JP6763958B2 - Copolymers and their use - Google Patents

Description

The present invention relates to copolymers, their synthesis, and the use of copolymers.

Polymers have traditionally been used to modify the rheology of a fluid by incorporating the polymer into the fluid. There is a need for polymers that can be used to regulate the flow and spray properties of petroleum-based fuels, such as gasoline and diesel fuels.

Liquid hydrocarbon fuels as such are typically not flammable. They must first be vaporized and mixed with air, or oxygen, to burn. Efficient atomization is a critical aspect of combustion of such fuels, as intermediate distillates or heavier petroleum fuel fractions have lower vapor pressures.

Atomization produces fine liquid fuel particles, the large surface area of which also results in rapid vaporization and thus rapid and efficient combustion. Even with efficient atomization, stoichiometric combustion cannot be achieved. In this regard, restrictions are imposed by the inability to reach a fully mixed state on the time and dimension scale of the combustion process and equipment. Therefore, it is necessary to supply excess air to the system for complete combustion.

Excess air helps increase combustion efficiency to the extent that it results in complete combustion. However, too much air can result in reduced heat recovery. All of the oxygen that is not involved in the combustion process and all of the nitrogen in the air is heated and therefore carries heat out of the chimney. Moreover, the more excess air there is, the higher the mass flow rate through the system and the shorter the time scale for heat transfer. Therefore, achieving efficient combustion and heat recovery requires a delicate balance between atomization and excess air, coupled with an optimized combustion chamber and heat recovery system design.

British Patent No. 1569344 relates to the use of polymers, especially polyisobutylene, to alter fuel properties in an attempt to improve combustion efficiency. Problems related to polyisobutylene have been found to be very difficult to handle, which is illustrated by its -75 ° C. Tg. Other known polymers, such as polylauryl methacrylate, also have the drawback of such low Tg. It has been found that other polymers, such as polyisobornyl (meth) acrylates, do not provide the desired rheological properties at an acceptable cost and have the drawback of inadequate solubility. European Patent No. 1260278 discloses a coating composition containing 80% by weight of isobornyl (meth) acrylate and a resin comprising 20% by weight or less of other monomers. Like most polymers with relatively high Tg, the disclosed polymers have the drawback of poor solubility of the polymers and have been found to make them unsuitable for changes in liquid rheology. Therefore, there is still a need for alternative polymers that can modify the rheology of liquids, such as petroleum fuels, at a reasonable cost and have acceptable solubility, especially in fuels.

An object of the present invention is to provide a polymer capable of modifying the rheology of such fuels in a manner that can positively affect the combustion efficiency of an internal combustion engine operated using petroleum fuels. is there. For another purpose, a polymer is provided that is fuel efficient and has better performance than polyisobornyl (meth) acrylate. For another purpose, a polymer is provided that has at least the same handling and performance properties as polyisobornyl (meth) acrylate, but at a lower price.

We have found that this object can be met at least partially by the polymers according to the invention, which will be further described in detail below.

In the search for polymers that have better handling properties but are active in improving fuel efficiency when used in fuels, Applicants unexpectedly found that such polymers were one in a particular amount. We have found that it occurs as a result when it contains a species or multiple bicyclic (meth) acrylate esters and a specific amount of styrene. It has also been found that this polymer has better price / performance than conventional polyisobornyl (meth) acrylates.

Therefore, the present invention describes the following monomers:
• Over 80% by weight of one or more bicyclic (meth) acrylate esters,
-For copolymers that can be obtained by copolymerizing less than 20% by weight of a combination of styrene and an optional additional ethylenically unsaturated monomer.

For the polymers of the invention that should be suitable for modifying the rheology of the fluid containing the polymer, the polymer must be sufficiently soluble in said fluid. The fluid can be any fluid. In certain embodiments, it is not fuel. Throughout this document, sufficient solubility in any fluid is determined by analyzing cloudy spots. The cloudiness point is determined using a 2 wt% solution of polymer in 80:20 Petrodiesel: gas vs. liquid diesel fuel (v / v). Sufficient solubility is defined as a cloudy spot below 10 ° C. Preferably, the haze point is less than 0 ° C. so that the polymer does not precipitate from the solution at a temperature of approximately 0 ° C. Details on the cloudiness point determination used in this analysis can be found in the experimental section below.

The bicyclic (meth) acrylate ester has a (meth) acryloyl group bonded to a 6-membered carbon atom crosslinked ring, and decahydronaphthyl (meth) acrylate and adamantyl (meth) acrylate are the groups of the monomer. Products such as are included, but preferably formula (I).

