TW204355B - Dispersant polymethacrylate viscosity index improvers - Google Patents

Abstract

This invention relates to copolymers derived from (a) monomers selected from the group consisting of (C1-C24) alkylmethacrylates and (C1-C24) alkyl acrylates and (b) a monomer selected from the group consisting of hydroxy (C2-C6)alkyl methacrylates and hydroxy(C2-C6)alkyl acrylates in which the number of carbon atoms in the alkyl groups averages from about 7 to about 12. These polymers are useful as additives to lubricating oils for providing viscosity index improvement, dispersancy and low temperature fluidity properties without adversely affecting fluoropolymer seals and gaskets.

Description

A6 B6 204355 5. Description of the invention (1) The present invention is based on (1) a monomer from (L-Cm) alkyl methacrylate and (C, -Ce /) alkyl acrylate; and (2) s is a polymer derived from a monomer of hydroxy (Ca-C,) alkyl methacrylate and hydroxy (Ca-C〇) alkyl acrylate, and it is a master in the alkyl The average number of atoms is between about 7 and about 12. These polymers can be used as additives for lubricating oils to improve their viscosity index, dispersibility and low-temperature properties, etc., so as not to cause bad color to fluoropolymer seals and gaskets. These new polymers are usually pseudo-dissolved or dispersed in refined lubricating oil before they are finally incorporated into mineral or synthetic base oils. The ideal lubricating oil for internal combustion engines, automatic transmission liquids, and hydraulic fluids must have a small viscosity change within a large temperature range, and must have a good separation and good performance at low temperatures. Mobility, including low pour point. Viscosity index (VI) is pseudo used to measure the degree of viscosity change with temperature; a high viscosity index value means that the lower the viscosity index is, the lower the viscosity index value is. Viscosity index changing additives with a high viscosity index value and good low-temperature fluidity can make the oil flow freely at the lowest possible operating temperature-generally assuming that the engine starts to run freely, and when the temperature increases to the operating range, The viscosity is still maintained at an appropriate level for good performance. At present, polymer additives have been used to improve engine lubricating oils and these properties have the performance of mandarin. Polymers of alkyl acrylates or alkyl methacrylates have been successfully used as viscosity index improvers and pour point depressants. In the polymer composition, by adding some polar, especially scouring comonomers, such as vinyl hybrid compounds, this paper is suitable for a. Home «quasi (CNS) A 4 wash grid m〇X 297« ) ------- ^ ----. U .--- · ---- {----- installed II ---- order ------ line {(please read first Note on the back and write this page again) Printed by the Ministry of Economic Affairs #Bijugong Consumer Cooperatives 81.9.20,000 204355 Λ (; Β6 V. Description of Invention (2) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs «Printed by Industrial and Commercial Cooperatives ( (N-vinylpyrrolidone, U-vinyl azole, vinylpyridine, etc.), dialkylaminoalkyl methacrylate, Ν, Ν-dialkylaminoalkylmethacrylamide, etc. , It can enhance its dispersion properties. However, under the grafting conditions of the salty comonomer containing ®, it will often produce poor shear stability. Moreover, the viscosity index improver contains When it is used as a co-monomer, it may cause a bad smell, or make the gasket or seal of a fluoropolymer in the automobile engine cracked by a fluoropolymer such as VifonTM roll elastomer reduce its effectiveness. 3,311,597 Shown is a method to improve the viscosity index and dispersion properties of poly (methacrylate) polymers. It can make the copolymerization of alkyl methacrylate and tetrahydrofuran methacrylate. Hydroxyethyl oethacrylate, hydroxypropyl methacrylate, M-vinyl Dtt pyrrolidone or t-butyUainoeUyl nehtacrylate. It is composed of alkyl methacrylate sugar and 9 -23 mol% methacrylic acid is copolymerized, and the poly (alkylmethylpropane sulfonate) polymer with improved pour point properties made by ethoxylation has been shown in the United States. Patent No. 3,5 9 8, 7 3 7 in which the average number of alkyl atoms in the alkyl group is between 12.5 and 14.3. And lauryl methacrylate-lauryl aethacrylate- Stearyl nethacrylatO copolymer containing 23% of its hydroxyethyl methacrylate is shown in US No. 3, 249, 545, which is used in oil formulations containing bisphenol anti-gasification agents . Used in other Among the methods of good dispersibility and viscosity index, "Zhou Zhuan (read the note on the back & read the notes on the back and then write a copy !!)-install · order.-Line (! This paper size is suitable for China's home-made standard ( CNS) A 4 specifications (210 X 297 mm) 81.9.20,000 A6 BC) 204355 V. Description of the invention (3) Li No. 418610A shows the use of polyalkyl (meth) acrylate, the waiting time is: 8 0- 9 5.5% by weight copolymer is derived from (C ·-!: · *) alkyl (meth) acrylate, and 0.5-20% is like hydroxy (C * -C *) alkyl (meth Group) Acrylate or polyalkylated (Bultialkoxylized) alkyl (meth) acrylate derived, or, can also make 〇-17 reset stoneware copolymer (C *-C β) alkyl Derived from (meth) acrylate. Poly (methacrylic acid vinegar) polymer for machine tool working oil as an additive, which contains 92-99% (Ci-Ci ·) alkyl methacrylate and 1-8% hydroxyl (C,- C3) Alkyl methacrylate, and the average molecular weight (Mn) of the polymer is between 20,000 and 60,000, the pseudo-annulation is shown in Japanese Patent No. 52-018202B. None of these ionomer additives are suitable for engine oil as an additive to improve dispersibility and viscosity index. The latter thrashing methods fail to make a single polymer with good dispersibility, good viscosity index, good compatibility with fluoropolymer sealing materials, and good low temperature fluidity. The purpose of the invention is to provide a single polymer with some comprehensive properties. The period of the invention is from (1) about 90 to about 98% by weight of monomers escaping from (Ct-Ca4) alkyl methacrylate and (L-Cm) alkyl acrylate; and (2) below 10 to about 2% of the replacement lotus is derived from monomers of hydroxy (C ·-!: ·) alkyl methyl propionate and hydroxy (Ca-C ·) alkyl acrylate, which are derived from polymerization Polymer, and in the backbone polymer (backbone polyner) side of the alkyl group, the average number of nitrate atoms is between about 7 to about 12. These polymers can be used as additives for lubricating oils. «Applicable to National Standard (CNS) A 4 grids (210 X 297 mm) at -5-This paper scale is 81.9.20 000 ------ Ί-ν —— 』· ---- {----- installed --------, 玎 ------ Μ _ (please read the notes on the back of the merits and do the manuscript 玎) Central Standard of the Ministry of Economic Affairs Printed by shoulder shell industry consumer cooperative 204355 Λ 6 Β6 Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (4) Improving the reed viscosity index, dispersibility, and low-temperature characteristics, but not dare to make fluoropolymer The seal H and the gasket cause bad color sound. Some of the new Yingying polymers, when used in lubricating oils, are usually dissolved or divided into mineral oils in refining, and are finally added with mineral or synthetic base oils. Examples of lubricating oils include crankcase oil, automatic liquid feed, hydraulic fluid, Quhan oil, and S-avoider fluid. Each monomer used in the present invention may be a single monomer or a mixture of monomers having different numbers of sulfonic atoms in the alkyl portion. In the alkyl part of (1) methacrylate and acrylate monomers and (2) hydroxyalkyl methacrylate and acrylate monomers, it is the performance characteristics of the polymer of the invention Important factor. That is to say, the average number (η) of nitrate atoms (Cn) in the side chain alkyl and hydroxyalkyl groups of the acrylate or methacrylate backbone polymer, you can get the maximum viscosity index after proper flooding. And maintain the oil solubility of polymer additives in both new and old oils (oil solubilty), where the additives are dispersed as a slurry_Generally, if the average number Cn is less than about 7, the polymer is made It will have poor solubility in the base oil, and the additives cannot be fully used as the improvement index of the partial failure index. Conversely, if the average number Cn is significantly greater than about 12, it can be found that it has poor low temperature flow properties. " Low-snack " one feed, here means a temperature below about one. Therefore, the average number of sulfon atoms in the alkyl group of acrylate or methacrylate monomers used in the preparation of the molecular additive should be between about 7 and about 12, and between about 8 and about 10 More ideal. If the monomers for use are all acrylates or almost all acrylates, the sulfonogen in the alkyl group of the side bond of the backbone polymer < please read the rule on the back: 11- ^ Item re-item. &Quot; page)

x ----- I II --- order — I This paper is again applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) 81.9.20,000 204355

