 FA03 FA19 FA28 FA29 GC07 JA15

Claims (20)

[Claims] 1. A copolymer of carbon monoxide with a C ₆ -C ₂₅₀ linear or branched dialkyl fumarate. Wherein alkyl composition of claim 1 in the range of C ₆ -C _0.99. Wherein alkyl composition of claim 2 in the range of from about C ₈ ~ about C _40. 4. The composition according to claim 3, wherein the alkyl has a linear structure. 5. A flow improver for use in an oily liquid comprising one or more copolymers of dialkyl fumarate having a C _{6 to} C ₂₅₀ alkyl having a linear or branched alkyl and carbon monoxide. 6. The composition of claim 5, wherein the alkyl ranges from C _{6 to} C ₁₅₀ . 7. The composition of claim 6 alkyl ranges from about C ₈ ~ about C _40. 8. The composition according to claim 7, wherein the alkyl has a linear structure. 9. A wax crystal modifier for use in crude oils containing at least one alkane species, comprising a dialkyl fumarate having a linear or branched alkyl in the range of from about C ₆ to about C ₂₅₀ ; ₃ -C ₃₀ alpha-olefins, ethylene, styrene, at least selected from carbon monoxide and vinyl acetate 1
The above modifier, comprising a copolymer of the two compounds. 10. The composition of claim 9 wherein the alkyl ranges from C _{6 to} C ₁₅₀ . 11. The composition of claim 10 alkyl is in the range of from about C ₁₅ ~ about C _40. 12. The composition of claim 11, wherein the alkyl has a linear structure and substantially the same molecular weight distribution as the crude alkane species. 13. A method of improving the flow properties of the oil liquid, against a large amount of oily liquid, dialkyl fumarate and C ₃ -C ₃₀ alpha having a C ₆ -C ₂₅₀ straight chain structure or a branched structure alkyl A small amount of at least one copolymer with at least one compound selected from the group consisting of olefins, ethylene, styrene and carbon monoxide is added (provided that the oily liquid is Carbon oxide). 14. A method for forming a copolymer, comprising dissolving a C ₆ -C ₂₅₀ linear dialkyl fumarate in a solvent selected from the group consisting of hexane, benzene, cyclohexane, chloroform, xylene, oil and heptane; Combining the dissolved dialkyl fumarate with an initiator selected from the group consisting of t-butyl peroxypivalate, benzoyl peroxide, t-butyl perbenzoate, and t-butyl peroxide in a reactor; After sealing the reactor, purging with purified nitrogen and pressurizing the reactor with one or more compounds selected from the group consisting of carbon monoxide and ethylene to a pressure in the range of about 100 to about 3000 psig; Heating the reactor at a temperature in the range of about 40 to about 200 ° C. for about 1 to about 48 hours to form the copolymer The how to. 15. A pressure ranging from about 500 to about 1200 psig and a temperature ranging from about 50 to about 100 ° C.
15. The method according to claim 14, wherein the solvent is hexane and the initiator is t-butyl peroxypivalate. 16. The method of claim 15, comprising cooling and depressurizing the reactor to recover the copolymer from the solvent. 17. A process for the preparation of a copolymer, comprising a group consisting of hexane, benzene, cyclohexane, chloroform, xylene, oil and heptane under free-radical polymerization conditions for a time and at a pressure sufficient to produce the copolymer. a C ₆ -C ₂₅₀ linear structure dialkyl fumarates of the selected solvent, at least one compound selected from the group consisting of ethylene and carbon monoxide and t-butyl peroxypivalate, benzoyl peroxide, t- The method as described above, wherein an initiator selected from the group consisting of butyl perbenzoate and t-butyl peroxide is attached. 18. A pressure and temperature ranging from about 500 to about 1200 psig.
18. The method of claim 17, wherein the temperature is in the range of from about to about 100 <0> C, the solvent is hexane, and the initiator is t-butyl peroxypivalate. 19. The method of claim 18 including cooling and depressurizing the reactor to recover the copolymer from the solvent. 20. A method for improving the flow characteristics of an oily liquid containing at least one alkane species, wherein the molecular weight distribution of the alkane species in the oily liquid is determined, and then the oily liquid a straight-chain structure or a branched structure dialkyl fumarate having alkane species and substantially the same molecular weight distribution in the liquid, C ₃ -C ₃₀ alpha-olefins, ethylene, at least one compound selected from the group consisting of styrene and carbon monoxide A small amount of at least one of the copolymers with the above.