(During the ceremony
R is H or -CH ₃ and
A is -CH _2- , -CH (CH ₃ )-or -C (CH ₃ ) _2- , and
One or more Ms are covalently bonded to the carbon of any of the bicyclic rings, preferably the carbon atom of the 6-membered ring, and consist of hydrogen, halogen, methyl and methylamino groups, or a plurality of them. (Selected from)
Is a product of. Non-limiting examples of bicyclic (meth) acrylate esters include isobornyl (meth) acrylate, bornyl (meth) acrylate, fentyl (meth) acrylate, isofentyl (meth) acrylate, norbornyl (meth) acrylate, cis, ( End) 3-Methylamino-2-bornyl (meth) acrylate, 1,4,5,6,7,7-hexachlorobicyclo [2.2.1] -hepta-5-en-2-ol (meth) acrylate (HCBOMA) and 1,4,5,6,7,7-hexachlorobicyclo [2.2.1] -hepta-5-ene-2 methanol (meth) acrylate (HCBMA), and such bicyclic (HCBMA). Contains a mixture of meta) acrylates. Chlorinated compounds are less preferred as they can release corrosive HCl when they are burned. A suitable bicyclic (meth) acrylate ester is isobornyl methacrylate. Bicyclic (meth) acrylate esters are known in their own right and may be prepared by known methods or may be obtained from commercial sources. Bicyclic (meth) acrylates are preferably selected from monomers that, when polymerized, form homopolymers that are soluble in liquids, preferably fuels, more preferably 80:20 petrodies: gas vs. liquid diesel fuels. To.

The ethylenically unsaturated monomers present at the option include:
1. 1. The (meth) acryloyl group is a C8 to C24 alkyl group, preferably a C10 to C22 group and a aliphatic alkyl group as defined herein (which is linear or branched, substituted or unsubstituted, saturated or unsaturated. Fat alkyl (meth) acrylate, which is a compound attached to (obtain). Examples of fatty alkyl (meth) acrylates include 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, and methacrylic acid ester 13.0 (CAS number: 90551-76). -1), tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, methacrylate ester 17.4 (CAS number: 90551-84-1), and stearyl (meth) acrylate are included. Preferred aliphatic alkyl (meth) acrylates, when polymerized, are selected from monomers that form homopolymers that are soluble in diesel fuels. In another embodiment, isodecyl (meth) acrylate, lauryl (meth) acrylate, methacrylic acid ester 13.0 (CAS number: 90551-76-1), methacrylic acid ester 17.4 (CAS number: 90551-84-1). ) And / or stearyl (meth) acrylates are used. In yet another embodiment, lauryl (meth) acrylate and / or methacrylic acid ester 13.0 (CAS No .: 90551-76-1) is used. Where appropriate, lauryl methacrylate is used;

2. 2. An aromatic vinyl monomer other than styrene having a vinyl group bonded to an aromatic group. Examples include substituted styrene, vinylnaphthalene, divinylbenzene, and mixtures thereof. Preferred substituted styrenes include ortho-, meta- and / or para-alkyl, alkyloxy or halogen substituted styrenes such as methylstyrene, 4-tert-butylstyrene, tert-butyloxystyrene, 2-chlorostyrene and 4-. Includes chlorostyrene. Aromatic vinyl monomers are preferably selected from those that, when polymerized, form homopolymers that are insoluble in liquids, preferably fuels, more preferably 80:20 petrodies: gas vs. liquid diesel fuels;

3. 3. An ethylenically unsaturated monomer different from the monomers in groups 1 and 2 defined above. Examples of such other monomers include lower alkyl (meth) acrylates (where lower alkyl means alkyl groups having less than 8 carbon atoms), such as methyl (meth) acrylate, ethyl (where Meta) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate and hexyl (meth) acrylate, and cationic, nonionic and anionic ethylenically unsaturated monomers (meth). Not limited, but ethylenically unsaturated acids such as (meth) acrylic acid, maleic acid, 2-acrylamide-2-methylpropanesulfonic acid, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N- [3- (dimethylamino). ) Procyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, (3-acrylamide propyl) -trimethyl-ammonium chloride, methacrylamide propyltrimethylammonium chloride, (meth) acrylamide, N-alkyl (meth) acrylamide , N-vinylpyrrolidone, vinylformamide, vinylacetamide, and N-vinylcaprolactam).

In certain embodiments of the invention, for any of the optionally present ethylenically unsaturated monomers, the monomers result in corrosive products in the exhaust gas system upon combustion, eg, HCl and H ₂ SO ₄ , respectively. , Chlorine or other elements, such as sulfur.

In certain embodiments, the ethylenically unsaturated monomer used is free of elements that increase the release of NOx compounds when the ethylenically unsaturated monomer is present in the fuel.

In yet another embodiment, all ethylenically unsaturated monomers are used in the fuel and when the fuel is burned, the resulting polymer is a NOx compound per kW generated by the engine that burns the fuel. Is selected to result in a reduced release of.