Λ () BG Central Standards Bureau of the Ministry of Economic Affairs t «Industry and Consumer Cooperatives Printed V. Description of Invention (5) The average number of children will change slightly. This average number of atoms makes it a commendable methacrylic sugar backbone polymer. The solubility parameters are consistent. It is generally known or understood by the industry to pursue these solubility parameters. Ideally, the monomer (1) is selected from (Ci-C ·.) Alkyl methacrylate and (C t-C,.) Alkyl acrylate; and the monomer (2) is from hydroxyl group. (C, -Ce) alkyl methacrylate and hydroxy (C ·-%) alkyl acrylate sugar. The alkyl portion of each monomer can be linear or branched. Among them, alkyl methacrylate and hydroxyalkyl methacrylate are preferred. In order to achieve balance in the improvement of viscosity index, good dispersibility, and low rent performance and other well-known performance persistence, a mixture of alkyl methacrylate and alkyl acrylate can be used. Therefore, in an example of the present invention, the monomer (1) usually contains (i) 0 to about 40% of alkyl methacrylic acid (vinegar or alkyl acrylate, wherein the alkyl group is with a 1 Those with up to 6 atoms, and their mixtures, (ii) about 30 to about 90% of alkyl methacrylates or alkyl acrylates, of which the alkyl group is clamped with 7 to 15 sulfonate , And their mixtures, and (Hi) 〇 to about 40% of alkyl methacrylates or alkyl acrylates, wherein the alkyl group is clamped with 16 to 24 sulfon atoms, and their mixtures; The monomer (2) contains less than 10% to about 2% of hydroxyalkyl methacrylate or hydroxyalkyl acrylate • The alkyl group contains 2 to 6 atoms and is dumped or more Replaced by multiple dysprosium hydroxyl groups. All the above percentages refer to weight, and the basis is based on the weight of the polymer, and the europium combination of (i), (ii), (iii), and (2) is equal to 100% by weight The polymer. In the polymer, the amount of (i) is preferably between 0 and about 25%, and the amount of (ii) is preferably between about 45 and about 85% ------... ---- 1 .---- · ---- {----- install--1 ---- order ------ line (I (please first. ?? 背 曲 之 注 * 事 ## 功Shi Dongwen) This paper is again applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) 81.9.20,000 ΑΓ) ΒΓ, 204355 5. Description of the invention (6); and between about 50 to about 60% is more ideal; (iii) the amount of pseudo is between about 5 to about 3 5%, and between about 25 to 35% is more ideal; and (2) the amount of It is preferably between about 4 to about 8%, and more preferably between about 5 to about 6%. Examples of the scaffold (1), that is, alkyl methacrylate or alkyl propionic acid, acid Ester, and the alkyl group is one with 1 to 6 atoms, also known as "lower" (lovr-cut) alkyl methacrylate or alkyl acrylate, including: methacrylic acid ( MHA), methyl and ethyl acrylate, propyl methacrylate, butyl methacrylate (BMA) and butyl acrylate (BA), isobutyl methacrylate (IBMA), hexyl methacrylate and Chenji Ester, hexyl acrylate, and their mixtures. Ideal lower alkyl methacrylic acid It is methyl methacrylate and butyl methacrylate. The monomer (1) printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is exemplified as alkyl methacrylate or alkyl acrylate and the alkyl group is Those with 7 to 15 atoms, also known as "intermediate w (Bid-cut) alkyl methacrylate or alkyl acrylate, including: 2-ethylhexyl acrylate (EHA), Isooctyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (IDMA, based on a mixture of branched (Cm) alkyl isomers), methacrylic acid Undecyl ester, dodecyl methacrylate (also known as lauryl methacrylate), tridecyl methacrylate, myristyl methacrylate (also known as myristyl methacrylate) , Pentadecyl methacrylate, and their mixtures. Other interesting users include: Dodecyl Methacrylate-Pentadecyl Ester (DPMA), which is dodecyl methacrylate, tridecyl ester, tetradecyl ester, and pentadecane Ester Zhizhi and 81.9.20,000 This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 204355 A6 ΒΓ > Central Standard of the Ministry of Economic Affairs and printed by the Hgong Consumer Cooperative Society V. Description of invention (7) A mixture of isobaric silver carp; and lauryl methacrylate-myristyl (LMA), which is a mixture of dodecyl methacrylate and myristyl methacrylate. Ideal intermediate alkyl methacrylates are lauryl methacrylate-myristyl and isodecyl methacrylate. Exemplary monomers (1), that is, alkyl methacrylates or alkyl acrylates and the alkyl group is those with 16 to 24 sulfur atoms, also known as high-cut alkyl methyl Acrylate or alkyl acrylate, including: cetyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, cosyl lethacrylate, methacrylic acid Eicosanyl esters, and their mixtures. Others can also be used, including: cetyl methacrylate-eicosyl (CEMA), which are cetyl methacrylate, octadecyl methacrylate, cosyl methacrylate, and methyl A mixture of eicosyl acrylate; and cetyl methacrylate-stearyl methacrylate (SMA), which is a mixture of cetyl methacrylate and octadecyl methacrylate. The ideal high alkylidene methacrylates are cetyl methacrylate-eicosyl methacrylate and cetyl methacrylate-stearyl methacrylate. The above intermediate and off-grade alkyl methacrylates are typical alkyl acrylate sugar monomers. They are usually prepared by standard esterification steps. Among them, industrial-grade long-chain aliphatic enzymes are used as raw materials. The leaven you supply is a mixture of different fermented leavens, which carry 10 to 15 or 16 to 20 sulfo atoms in the alkyl group. Therefore, for the purpose of cost-inventing, alkyl methacrylic acid _ not only refers to the listed «other alkyl methacrylate products, but also refers to the majority of the alkyl methacrylate and use * The listed treats (^ tw ^ Notes to be filled on the back of this page to fill out this page) This paper is once again universal Chinese National Standards (CNS> A 4 specifications (210 X 297 public goods) 81.9.20,000 ΛΓ > ΒΓ) 2 〇435δ V. Description of the invention (8) When the mixture D formed by special alkyl methacrylates uses some commercially available leaven for the production of diacrylate and methacrylic acid, it will result in the formation of the above-mentioned LMA, DPMA, SMA, and CEMA monomer mixture. Exemplary monomers (2) are some alkyl methacrylate and alkyl acrylate monomers with one or more hydroxy groups in the alkyl part, especially the hydroxyl group is located at / 3 of the alkyl group -Position (2nd position). The ideal hydroxyalkyl methacrylate and hydroxyalkyl acrylate monomers, such as those in which the substituted alkyl is (C ·-(:) alkyl, but in linear or branched form. The hydroxyalkyl methacrylate and hydroxyalkyl acrylate monomers suitable for use in the present invention include: 2-hydroxyetheyl «ethac-rylate (HEMA), 2-hydroxyluan ethyl acrylate, 2-Hydroxypropyl methacrylate, 1-methyl-2-hydroxy-ethyl methacrylate, 2-hydroxyethyl acrylate, 1-methyl-2-hydroxy acrylate, 2-hydroxymethacrylate Ester and 2-hydroxyacrylic acid ester. The ideal hydroxyalkyl methacrylate and hydroxyalkyl acrylic monomers are HEMA, methyl-2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate The mixture of the latter two monomers is generally called "hydroxypropyl methacrylate" (HPAH), which is a more ideal hydroxyalkyl methacrylate, and each component of HPMA The same is true among the applicable hydroxyalkyl methacrylate and hydroxyalkyl acrylate monomers. Yu is a monomer that is substantially free of impurities and impurities of crosslinker precursors or crosslinker precursors, and they are the ones that accompany the method of making monomers. "Crosslinker" The term pseudo refers to any multi-functional substance that can cause the polymer to be branched, such as B-1 0- This paper standard is universal Chinese National Standard (CNS) A 4 specifications (210 X 297 public goods) < 膙 1 Reading ¾ back Of; .t * f-Jfi * «script ΪΙ) X ------------- f ----- installed ------- order ------ line { Printed 81.9.20,000 A6 ΒΓ, 2Q4S55 by the Hgong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) Ethylene glycol diaethacrylate. The presence of these cross-linking agent substances will reduce the properties of the various additives of the present invention due to the formation of condensate and related problems. The ideal hydroxyalkyl methacrylates and hydroxyalkyl acrylates contain less than about 0.5%, more ideally less than about 0.2%, and most ideally 0.1% by weight or less It is the best polymer for the two precursors or the cross-linking precursor substance β. The monomer (1) contains the following three monomers, that is, the body (i) 傜 苗 from methacrylate methylmethacrylate, methyl One or more monomers in butyl acrylate and isobutyl methacrylate, the monomer (ii) is derived from 2-ethylhexyl methacrylate, isodecyl methacrylate , Dodecyl methacrylate-pentadecyl methacrylate, and one or more monomers of lauryl methacrylate-myristyl ester, monomer (iii) Limium from cetyl methacrylate- One or more monomers of stearyl amide and cetyl-eicosanyl methacrylate; and monomer (2) is from 2-hydroxyethyl methacrylate. 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl-2-hydroxyethyl acrylate, 2-hydroxymethyl One or more monomers of butyl acrylate and butyl 2-hydroxyacrylate. The ideal polymer is the monomers (1) used, which are about 10¾ of methyl methacrylate, about 55% of isodecyl methacrylate, and about 30% of cetyl methacrylate. -Stearyl acetyl ester or cetyl methacrylate-eicosanyl ester, and the monomer (2) used is assumed to be about 5% of 2-hydroxymethacrylate and 1-methyl-2 -A mixture of ethyl hydroxymethacrylate. ------- Π-_ ____ This paper scale is applicable to 80 standard (CNS) A4 specifications (210 X 297 mm) 81.9.20 000 ------- * ---- \ Bu ------ ^ 丨 {----- 装 -------- iT ------ 线 f-(Please note the matters on the back of the first ## write this page) Ministry of Economic Affairs Printed by the Central Standard Residence tH Industrial and Consumer Cooperative