In yet another embodiment, all ethylenically unsaturated monomers are granular material per kW generated by the engine that burns the fuel when the resulting polymer is used in the fuel and the fuel is burned. Is selected to result in reduced emissions (compared to burning the same fuel without polymer).

Copolymers may be synthesized by conventional methods known to those skilled in the art for vinyl addition polymerization, such as, but not limited to, solution polymerization, precipitation polymerization, and dispersion polymerization (including suspension and emulsion polymerization).

In certain embodiments, the polymer is formed by suspension polymerization, where the water-insoluble or water-insoluble monomer is suspended as droplets in water. Suspension of monomer droplets is maintained by mechanical stirring and addition of stabilizers. Alkali metal salts of surface active polymers such as cellulose ether, poly (vinyl alcohol-co-vinyl acetate), poly (vinylpyrrolidone), and (meth) acrylic acid-containing polymers and colloidal (water-insoluble) inorganic powders, such as Tricalcium phosphate, hydroxyapatite, barium sulfate, kaolin, and magnesium silicate can be used as stabilizers. In addition, small amounts of surfactant, such as sodium dodecylbenzenesulfonate, can be used with stabilizers. Polymerization is initiated using an oil-soluble initiator. Suitable initiators include peroxides such as benzoyl peroxides, peroxy esters such as tert-butyl peroxy-2-ethylhexanoate, and azo compounds such as 2,2'-azobis (2-methylbutyronitrile). ) Is included. Upon completion of the polymerization, the solid polymer product can be separated from the reaction medium by filtration and washed with water, acid, base, or solvent to remove unreacted monomers or release stabilizers.

In another embodiment, the polymer is formed by emulsion polymerization, where one or more monomers are dispersed in an aqueous phase and the polymerization is initiated using a water soluble initiator. Monomers are typically water insoluble or very sparingly soluble in water, and surfactants or soaps are used to stabilize the monomer droplets in the aqueous phase. The polymerization is carried out in swollen micelles and latex particles. Other components that may be present during emulsion polymerization include chain transfer agents for controlling molecular weight, such as mercaptans (eg, dodecyl mercaptan, small amounts of water-soluble organic solvents for adjusting the polarity of the aqueous phase). For example, but not limited to, acetone, 2-butanone, methanol, ethanol, and isopropanol, and electrolytes for controlling pH. Suitable initiators include alkali metal or ammonium salts of persulfate ions. For example, ammonium persulfate, water-soluble azo compounds such as 2,2'-azobis (2-aminopropane) dihydrochloride, and redox systems such as Fe (II) and cumenehydroperoxide, and tert-butylhydroperoxide-Fe. (II) -Sodium ascorbate. Suitable surfactants include anionic surfactants such as fatty acid soaps (eg sodium stearate or potassium), sulfates and sulfonates (eg dodecylbenzene). Sodium sulfonate), sulfosuccinates (eg, sodium dioctyl sulfosuccinate); nonionic surfactants such as octylphenol ethoxylates and linear and branched alcohol ethoxylates; cationic surfactants such as cetyltrimethylammonium chloride. Also includes amphoteric surfactants. Anionic surfactants, and combinations of anionic and nonionic surfactants are most commonly used. Polymer stabilizers such as poly (vinyl alcohol). -Co-vinyl acetate) can also be used as a surfactant. Solid polymer products without an aqueous medium can be destabilized / aggregated in the final emulsion, followed by filtration, solvent precipitation of the polymer from latex, or. It can be obtained by several processes, including spray drying of latex.

Those skilled in the art will appreciate that certain surfactant and initiator systems can leave unwanted residues in the polymer in the fuel. Again, these may include sulfur-containing species, as well as halides, as well as monovalent and polyvalent metals, or ions thereof. Alternative surfactants and initiators that do not leave such residues can be selected, or isolation / purification processes can be selected that remove or minimize any unwanted residues.

In certain embodiments, the present invention describes the following monomers:
• Over 80% by weight of one or more bicyclic (meth) acrylate esters,
With respect to copolymers that can be obtained by copolymerizing less than 20% by weight of styrene and optionally additional ethylenically unsaturated monomers.

In certain embodiments, the copolymer is
Bicyclic (meth) acrylate ester (a) from more than 80% by weight to 99.95% by weight,
0.05 to 15% by weight styrene (b), and an optional ethylenically unsaturated monomer (c) that is not the monomer (a) or (b)
Is polymerized from.

Throughout this document, the weight percent (% by weight) of the monomers that make up the copolymer is based on the total weight of the monomers used, with the total weight of the monomers totaling 100% by weight.

In certain embodiments, the copolymer is
81-99.95% by weight, preferably 82-99.95% by weight, more preferably 83-99.95% by weight, even more preferably 85-99.95% by weight, most preferably 90-99.95% by weight. % Bicyclic (meth) acrylate ester (a),
0.05-12% by weight, preferably 1-10% by weight, more preferably 2.5-8.0% by weight of styrene (b), and 0-19% by weight, not monomer (a) or (b). , Preferably from 0 to 18% by weight, more preferably from 0 to 15% by weight of ethylenically unsaturated monomers.

For each of the embodiments, the sum of the monomers (a) and (b) is greater than or equal to 83% by weight of the total monomer composition, more preferably greater than or equal to 90% by weight. , Most preferably greater than or equal to 95% by weight, and most preferably greater than or equal to 99% by weight.

Preferably, in each embodiment, the amount of other ethylenically unsaturated monomers other than a) or b) does not exceed 10% by weight, more preferably no more than 5% by weight, even more preferably 1% by weight. In certain embodiments, the monomers a), and styrene together make up 100% by weight of the monomers used to form the copolymer.

Under certain conditions, the copolymer is not composed of at least one bicyclic (meth) acrylate ester, at least one aliphatic alkyl (meth) acrylate, and at least one lower alkyl (meth) acrylate. They also consist of at least one bicyclic (meth) acrylate ester, at least one aliphatic alkyl (meth) acrylate, at least one lower alkyl (meth) acrylate, and at least one aromatic vinyl monomer. It does not have to be a copolymer, in particular a copolymer in which the weight percent of the bicyclic (meth) acrylate is more than 15 weight percent higher than the amount of aromatic vinyl monomer. In embodiments with this condition, the copolymer comprises greater than 20% by weight, preferably greater than 10% by weight, more preferably greater than 5% by weight of the aliphatic alkyl (meth) acrylate. In another embodiment of this condition, the copolymer comprises a lower alkyl (meth) acrylate of greater than 20% by weight, preferably greater than 10% by weight, more preferably greater than 5% by weight.

Under different conditions, the copolymers are at least one bicyclic (meth) acrylate ester, at least one aliphatic alkyl (meth) acrylate, optionally at least one aromatic vinyl monomer, and optionally another. It is not composed of ethylenically unsaturated monomers. In embodiments with this condition, the copolymer is 20-95% by weight bicyclic (meth) acrylate ester, 5-80% by weight, preferably 5-40% by weight of aliphatic alkyl (meth) acrylate, 65% by weight. Not composed of aromatic vinyl monomers up to, and optionally other ethylenically unsaturated monomers. In embodiments with this condition, the copolymer comprises greater than 20% by weight, preferably greater than 10% by weight, more preferably greater than 5% by weight of the aliphatic alkyl (meth) acrylate. In another embodiment of this condition, the copolymer comprises more than 20% by weight, preferably more than 10% by weight, more preferably more than 5% by weight of aromatic vinyl monomer. In another embodiment of this condition, the copolymer comprises more than 20% by weight, preferably more than 10% by weight, more preferably 5% by weight of other ethylenically unsaturated monomers.

Surprisingly, styrene homopolymers have a very high cloud point (> 150 ° C) in 80:20 petrodies: gas vs. liquid diesel fuels, but in small amounts this monomer is copolymerized with isobornyl methacrylate. It has been found that it can be polymerized to give a highly soluble copolymer with a desired cloud point below 12.5 ° C. Moreover, in a very specific concentration range for styrene, it was found that the haze of the copolymer was even lower than that of poly (isobornyl methacrylate), which had a haze of 0.5-3 ° C. Was done. In a preferred embodiment, the copolymer has a haze point below 0 ° C.

If so, small amounts of divinylbenzene can be used in the monomer mix, especially to control the molecular weight and molecular weight distribution of the polymer and / or to control the rheological behavior of the polymer solution. .. Typically, the divinylbenzene level is less than 5%, preferably less than 2%, more preferably less than 1%.

In the copolymers of the invention, the monomers may be arranged in any way, eg, in blocks or randomly. Preferably, the copolymer is a randomly placed copolymer.

The weight average molecular weight (Mw) of the copolymers of the present invention is preferably at least 200,000 D, 250,000 D, or at least 400,000 D when measured according to the methods presented in the experimental section. For such polymers, the effect on the rheology of the fluid in which they are dissolved is very cost effective. The upper molecular weight is determined by the solubility in the fluid in which it is intended to be used. A suitable Mw is less than 50,000,000, preferably less than 25,000,000. Polymers with the composition of the present invention and molecular weights of 100,000 to 50,000,000, preferably 250,000 to 5,000,000 D, have been found to be useful at low concentrations, which make them useful. It has been made particularly suitable for use in fuels, especially in additive packages for fuels. The polydispersity index (PDI) of the copolymers of the present invention, that is, Mw / Mn, is appropriately 1 to 10, preferably 1 to 5. Therefore, in certain embodiments, the Mn of the polymer of the present invention is 20,000 D or more.