A (i BG 204355 V. Description of the invention (10) (please refrain from it first? Write down this page before writing this page) Another ideal polymer is the monomer (1) which contains about 20% Butyl methacrylate or isobutyl accounts for about 45% of isodecyl methacrylate, and about 30% of hexadecyl methacrylate-stearyl B methacrylate or cetyl methacrylate-eicosane Ester, and the monomer (2) is about 5% of a mixture of 2-hydroxymethacrylate and propan-2-methyl-2-hydroxymethacrylate. Another ideal polymer is The monomer (1) contains about 15% of butyl methacrylate or isobutyl methacrylate and about 80% of lauryl methacrylate or dodecyl methacrylate- + pentane vinegar. The body (2) is about 5% of a mixture of 2-hydroxymethacrylate and 1-methyl-2-hydroxyethylacrylate. Another ideal polymer is The monomer (1) contains about 5 to about 10¾ of methyl methacrylate, about 85 to about 90% of lauryl methacrylate-myristyl, Isodecyl methacrylate, or dodecyl-pentadecanyl methacrylate, and cetyl methacrylate-eicosyl methacrylate account for 0 to about 15%, and the monomer (2) is Approximately 5% of a mixture of propyl 2-hydroxymethacrylate and 1-methyl-2-hydroxyethyl methacrylate. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs for automatic liquid delivery A particularly desirable polymer composition is one in which the monomer (1) contains from 0 to about 5% of methyl methacrylate and from about 80 to about 90% of lauryl methacrylate-meat bean 》 Sugar • And cetyl deer eicosyl methacrylate, which accounts for 0 to about 10% • The monomer (2) is a kind of 2-hydroxymethacrylate propionate and 1- It is a mixture of methyl-2-hydroxyethyl methacrylate. -12- 81.9.20,000 This paper is again applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm)

Α6 BG 20435ο V. Description of the invention (11) {Please clear the precautions on the back before writing this page) Another ideal polymer composition for automatic liquid delivery, which is the monomer (1) Contains 0 to about 20% butyl methacrylate, about 65 to about 90¾ lauryl methacrylate-myristyl, and 0 to about 10% cetyl methacrylate-di Decane ester, and monomer (2) is a mixture of 2-hydroxymethyl acrylate and 1-methyl-2-hydroxyethyl methacrylate, which accounts for about 5% of the total. Printed by the Staff Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, in addition to the average number (η) of atomic atoms (Cn) in the side chain alkyl groups and hydroxyalkyl groups of acrylate or methacrylate backbone polymers, methacrylate and The nature of the alkyl portion of the acrylate monomer is also an important factor. The performance of the polymer of the present invention is an important factor to be treated. For example, a mixture of (GC ·) alkyl methacrylate or acrylate, (CT-Cie) alkyl methacrylate or acrylate, and Ute-Ca4) alkyl methacrylate or acrylate can make They co-polymerized with hydroxyalkyl methacrylate, which resulted in an average number of polymer atoms in the alkyl side chain of about 9. At this time, a good balance can be obtained between the properties of the viscosity index and the solubility in the base oil; moreover, the alkyl methacrylate portion of the polymer is in the shape of a pan, and it will interact with the pan in the base oil The interaction between the qualitative and the ingredients makes the low-temperature properties improve, that is, stickiness, low-temperature pumpability, and low-temperature cranking engine startup (lH-cranking engine startup). S — In the aspect, if a single (C1D) or (Cie) alkyl methacrylate monomer and hydroxyalkyl methacrylic acid are copolymerized so that the average number of nitrate atoms on the alkyl side reaches approximately 9, then The formed polymer addition_ has satisfactory oil solubility, but the ability to interact with the pan is quite limited. Even though the Cn values of the two types of polymers are similar, the low temperature properties at this time are not good, such as -1 3 -81.9.20,000 This paper scale is applicable to Chinese national standards (CNS> A4 specifications (210 X 297 mm)

20435S Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (12) For example, due to the accumulation of viscosity, the pumpability (puBpability) is poor. Therefore, in order to obtain a good low-rent performance and to maintain a good balance between the viscosity index properties and the solubility in the base oil, it is desirable to make the monomer (1) part contains about 5 to about 40, ideal The situation is about 5 to about 35, and the more ideal shape is about 25 to about 35 weight alkyl methacrylate and (cie-CM) alkyl acrylate, and the alkyl portion of the Between (Cie-C, D). Low temperature performance like the viscosity under high shear and low shear conditions. For example, the low-temperature cranking startability of an engine measured with CCS (Cold-Cranking SiniulatDr) viscosity is related to the viscosity under high-shear conditions. On the other hand, the oil pumpability at low temperatures measured by a mini-rotary viscometer (MR V) is related to the viscosity under low shear conditions. As the higher alkyl methacrylate and acrylate images are in the shape of a pan, it can be used as a pour point dispersant to change the structure or morphology (aorpho logy) of the pan in the base oil at low temperature. The amount of higher alkyl methacrylate or acrylate depends on the properties of the higher alkyl methacrylate or acrylate, base oil, and desired low temperature properties. In general, the larger the number of atoms in the alkyl portion, the more monomers will be, and the less the use of such monomers. Furthermore, because some of the degraded alkyl methacrylates are waxy, using too much Dong Di will congeal the base oil (congealing) and lose low temperature fluidity. The high-, medium-, and low-alkyl methacrylates «appropriate ratio depends on the base oil used in the formulation and the desired performance level. Once the optimum of high-cut Bonoaer -14- (please read 51 " 背 而 之 注 & event # 蝌 写 衣 页) • τ 'Λ 丨 installed ------- order ------ I. This paper is again applicable to China National Standard (CNS) Grade A (210 X 297 mm) 81.9.20,000 2〇435〇 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (13) After the chemical use is determined, the intermediate and lower alkyl monomers can be adjusted to obtain the most appropriate viscosity index and solubility. The balanced formula will have alkyl S (Cn) between about 8 and about 10. Therefore, when the various monomers in the ideal range include hydroxyalkyl methacrylate and acrylate monomers, and the average number of sulfon atoms of the side chain alkyl groups in the backbone polymer is also in the ideal range, add this After the invention of the polymer, the engine oil formulation can have the same viscosity and low flow properties as the oil with a lower full viscosity grode. Buttocks, SAE 10W-30 oil can meet the pumpability of SAE 5W-30 oil. Within these ideal limits, the polymers of the present invention can also provide lower CCS viscosity while maintaining good low temperature pumpability of the lubricating oil (measured by MRV), thus allowing the use of higher viscosity base oils. Therefore, the polymer of the present invention allows the further use of some base oils in blended oils, resulting in lower cost, less fuel consumption and maintaining a cleaner engine, because the ratio of some heavier base oils Lighter base oils are less volatile and can reduce the problem of piston deposit formation at high operating temperatures, especially in diesel engines. In order to make the polymer of the present invention have good polymer solubility, viscosity index, dispersibility and low temperature properties (such as pour point and low temperature shaking engine starting performance), low (C ^ -h) alkyl methacrylate, such as A Based on methyl acrylate, its service level can be between 0 and about 25%, and generally it is between about 5 and about 15% by weight of the polymer. The polymer solubility (polyeer solubility) pseudo-refers to the properties of more hydrophilic or thumping monomers, for example, it has a low content of alkyl (C, -Ca) in the alkyl part, which makes the polymerization -15- (please read first Remarks on the back & matters, and two copies of this article) This paper is in accordance with the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) 81.9 · 20,000 Α6 Β0 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (14) It is more insoluble in base oil than some polymers formed by monomers with higher hydrophobicity, such as alkyl sulfide with high sulfonate content (C4 or more). Therefore, if more than about 10% of methyl methacrylate is added to some polymers, the future depends on the level of use of other polar monomers (ie, hydroxyalkyl methacrylate), which is The solubility in some base oils may not be sufficient to allow the additives to fully perform their function as dispersibility and viscosity index improvers. On the other hand, if lower (c4-c ·) alkyl methacrylates are used, such as butyl methacrylate or isobutyl methacrylate, the amount of these monomers may range from 0 to about 40 weight %, The ideal situation is between 20-3 5%, so that the above properties, including the solubility of the base oil, get the most appropriate balance. The weight average molecular weight (Mw) of the polymer of the present invention is not very important. It must be sufficient for the lubricant to have desired properties. When the weight average molecular fi of the polymer increases, it will become a more effective crowding agent; however, it will undergo mechanical degradation in some special applications. Therefore, Hw mainly depends on the efficiency, cost, and application category of the increase in ownership. Generally, the polymer lubricating oil of the present invention is added with a Mw pseudo-range between about 100, 100,000 and about 1, 0 0 0, 0 0 0 (measured by GPC permeation chromatography, GPC measurement, use Poly (alkyl methacrylate) broadcast standard, the ideal situation is to make Mw between about 300,000 to about 800,000 to meet the special applications of oil products, that is for Used for engine oil and automatic transmission liquid. Those with a weight-average molecular weight M of about 100,000 to about 3,000, 0.001 are suitable for hydraulic fluids, gear oils, etc. Those who are familiar with this technology can appreciate the points referred to in the present invention " 16- ------ 3 ---- 1-l · ---- ^ ----- installed- ------ 1T ------ gas < please read the introduction and the note and the article will be written and congratulated) This paper size is applicable to the Chinese National Standard (CNS) A 4 specifications (2i0 X 290) %) 81.9.20,000 Α6 ΒΓ) Fifth, the description of the invention (15) There are two components of the quantum system and its support method. For example, the molecular M determined by GPC analysis will produce different values than the molecular director calculated by other methods. It is not for the molecular * itself that the handling characteristics and performance of the molecular additive (shear stability and thickening force under use conditions) are important. In general, shear stability is inversely proportional to molecular weight, and the use of additives with very low shear stability can make more polymers obtain a good effect of increasing crowd. The shear stability index (SSI) can be directly related to the polymer molecule Licheng W, which is used to calculate the percentage of viscosity loss caused by the addition of isolated molecules due to shear. It can be based on ASTM D-2603-91 (by the United States) Printed by the American Society for T esting and M ateria 1 s). Generally, polymers with higher molecular weights will have a greater degree of decrease in molecule Λ under high-normal conditions. Therefore, polymers with larger molecular weights will also have larger SSI values. The SSI range of the polymer of the present invention is between about 10 and about 75% for low molecular weight Dong polymers, and preferably between about 10 and about 25%. In general, it is between about 30 to about 50% of W. To obtain the desired SSI value, the polymer can be sheared by changing the reaction conditions or the product of known molecular weight. The Ministry of Economic Affairs, Central Bureau of Standards, Staff and Consumers Cooperative printed the representative examples of shear stability observed by the weight-average molecular weight (Kw) of different oil additives. These include: Fu Tong ’s poly (methacrylate) additives, For those with 1 3 0, 0 0 0, 4 9 0, 0 0 0, and 880,000, the SSI values (210T1) obtained from the oil formula for the 2000 mile road shear test were 0, 5 and 20%; ATF (Automatic Transmission) with -17- 81.9.20,000 (" " Please read the note on the back & rewrite this item π) for installation. 丨 The standard of this paper is applicable to the China Standard (CNS) A 4 specifications (210 X 297 mm) A6 B6 V. Description of the invention (16) Fang Zuo 20, 0 0 0 miles off speed road test, its 331 value (210 Bian) are 0, 35, and 50%; and Liquid for 100 hours ASTM D-2882-90 pump test, the SSI value of 100T) were 18, 68, and 76% (Effect of Viscosity Index Inprover on In-Service V iscosityof H ydrau 1 ic F 1 uids, R . J. K opko and R · L. Staabaugh, Fuel and Lubricants Meeting, Houston, Texas, June 3-5, 1975, Society of Autoaofive Engineers). The oil-soluble polymer of the present invention printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs can have a polydispersity index (polydispersity index) between 1.5 and about 15, and between 2 and 2. It is suitable to be between about 4. The multi-point failure index (Mw / Mn) is like a measure of the narrowness of the molecular weight distribution. If the polymer separately encounters coibination and disproportionation, it will involve _termination (chain ternination), which will have a minimum value of 1.5 and 2.0, and a larger value means that the distribution range gradually increases. The ideal situation is to make the molecular weight distribution as small as possible, but it is often limited by the manufacturing method. A narrow atomic weight distribution is achieved (Low Mw / Mn) several methods include the use of one or more of the following methods: anionic polymerization, continuous feed search tank reactor (CFSTR) technology, low conversion polymerization, temperature control during polymerization, etc., and polymerization Mechanical shearing (i.e. homogenization) of materials, etc. Preferably, the polymer of the present invention having a polydispersity index of 2 to about 4 is used because some polymers can The use of additives is more effective than the specification of engine oil viscosity, which means that compared to additives with a polydispersity index of about 10, the additives can be used by about 5 to 10% less than -1. 8-81.9.20,000 The size of the paper is in accordance with the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm) 5. Description of the invention (17) Λ (5 ΒΓι The central standard of the Ministry of Economic Affairs is printed by 100 OH base oil The viscosity rate is between about 9 to about 20 centipoises (ζΙΟΟΌ). Therefore, a completely effective polymer additive should be able to balance the shear stability and the capacity to increase the congestion at a low dosage level and produce without detracting from other characteristics (such as sub-dare) Low-rent liquidity. In addition, it also shows chemical neutrality for the seals and charm rings made of polymer. Generally speaking, the performance properties of engine oil, automatic liquid delivery formula, etc. can only be achieved by using two, three, or more different additives, that is, using different dispersion_, viscosity index improvers , And dumping inhibitors, etc., are mixed to make them together. The additive of the present invention can be used to obtain a combination of various performance properties through a single polymer. The polymer of the present invention is prepared by mixing monomers (1) and (2) in the presence of polymerization initiator I, diluted two, or together with a silver carp transfer agent. Inverse S can be carried out with stirring in the atmosphere of emotion. The reaction temperature is about 60 to 140 °, and preferably 115 to 125¾. Usually, batch reaction will produce exotherm, and reach the polymerization temperature of 115-120 t :. The reaction usually takes about 4 to 10 hours, or continues until it reaches the desired degree of polymerization. As those familiar with this technology know, the time and temperature of the reaction depends on the enlightenment used, and can be changed accordingly. The enlightening agent used in this polymerization reaction is any conventional compound capable of generating free radicals, such as peroxy compounds, peroxy compounds, and even cyanogen compounds, including: acetyl peroxide , Benzene acetylation meets gas, laurel acetylation gas, t-butyl peroxyisobutyrate (t-butyl peroxyisobutyrate), acetylation gas, cumene hydroperoxide (cumene hydroperoxide -19) -< Please read the notes on the back and then write this page) — Binding. Order. This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm) 81.9.20,000 V. Description of invention (18)), 1,1-bis (third butyl peroxy group) -3,3,5-trimethyl hexane, even bait bisisobutryl (a ζ 〇bisis 〇butyr ο nitri 1 e ), And t-butyl peroctoate. The concentration of the elicitor is usually between 0.025 and 1% by weight of the total weight of the monomer, and 0.05 to 0.25% is preferred. The bond transfer agent can also be added to the polymerization reactor to control the molecular weight of the polymer. The ideal silver carp transfer agent is alkyl aercaptan (alkyl aercaptan), such as lauryl (dodecyl) sulfur fermentation, and the chain transfer agent is used at a concentration of 0 to about 0.5 weight stoneware. Commonly used in the dilution of polymerization reaction moles, including: aromatics such as benzene, toluene, xylene; aromatic naphtha; aromatic cyanide (aromatic naphtha); cyanide hydrocarbons, such as ethylene dichloride; esters, such as ethyl propionate_ Or butyl acetate; and petroleum oil (petroleun oil) or synthetic lubricant. After the polymerization reaction, the polymer solution formed has a polymer content ranging from about 50 to 95 weight stone. After separation, the polymer can be used directly in mineral or synthetic base oil, or the polymer and dilute conversion agent can be dissolved and used in a shrinking form. If it is used in a concentrated form, the polymer concentration can be adjusted to the desired level by adding other diluents (paraffinic base oil). In the concentrate, the ideal concentration of the polymer is between 30 and 70% by weight. If the flag body is directly incorporated into the foot slip base oil, the more ideal thinner at this time is any kind of «material oil • Biru 100-150 neutral oil (100N or 150N oil), which is the final lubricating base oil. Can be compatible. When the polymer of the present invention is added to the lubricating base oil as an alternative, such as automatic liquid delivery, hydraulic fluid, and engine oil, whether the polymer is pure polymer or concentrated, the final polymer in the lubricating base oil For the supply of between -20-This paper is again in accordance with the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm > (please first 1¾) ¾ Note & matters on the back then fill out this page). Dedication · Printed by the Ministry of Economic Affairs, Central Bureau of Standards and Staff Consumer Cooperatives 81.9.20,000 Printed by the Ministry of Economic Affairs, Central Bureau of Standards, Negative Labor Consumer Cooperatives 5. Invention description (19) Approximately 0.5 to 15% by weight, and approximately 1 to 8% It is more ideal to ask, depending on the needs of special application occasions. For example, in the oil, automatic traditional and anti-avoider liquids, the pseudo-range is between about 1.5 and about 5%, and the oil for special purposes And in hydraulic fluids, it can be between 10% and 15%. The lubricating base oil can be exact oils (paraffins or naphthenes) or synthetics (the concentration of polyolefins depends on the desired viscosity of the lubricating oil) Depends on the nature and the shear strength of the lotus ; In general, if a low molecular weight polymer is used, the blend can achieve a thickening effect of Didang at a relatively high degree, and if a high molecular weight polymer is used, a lower amount can be used in the oil. Pan Du. The polymer of the present invention can be evaluated according to various performance test methods commonly used in lubricating oils. H is discussed later. For engine oils containing viscosity index improvers, the viscosity index (VI) value is usually pseudo-between 120 Between about 230, depending on the blend specification, you should ideally use a value above about 140. The higher the value, the smaller the change in viscosity when the curvature increases or decreases. The viscosity index improvement of the present invention Viscosity index value of the composition that can be lifted off (Example 4), maintaining good dispersion power (Example 5), good low-temperature shaking engine startability (Example 7), and made of gas-containing polymers The sealing material has good chemical neutrality (Example 6). The lubricating oil additive of the present invention can also be evaluated by its engine cleanliness (eagine cleanliness) in the Sequence UE test. Dong Additive The sludge dispersant under the rent and medium temperature operating conditions is exceptional, and according to the ASTM Research Report-21- This paper scale is applicable to the Chinese Standard (CNS) A 4 specification (210 X 297 mm) 81.9 .20,000 (please read first-'. *.? Note on the back * Please save this page to write this page) — Binding · Order. Centralized Bureau of Ministry of Economic Affairs Employee's Consumer Cooperation Du Printed 5. Description of Invention (20)