The glass transition temperature of the copolymers of the present invention is preferably 50-220 ° C, more preferably 65-210 ° C, and in another embodiment 95-200 ° C, as determined by differential scanning calorimetry (DSC). .. In this document, the glass transition temperature (Tg) was measured using DSC Q200 (TA Instruments, New Castle, Delaware) by the following program:
1) Start DSC execution at 20 ° C. for 15 minutes at an isothermal temperature;
2) Inclinate the temperature at 10 ° C./min to over approximately 20 ° C. of Tg of material;
3) Run isothermal for 5 minutes at that temperature;
4) Lower the temperature of Tg from over 20 ° C to 20 ° C at 20 ° C / min;
5) Run isothermal at 20 ° C for 5 minutes;
6) Start the adjustment mode every 60 seconds under process conditions of ± 1.280 ° C .;
7) Inclinate the temperature to 180 ° C at 2 ° C / min.

The composition of the polymer can be estimated as reliable from the relative amount of monomers supplied during the polymerization. Alternatively, the composition of the copolymer is appropriately determined from the carbon-13 NMR spectrum using a Varian MR-400 MHz and / or Agilent DD2 MR 500 MHz NMR spectrometer.

The polymers of the present invention are advantageously added to petroleum-based fuels that are advantageously suitable for operating combustion engines, such as fuels customarily known as gasoline and diesel fuels. The polymer is preferably added to the fuel in an amount effective to obtain the effect of improving combustion efficiency. Typically, the polymers of the present invention are fueled at concentrations less than 10,000 ppm (per million copies), eg, from 5, 10, 50, 100 or 500 ppm to preferably 3000 or 5,000 ppm. Is added. The term "ppm" is equal to 1 mg per kg. In certain embodiments, the copolymer is present in the fuel composition in an amount ranging from 10 ppm to 300 ppm, more preferably from 10 ppm to 100 ppm, eg, 25 ppm to 80 ppm, based on the total weight of the fuel composition. ..

The advantages of the copolymers of the present invention are: (1) they are more suitable for adjusting the flow and spray properties of petroleum fuels than conventional polymers; (2) the frosting point of the copolymers is the polymer at a temperature of 0 ° C. Low enough to allow the handling of; (3) the cost of these copolymers is lower than that of poly (isobornyl methacrylate) and other conventional polymers; and (4) they are used in fuels. Is to be able to be used in additive packages for.

As used herein, "gasoline" refers to liquid hydrocarbon fuels suitable for the practice of spark ignition engines, as is commonly known in the art, petroleum raw materials, renewable raw materials, and theirs. Contains fuels such as a mixture of.

As used herein, "diesel" refers to liquid hydrocarbon fuels suitable for the operation of compression ignition engines, as is commonly known in the art, petroleum raw materials, renewable raw materials, and theirs. Contains fuels such as a mixture of.

The term "consisting", wherever used herein, also includes "consisting substantially", but its strict meaning of "consisting entity". It may be limited to any option.

Throughout the description and claims of the present specification, the terms "comprise" and "contain" and variations of the term, such as "comprising" and "comprises", are referred to as "comprising" and "comprises". It means "inclusion but not limited to" and does not exclude other parts, adducts, ingredients, perfections or processes. Further, it is understood that the singular includes the plural unless otherwise required by the context, and in particular, where indefinite articles are used, the present specification contemplates the plural as well as the singular unless otherwise required by the context. It should be.

When upper and lower limits are presented for properties, eg, concentrations of fuel components, the range of values defined by the combination of any of the upper limits and any of the lower limits may also be implied.

Various aspects and embodiments of the detailed description as disclosed herein illustrate specific methods for making and using the present invention, along with the claims and detailed description. It should be recognized that it does not limit the scope of the invention when considered. It is also recognized that features from different aspects and embodiments of the invention may be combined with features from any other aspect and embodiment of the invention.

In the context of the present invention, the term "(meth) acrylate" refers to acrylate or methacrylate, and "(co) polymer" refers to a polymer or copolymer. The terms "polymer" and "copolymer" are used interchangeably herein.

In addition to hydrocarbons and polymers, gasoline and diesel fuels may contain other additives as commonly used in the art. To determine the solubility in diesel, 80:20 petro diesel (B0): gas to liquids (GTL) diesel fuel (v / v) is used according to the EN 590 diesel fuel standard. This fuel is considered to be the most demanding fuel for polymer solubility. Therefore, polymers that pass this fuel solubility standard are considered useful for dissolution in any fuel.