No. D-2: The conditions described in 1002 were carried out. Engine parts are evaluated and evaluated at the end of the 12-day test period. The cleanliness is rated according to the Coordinating Research Council (CRC) review criteria. The value 10 represents the cleanest engine; general sludge (average sludge) and shake The armature (rocker ar · cover, RAC) sludge has a visual value of greater than 9.00 and 7.00. The composition of the present invention is also fluorinated with "fluorine polymer (fluoroeUstoaer)-" Compatibility test. This test (engine seal H compatibility test, Example 6) You use If to estimate the degree of compatibility between the lubricating oil additive of the present invention and the materials used for engine seal H, ϋ ring, etc. ). During the test, the seal H or gasket material was immersed in the liquid containing the lubricating oil addition test sample, and the elongation standby (percent elongation at break, or% ELB) was measured after 7 days. The relative change value of% ELB is between 0 and 15%, which represents a neutral condition, that is, the engine seal has good compatibility. The composition of the present invention also depends on the method used to measure the viscosity performance at low temperature, low shear rate, and high shear rate, that is, according to the SAE J300 eaves oil viscosity classification (SAEJ 3 0 0 E ngine 0 i 1 V isc 〇 sity C 1 assificati η, January 1991). Under these conditions, the viscosity of the formulated oil should be low enough to allow the engine to shake at a sufficient speed when starting, and to properly lubricate all engine parts. The cold-cranking siDulator (CCS) test is used to evaluate the apparent viscosity of oil under the most difficult conditions of engine shaking and starting. It is based on ASTM D-5293 -22- (Please read the phonetic notation first? Matters before ^ write this page) 丨 Install _ Order. Pro! This paper is applicable to the Chinese National Standard (CNS) Grade 4 (210 X 297 mm) 81.9.20,000 V. Description of the invention (21) < Please t w -'-'- v Please pay attention to the matters on the back to fill in this ranunculus ) -92 The steps described were carried out. For example, the CCS viscosity specification for SAE 5W-30 grade oil is 35 poise at 25 t: hour, and many viscosity index improvers currently on the market are difficult to meet this requirement. Mini-rotary viscometer ("ini-rotary viscoieter", MRV) has been used to measure low-temperature and low-shear performance at engine start. The MRV test (Example 8) confirms the pumpability of the oil, that is, the oil must be able to flow adequately, and after the engine is started, it can be pumped to all engine parts to provide proper lubrication. The improved dispersive viscosity index of the present invention, after being formulated with many different types of base oils, can provide good low temperature performance. The following examples are intended to illustrate the present invention and are not intended to limit the scope of the invention. The scope of the invention is limited to those described in the application section. Unless otherwise noted, all ratios and percentages of apricots refer to weight, and all pharmaceuticals refer to those with good commercial quality. Examples 1 to 3 illustrate the synthetic method for manufacturing the polymer of the present invention, and examples 4 to 7 The performance data of the oil formulation containing the polymer of the present invention is exemplified. Example 1 Printed by 30.0 parts of cetyl methacrylate-eicosyl methacrylate (100% basis; 95% purity) and 55.0 parts of isodecyl methacrylate printed by β Industry and Consumers Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs 10 0% basis; 98% purity), 10.0 parts of methyl methacrylate, 5.0 parts of hydroxypropyl methacrylate, 0.06 parts of dodecyl sulfatase, and 0.10 parts of 1, 2 The tributylperoxy group) -3,3,5-trimethylhexene cracked into a monomer mixture. In addition, it is composed of 20.0 parts of the basic raw material of stone oil (100N oil) and 0.0 28 parts of 1,1-bis (the third butyl group) _3,3,5-trimethyl hexane. h β β 1 charg β). Then, the post-feed is injected into the IK-23- 81.9.20,000 paper, which is again in common use with the China Standard (CNS) A 4 specifications (210 X 297 public goods)

Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of invention (22) The anti-knife (kettle), which is equipped with a rent meter and Then »o» »atchTM, is used to control the pass, and install There is a water-cooled through-flow condenser with a nitrogen outlet, a stirrer, a ® gas inlet, and a dropping funnel to control the dropping amount of the monomer mixture. The contents of the flask were heated to 12QTC and maintained at this temperature. Along with this, the monomer mixture (100 parts) was added uniformly over 90 minutes, and if necessary, it was heated or cooled to maintain the polymerization temperature between 115-120t :. After the monomer feed is added for 20 minutes, add the first batch of enlightenment added in three times, each containing 0.10 parts of 1,1-bis (third butyl gas group) -3,3, A composition formed by dissolving 5-trimethyl hexane in 10.0 parts of paraffinic base oil. The remaining two batches of heuristics are added every 20 minutes; S. Twenty minutes after the last batch of enlightenment was added, approximately 62 parts of hemp base oil was added to achieve a theoretical solid content of 50% polymer in the oil batch. During the pitching polymerization, the batch temperature is maintained between 115-120 * 0. Thirty minutes after adding the paraffin base oil, this batch of suspension will be in a uniform state, at which time it can be considered that the polymerization reaction has been completed. The conversion rate from monomer to polymer is about 95%, and the polymer has a typical stability index (SSI) of 45 (according to ASTM D- 2 6 0 3- 9 1). Example 2 The same procedure as in Example 1, except that the monomer mixture used contained 145 parts of cetyl-eicosanyl methacrylate, 225 parts of isodecyl methacrylate, and 99 parts of methacrylic acid Butyl ester, 24 parts of hydroxypropyl methacrylate, and 0.19 parts of p-cumyl perhydrogenated. After the feed is 106 parts of arsenic base oil, which contains 0.1 g of p-cumene-24-This paper scale is applicable to the National Four Standards (CNS> A 4 specifications (210 X 297 public goods) 81.9. 20,000 < ϊ > νl.Μίϊν Contrary note & matter and then add this page) • 1 ^ ----- I l · IIII order-20 V. Description of invention (23) Gas and 0.83 copies Of 25% tallow-third octyl phenyl dimethyl ammonium chloride (ta 11 ο η-t-〇cty 1-pheny 1 di η ethy 1 a ο niuch 1 〇ride, formulated with mixed butanase) . In addition, in a 30-minute interval, the enlightening agent was added three times, each of which added 0.13 parts of p-cumene, and each of them contained 0.83 parts of tallow and third octylbenzene. Dimethyl ammonium cyanide (mixed with butyrate), they are dissolved in 3.6 parts of paraffinic base oil. This batch contains 52% of the theoretical solids of the polymer. The conversion rate from monomer to polymer was about 93%, and the SSI value of the polymer was 73.3. Example 3 The monomer mixture is composed of 5.0 parts of methacrylic hexadecane-eicosyl ester (100% basis; 95% purity) and 85.0 parts of isodecyl methacrylate (100% basis; 95%) Purity), 5.0 parts of methyl methacrylate, 5.0 parts of hydroxypropyl methacrylate, 0.29 parts of dodecyl fermented yeast, 0.13 parts of tert-acid tributyl ester Hexyl hexanoic acid third butyl ester), and 4.9 parts of hemp base oil (100N oil) formulated. A part of the above monomer mixture (40%) is injected into the "gas blasting counter" device, which is equipped with a thermometer and TheriowatchTM to control the temperature, and a water-cooled blast condenser with a Λ gas outlet, Mixer, nitrogen inlet, and dropping funnel to drop the monomer mixture. The contents of the reactor are heated to 105 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs and allowed to radiate to 1301C before being controlled by cooling to maintain the temperature below 130¾; hungry at 1〇5 * 〇 After about 5 minutes, the exotherm has not started yet, then slowly heat the batch to 115-120 t; until the exotherm begins. During the exothermic period, when the temperature reaches 115 υ, the remaining monomer mixture is added evenly over 45 minutes. At this time, -25-81.9.20,000 ft scale of the general Chinese National Standard (CNS) A 4 specification ( 210 X 297 mm)% 〇4 dip 0 A6 B6 V. Description of the invention (M) By cooling, the heat release is controlled below 1251. Then, make Zudu maintain a sickle for another 30 minutes between 115-120 C. At this time, the first lozenge added in three times _-each containing 2.10 parts of tributyl caprylate and 9.8 parts of lOON oil-add it to the reactor, and then, make the tilting batch type in the same Maintain 30 points under the pass. The other two batches of enlightenment were added at 30 minutes each. After adding 30 minutes of the last potentiator, approximately 65 parts of 1QQN base oil was added to dilute the batch to contain approximately 50% polymer. Then, increase the batch sniper to 130Ό and maintain it for 30 minutes. Finally, the dilute polymer solution has an SSI value of 13.2. Example 4 Viscosity index (VI) You use to measure the effect of temperature changes on the viscosity of oil products. The viscosity index is a random value based on the calculation of lotus kinematic viscosity (centistoke) measured at 40 υ and 100 υ according to ASTM D-22 7 0-74. Table 1 lists some data of viscosity index improvement _ being formulated into two different base oils. Viscosity index improver (VII) composition Bu 2 represents a conventional poly (alkyl methacrylate) additive, which does not contain hydroxyalkyl methacrylate monomer; VII compositions 3-7 are all polymers of the present invention The representative, which contains poly (MMA / IDMA / CEKA / HPKA), the monomer content of phase is respectively 9-10 / 53-56 / 28-30 / 4-6 parts by weight. (Please read first-the notes on the back and then write this page) The paper printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is applicable to the Chinese In-House Standard (CNS) Grade 4 (210 X 297 public goods) 81.9 .20 * 000 A6 B6 V. Description of the invention (25) Table 1 Viscosity index value Printed by the Central Bureau of Standards of the Ministry of Economic Affairs Beigong Consumer Cooperatives Formula 1 Formula 2 VII 96 HPMA 100 · 40 ° VI 100 ° 40 ° VI 1 0 11.0 57.1 189 10 .6 54. 9 187 2 0 10.6 55.8 186 10 .3 5 3 .6 185 3 4 10.6 53.5 195 10 .2 50.5 197 4 4 10.9 54.4 19 7 10 .5 51.5 201 5 5 10.4 52.3 195 10 .1 49.5 197 6 5 10.7 50.7 211 10 .5 51.0 203 7 6 9.8 42.9 192 9 .5 46.0 199 Example 5 of the present invention "oil additives", its S Θ qu θ η ce VE VE (engine cleanliness) performance support The sludge values (S 1 udg value) shown in Table 3 0 and Table 2 are assumed to be rocker cover sludge and average sludge (the target values are greater than 7.0 and 9.0, respectively, while 1 0. 0 Represents the cleanest engine) 〇In each formula, M to S contains 4-8% of the oil additives under test, 8-10% Commercial DI package (DI pa ckage), and 82-87% of stone alpha base oil. Commercial DI bags usually contain anti-wear or anti-gasification ingredients, such as zinc dialkyl dithiophos (z in c dialkyl dithiophos P hat β); no ash content and two. For example, polyisobutene strip amber sleeping imine (polyrso buten e based succinii id β); cleaning agents, such as metal phenates or sulfonates; friction modifiers, such as sulfur-containing organic compounds; and defoamers, such as silicon liquids: -27- (please read the back of the first Note * -The matter will be «Write this page). Binding. —— Therefore, this paper is again in accordance with China National Standard (CNS) 4 specifications (210 X 297 mm) 81.9.20,000 2〇43δ〇

A6 BG V. Description of the invention (26) Hite cTM 993 sold by Ethyl Corporation in the United States and Aioco® Alpha-8004 sold by Meihua A · ογ Chemical Company. The tested oil additive contains poly (MMA / IDMA / CEMA / HPMA), and its relative monomer components are 9-10 / 5 3-5 6 / 28- 3 0/4 -8 parts by weight. The paraffinic base oil used is assumed to be Exxon 100N or 150N oil. The composition of the various test formulations is as follows: N 4.7% additive / 8% HitecTM 9 9 3 DI package / 87% 150N oil N 4.5% additive / 8% HitecTM 9 9 3 DI package / 87% 1501 (oil 0 6.9% Additives / 10% & 弸 〇〇〇 @ 典 -8004 01 pack / 83% 1001 »oil P 6.7% added PB / 10% Aioco® Α-β004 DI pack / 83% 100N oil Q 7.7% added剤 / 10% A-80 04 DI pack / 82% 100H oil R 6.5% added 剤 / 10% A * oc.® A-80 04 DI pack / 83% 100N oil S 4.4% added thin / 10% Aboco ® A-80 04 DI pack / 78% 100N oil / 7% 150N oil ^ _ι_ Sequence VE test (engine cleanliness)% HPMA sludge in formula additives (shake away (please note on the back of the wift * thing (0, write this page) • 丨 Install-Book i 丨 Line | Ministry of Economic Affairs Central Standard Residence Staff Consumer Cooperative Printed N 5% 9.3 / 9.4 N 5% 9.3 / 9. 1 0 5% 9.4 / 9.4 P 5% 9.2 / 9.4 Q 5% 9.3 / 9.6 R 4% 8. 1/8. 0 S 8% 9.4 / 9.5 -28- This paper is again applicable to the China Standard (CNS> A 4 specifications (210 X 297 mm) 81.9 .20,000 A6 _ B6 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of Invention (27) Example 6 The composition of the present invention, for It performs compatibility test with the gasified hydrocarbon polymer used in the engine seal H, 14 circles, etc.-to be the VitoηTM fluorocarbon one (engine seal H cap capacity test). This test is false in Under the conditions similar to ISO-37-1977 (Ε) Step R (developed by the Technical Committee of the International Organization for Standard (IS0 / TC / (45))), the S3A ® bell test was used The evaluation method is as follows: In the beaker, dip the three-point S3A dumbbell-shaped sample made of Viton ™ Fluoride (AK6) into the test solution, so that there are 80 test solutions in each test sample. Volume). The test solution contains 5% (by weight) of the dispersible viscosity index improver composition to be tested and a suitable detergent-inhibitor (DI) package, which is Then, the beaker is covered with a watch glass and placed in a forced-circulation air oven, maintaining a degree of 149-151 t; between, the sample is placed under the above conditions for 7 days, and then taken out , Let it cool, and then gently rinse with hexane to remove the residual test liquid. Then, the test specimen was air-dried, and the tensile strength and elongation characteristics (percent elongation at break or% ELB) were measured at a 5.75 inch / min elongation rate using a standard strain-strain measurement step. The elongation of the specimen is tested and compared with the elongation number of the untreated VitonTM elastomer sample. The results are listed in percentages. [% ELB treated 1% ELB untreated] -X 100 = 96ELB change [% ELB unprocessed] -29- (please read the back-to-back memorandum Λ-item to write this page) ”—install, order 4 Specifications (210 X 297 mm) 81.9.20,000 Λ6