The B0 fuel according to EN590, SS-EN590: 2009 in the present invention has a cetane number of ≧ 51.0 and a cetane index of ≧ 46.0 and is completely biofuel free and therefore the amount of fatty acid methyl ester. It is noted that is essentially 0%. Shell ™ "Gas to Liquids" or "GTL" technology (officially known as SMDS (Shell Middle Distilate Synthesis)) is a paper distributed in the 5th Synfuels Wordwide Symposium, Washignton, DC, November, 1985, "The It appears in the November, 1989 publication of the same title from Shell Middle Distillate Synthesis Process ", van der Burgt et al and Shell Interational Petroleum Company Ltd, London, UK.

The copolymers of the present invention are preferably soluble in such 80:20 petrodies: gas vs. liquid diesel fuels (v / v). The polymer is considered soluble according to the present invention if at least a 2.0 wt% solution of the polymer in fuel at 25 ° C. can be made after heating as needed. Preferably, a 2.0 wt% solution of the polymer in fuel can be made at 8 ° C. In another embodiment, a 9.1 wt% solution of polymer in fuel can be made at 25 ° C. Preferably, the copolymer of any embodiment of the invention has a fog point below 10 ° C, more preferably a cloud point below 5 ° C, and even more when analyzed as described in the experimental section below. It preferably shows a cloudiness point of less than 0 ° C.

A series of exemplary invention copolymers and comparative copolymers have been made using various combinations of isobornyl methacrylate and styrene. Isobornyl methacrylate was obtained from Sigma-Aldrich or Evonik (VISIOMER® Terra IBOMA). Styrene and polystyrene (280,000 Mw) were obtained from Sigma-Aldrich.

Molecular weight:
The molecular weight of the polymer was determined using GPC-MALS.
Column: Phenogel Guard 10 ^∧ 6A
Column oven: 40 ° C
Mobile phase: Tetrahydrofuran Detection: Waitt Down Heleus 18-sided MALS 633 nm and Waitt Optilab T-REX Refractive Index detector.

Cloudy Point Determining Method- 0.40 g of polymer and 19.6 g of 80:20 petro diesel: gas vs. liquid diesel fuel (v / v) were charged into 40 mL clear vials of all polymers except polystyrene . The vial was loosely capped and the mixture was stirred at ambient temperature (about 20-25 ° C.) for 1 hour using a magnetic stir bar and stir bar. The mixture was then heated to about 70-80 ° C. with stirring until a uniform solution was obtained. After the solution had cooled to ambient temperature, the cap was removed and the thermometer was introduced into the vial. The solution was cooled by immersing the vial in a dry ice / isopropanol bath with stirring with a thermometer. The reported haze point is the temperature at which the solution is visibly cloudy or cloudy. As a test, as soon as the haze point of the polymer is determined, the clear polymer solution is cooled using a dry ice / isopropanol bath below the originally observed haze point, then the cloudy solution with stirring with a thermometer. Was warmed past the point where it became transparent again. When the temperature at which the transparent polymer solution became cloudy and the temperature at which the cloudy polymer solution became transparent were within 1 ° C. (preferably within 0.5 ° C.) of each other, it was determined that a clouding point was confirmed. For polymers with haze points below 10 ° C., be careful to remove water from the polymer solution while cooling them; this is a crude for vials into which a thermometer is inserted. , Conveniently done by using a parafilm that produces a flexible covering.

Cloudy point determination method-poly (styrene)
1.3317 g of poly (styrene) and 65.65 g of 80:20 petro diesel: gas vs. liquid diesel in a four-necked 500 mL round-bottom flask equipped with an overhead mechanical stirrer, thermometer, condenser and diaphragm / stopper. Fuel (v / v) was added. The resulting mixture was heated to 150 ° C. for a total of 3 hours with stirring. After 3 hours at 150 ° C., polystyrene was not completely dissolved in this fuel. Based on this observation, the haze point of polystyrene in 80:20 petrodiesel: gas vs. liquid diesel fuel (v / v) was estimated to be above 150 ° C.

Polymerization procedure Preparation of copolymer by emulsion polymerization process Material:

The 1 L four-necked round-bottom flask was equipped with an overhead mechanical stirrer; a Y-tube with a condenser and thermometer at the top of the nitrogen purge outlet; and two diaphragms. Deionized water and Aerosol OT-75PG were charged into this flask. A thermostat-controlled water bath was used to bring the reaction temperature to about 50 ° C. An 11-minute subsurface nitrogen purge was then initiated via a needle inserted through one of the diaphragms, maintaining a stirring rate of 200 rpm.

A mixture of isobornyl methacrylate and styrene, as well as acetone, was charged into the reaction vessel while maintaining a nitrogen purge. Subsurface nitrogen purging was continued after the addition of monomer / acetone.

A reducing agent solution consisting of sodium ascorbate and iron (II) sulfate heptahydrate dissolved in deionized water was prepared in a separate container. Iron (II) sulfate heptahydrate was added after the ascorbate had dissolved and just before the use of the reducing agent solution.

After the addition of monomer / acetone, the reaction was purged with nitrogen for an additional 15 minutes, then the resulting dark blue ascorbate solution was added in one shot to the reaction vessel by syringe while maintaining the subsurface nitrogen purge.

An oxidant solution consisting of t-butyl hydroperoxide (70%) in deionized water was prepared in a second separate container. Approximately 12 minutes after the addition of the reducing agent, the oxidant solution was added to the reaction in one shot by syringe while maintaining the subsurface nitrogen purge.

Within about 6 minutes, the onset of exotherm was observed, giving priority to superficial nitrogen parsing and stopping subsurface nitrogen parsing. As the reaction proceeded, a bluish color was observed in the emulsion, which became more and more translucent, with a slight increase in viscosity. The reaction temperature reached a maximum of about 55 ° C. (initial temperature: 49.7 ° C.), after which it began to drop after about 30 minutes. The reaction temperature was then maintained at 48-50 ° C. using a water bath. After a total reaction time of 4.5 hours, the reaction was cooled and poured through a cheesecloth into a container.

Solid polymers were isolated by adding undiluted emulsified polymer to a large excess of methanol. The resulting precipitate was collected by vacuum filtration and washed thoroughly with methanol.

When the molecular weight of the product of Example 7 was measured by conventional GPC-MALS and found to be Mn: 1,700,000; Mw: 3,150,000; PDI: 1.91 and analyzed by NMR. , The composition was found to be 90.5% by weight isobornyl methacrylate; 9.5% by weight styrene. Solids (measured by weight measurement-two ways): 26.99%.

For the products of Examples 9-12, the amount of TBHP used was reduced to 0.0195 g. For Examples 13-15, 0.039 g TBHP and 0.072 g sodium ascorbate were used. In Example 10, Example 12, Example 14, and Example 15, no co-solvent was used. In Example 11, Example 12, and Example 14, the amount of sodium dioctyl sulfosuccinate was 2.055 g.

The results show that surprisingly low fogging points are observed for the polymers of the present invention, allowing their use as a fluid thickener over a wide temperature range.

The products of the present invention having the P number in the usage experiment table 1 were evaluated for their effect on diesel rheology and their effect on ignition delay, combustion period, and maximum pressure increase in the combustion research unit. First, the concentrate was made in diesel containing at least 2.5% by weight of copolymer, which was then diluted with fuel.

The data obtained show that when the product according to the invention is used in diesel fuel, it improves the fuel efficiency of a direct injection diesel engine operating on said fuel and of the released NOx per kW of released energy. It was shown that the amount was reduced. We do not want to be bound by this theory, but the improved efficiency is that the rheology modified for the use of polymers in the fuel results in improved atomization and more complete combustion of the fuel. it is conceivable that.
The present invention includes the following aspects.
Item 1.
A total of 100% by weight,
One or more bicyclic (meth) acrylate esters (a) in excess of 80% by weight,
It can be obtained by copolymerizing 0.05 to 15% by weight of styrene (b), and optionally one or more ethylenically unsaturated monomers other than the monomers (a) or (b). A copolymer that can be a copolymer in which the weight percent of the monomers is based on the total weight of all the monomers.
Item 2.
The bicyclic (meth) acrylate ester has the formula

(In the formula, R is H or -CH ₃ , A is -CH _2- , -CH (CH ₃ )-or -C (CH ₃ ) _2- , and M is the carbon of the 6-membered ring. Covalently bonded to an atom and selected from hydrogen and methyl groups, or a group of multiple of them)
Item 2. The copolymer according to Item 1.
Item 3.
The copolymer according to 1 or 2, which is a random copolymer.
Item 4.
A total of 100% by weight,
81-99.95% by weight, preferably 82-99.95% by weight, more preferably 83-99.95% by weight of the bicyclic (meth) acrylate ester (a),
Includes 0.05-12% by weight of the styrene (b) and 0-19% by weight of the ethylenically unsaturated monomer, which is not the monomer (a) or (b), with all weight percent of the monomer being Item 2. The copolymer according to Item 1, 2 or 3, based on the total weight of the monomer.
Item 5.
A total of 100% by weight,
85-99.95% by weight of the bicyclic (meth) acrylate ester (a),
1-10% by weight of the styrene (b), and • 0-10% by weight of the ethylenically unsaturated monomer, which is not the monomer (a) or (b), and the weight percent of the monomer is of all monomers. Item 4. The copolymer according to item 4, based on total weight.
Item 6.
A total of 100% by weight,
90-99.95% by weight of the bicyclic (meth) acrylate ester (a),
2.0 to 8.0% by weight of the styrene (b) and 0 to 5% by weight of the ethylenically unsaturated monomer that is not the monomer (a) or (b), with a weight percent of the monomer. Item 5. The copolymer according to Item 5, based on the total weight of all monomers.
Item 7.
Item 2. The copolymer according to any one of Items 1 to 6, wherein the total of the bicyclic (meth) acrylate ester and the styrene is contained in an amount of 83% by weight, preferably 90% by weight or more of the total monomer. ..
Item 8.
Item 7. The copolymer according to Item 7, wherein the total of the bicyclic (meth) acrylate ester and the styrene is contained in an amount of 95% by weight or more, preferably 99% by weight or more.
Item 9.
Item 8. The copolymer according to Item 8, which is produced from isobornyl methacrylate and styrene.
Item 10.
Item 8. The copolymer according to any one of Items 1 to 9, which has a cloudiness point in the fuel at 12.5 ° C. or lower, preferably 0 ° C. or lower.
Item 11.
Item 8. The copolymer according to any one of Items 1 to 10, which has an average weight average molecular weight of 100,000 to 50,000,000 D.
Item 12.
A fuel additive package comprising the copolymer according to any one of Items 1 to 11.
Item 13.
Item 6. The method for preparing a copolymer according to any one of Items 1 to 11, which comprises a step of radically polymerizing a specific monomer.
Item 14.
A method for preparing a fuel additive package, comprising the step of preparing a solution containing the copolymer according to any one of Items 1 to 11 and one or more other fuel additives.
Item 15.
The use of the polymer or additive package according to any one of Items 1 to 12 for modifying the rheology of the fluid by dissolving the polymer in the fluid which is not a fuel for a combustion engine. ,use.

Claims (14)

A total of 100% by weight,
83-99.95% by weight bicyclic (meth) acrylate ester (a),
- 0.05 to 15% by weight of styrene (b), and the weight percent of monomer (a) or (b) by including copolymer 0-19 weight% of an ethylenically unsaturated monomer not (monomer, all Fuel additive package containing ( based on the total weight of the monomer ) . The bicyclic (meth) acrylate ester has the formula
(In the formula, R is H or -CH ₃ , A is -CH _2- , -CH (CH ₃ )-or -C (CH ₃ ) _2- , and M is the carbon of the 6-membered ring. Covalently bonded to an atom and selected from hydrogen and methyl groups, or a group of multiple of them)
The fuel additive package according to claim 1. The fuel additive package according to claim 1 or 2, wherein the copolymer is a random copolymer. The copolymers total 100% by weight.
85-99.95% by weight of the bicyclic (meth) acrylate ester (a),
- 1 to 10% by weight of the styrene (b), and not the monomer (a) or (b), the weight percent of including (monomer 0-10% by weight of the ethylenically unsaturated monomers, all The fuel additive package according to claim 1, 2 or 3 ) , based on the total weight of the monomer. The copolymers total 100% by weight.
90-99.95% by weight of the bicyclic (meth) acrylate ester (a),
- 2.0 to 8.0% by weight of the styrene (b), and not the monomer (a) or (b), 0 to 5 weight percent of the weight% of said ethylenically unsaturated monomers including (monomer Is based on the total weight of all monomers ) , the fuel additive package according to claim 4. The fuel according to any one of claims 1 to 5, wherein the copolymer contains the sum of the bicyclic (meth) acrylate ester and the styrene in an amount of 90% by weight or more of the total monomer . Additive package . The fuel additive package of claim 6, wherein the copolymer comprises the sum of the bicyclic (meth) acrylate ester and the styrene in an amount of 95% by weight or more. The fuel additive package of claim 6, wherein the copolymer comprises the sum of the bicyclic (meth) acrylate ester and the styrene in an amount of 99% by weight or more. The fuel additive package according to claim 7 or 8, wherein the copolymer is produced from isobornyl methacrylate and styrene. The fuel additive package according to any one of claims 1 to 9, wherein the copolymer has a cloudiness point in the fuel at 12.5 ° C. or lower. The fuel additive package according to any one of claims 1 to 9, wherein the copolymer has a cloudiness point in the fuel at 0 ° C. or lower. The fuel additive package according to any one of claims 1 to 11 , wherein the copolymer has an average weight average molecular weight of 100,000 to 50,000,000 D. A method for preparing a fuel additive package, comprising the step of preparing a solution containing a copolymer and one or more other fuel additives .
The copolymers total 100% by weight.
83-99.95% by weight bicyclic (meth) acrylate ester (a),
0.05 to 15% by weight of styrene (b), and
0-19% by weight ethylenically unsaturated monomer that is not the monomer (a) or (b)
(Percent weight of monomer is based on total weight of all monomers),
The method. For modifying the rheology of the fluid, to the use of the fuel additive package of any one of claim 1 to 12 additive package for a fuel in the fluid is a fuel for a combustion engine Use by dissolving the copolymer contained in .