BG 5. Description of the invention (28) The greater the negative value of% E L B, the greater the aggressiveness of the test liquid to V i t ο η ΤΜ < * elastomer sample. Under the above test conditions, if the test solution can reduce the original (untreated)% ELB value by more than 45% (in% ELB change = a 45% table), it can be considered as a strong attack on the sample Therefore, it is not compatible with Vito nTM fluoroelastomer engine seal H. The% ELB change value between 0 and 5% represents the neutral condition, so it is compatible with the engine seal. The% ELB change value is about -20% or lower, that is, the greater the negative value, the poorer the compatibility of the seal. % ELB test results will be greatly appreciated due to the method of use of the equipment, so with each new set of immersion test samples, a separate control result of the untreated sample is important. The lubricating oil additive of the present invention and Representative commercial cyanide oil products are added, the performance of the engine seal H compatibility test is shown in Table 3. Samples of VitonTM fluoroelastomers are immersed in the test solution containing the addition shown. The% ELB change value is pseudo-averaged by the average value of the three test samples in the test solution. In all cases, hold! The test solutions all contain 1.5% (U0ATM 2 6 7 (commercial detergent-inhibitor (DI) package supplied by Chevron Chemical Company *. A-reference substance: commercial poly (alkyl methacrylate sugar> Cyanide viscosity index improver

B-Comparative product: Commercial polyene smoke nitrogen-containing viscosity index improved HI composition C to H represents the polymer addition of the present invention _ (military body type and relative weight Λ part shown below) (ΜΜΑ stands for methyl Methyl acrylate, IDMA stands for isodecyl methyl propanoate, CEMA stands for hexadecyl methacrylate--30- This paper is again suitable for the B0 home standard (CNS) A 4 specification (210 X 297 mm ) (^ First read ^? Back of the page; ± 6 things ^ replanting. Drive this page) ·-installed · booked. Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 81.9.20,000 A6 B6 5. Description of the invention (29) Eicosanyl ester, LMA stands for lauryl methacrylate-myristyl, HPMA stands for hydroxypropyl methacrylate): C KMA / LMA / HEMA (/ 8/88/4) D HMA / IDMA / CEHA / HPMA ( 10/56/30/4) E MMA / IDMA / CEMA / HPMA (10/56/30/4) F HMA / IDMA / CEHA / HPMA (1 0/56/2 9/5) G MMA / IDMA / CEHA / HPMA (1 0/56/29/5) H MMA / IDMA / CEMA / HPMA (9/53/29/9) Table 3 Engine seal compatibility test additive type% ELB change value (please read the back first (Notes on I will write this page again) • Installed. Printed by R-Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs Α-Compare Contains m -47 Β-Control cyanogen -39 C \% HENA 0 DK% HPMA -2 Ε A96 HPMA -1 F 596 HPNA 3 G 596 HPMA -2 Η 9 96 HPMA -3 order. This paper is also suitable for Chinese and Western Η National Standard (CNS) A4 specifications (210 X 297 public goods) 81.9.20,000 V. Description of the invention (30) Example 7 Adding m to the lubricating oil of the present invention, its low-temperature shaking controller (ccs) μ撖 shown in Table 4. To be tested, add _ Nao base oil into a blend, which is a mixture of 22.4% (active) polymer additive, 11.4% DI package (LZ-7838 G supplied by Lubrizol) and a calculated amount of 100N oil Made. For example, if the polymer additive is present in 100N oil at 50% solids, then 4.48 parts of the polymer additive oil solution is mixed with 11.4 parts of 1 ^ -78386 and 84.12 parts of 100 »(oil phase, to Formulated into the final oil composition to be tested. The CCS viscosity specification of SAE 5W-30 鈒 oil is less than 35 poises (one 25t :). Table 4 Low temperature shaking chess simulator (CCS) test · Polymer addition composition CCS Viscosity (please read "Notes on the back ^ Matters first and then write this page") I install · order · «Printed by the Ministry of Economic Affairs of the Ministry of Economic Affairs and the Consumer Cooperative Society *% MNA% I DMA% CEMA% HPNA Po, -25t: 0 70 30 0 33.9 0 65 30 5 34.5 0 60 30 1 0 34.2 5 65 30 0 34.0 5 60 30 5 33.6 5 55 30 10 32.5 10 60 30 0 36.0 10 55 30 5 33.8 10 50 30 10 3 3.9 -3 2- This paper is also suitable for JB China National Standards (CNS) A 4 Λ (210 X 297 ϊ) 81.9.20,000 V. Description of the invention (31 A6 B6 Example 8 Mini Rotary Viscometer (MRV) table The viscosities are for two different test methods, which measure the oil pumpability of the low-fill engine after starting. A.STM D-3829-87 provides 0 to one The viscosity support method in the 4〇 Offi range and description of the standard MRV test step bran. ASTM D- 4 684-89 provides a viscosity measurement method in a temperature range of 1 5 ~ 3 0 t: TP- 1 MR V test step bran. Table 5 lists 2 sets of data of 5 different SAE 5W-30 oil formulations made from 5 different commercial base oils. One set uses commercial poly (alkyl methacrylic acid) Esters) cyanide viscosity index improvers, another group uses the poly (10 MMA / 55 IDMA / 30 CEMA / 5 HPMA) additive composition of the present invention. SAE J300 engine oil viscosity classification (January 1991) allows SAE According to ASTM D-4684-89 test procedure, the maximum viscosity of 5W-30 oil is 300 poises (one 301C). (Please read the note ¾ on the back and then fill out this page) Pack. Order · Central Standards Bureau of the Ministry of Hydrocarbon Economy Printed by the 8-Consumer Cooperative Society -33- Apparel paper size is applicable to the specifications of the Zhongjia «Zen (CNS) A 4 (210 X 297 mm) 81.9.20,000 5 'Invention Description (32) Table Λ6 B6 Viscosity Index Improver Spring onion

MRV pumpability (test viscosity, -30TC, source of the base oil TP-1 MRV Std HRV Commodity A 85.3 74.1 Commodity B 78.4 74.5 Commodity C 72.2 66.1 Commodity D 64.2 64. 2 Commodity E 73.1 71.2 Inventive A 86.9 67.8 The present invention B 75.7 73.5 The present invention C 62.8 63.5 The present invention D 60.4 57.2 The present invention E 6 1.2 63.7 (Ji first read the notice on the back? Please fill out this page before filling in) 丨 Installed. Thread · Line-Central Standard of the Ministry of Economic Affairs Printed by employee consumer cooperatives A—100N base oil after solvent extraction B—solvent extraction, 100N base oil after solvent dewaxing C cracking with added radon, 100N base oil after catalyst decalcification D—solvent thin extraction, Dissolved_100N base oil after dewaxing E-solvent extraction, post-treatment after adding raffinate, and 10 0N base oil after dewaxing after dissolving fff-34- This paper is also suitable for CNA Grade 4 specifications 210 X 297 mm) 81.9.20,000

Claims (1)

A8 B8 C8 D8 Ministry of Economic Affairs t Central Standards Bureau B Industrial and Consumer Cooperation Du Printed Patent Application No. 81107351 Amendment to apply for patent patent nursery 1. A polymer formed by the polymerization of monomers containing the following components: (1) 90 The reason for the replacement of 98% is from ({Μ · 4) alkyl methacrylate and (k-C24) alkyl acrylate monomer, and (2) less than 10 to 2% by weight selected from hydroxyl groups ( CB-Ce) monomers of alkyl acrylate and hydroxy (C, -C ·) alkyl acrylate; where the average number of sulfonic atoms in the alkyl group is pseudo between 7 and 12. 2. The polymer as claimed in Item 1 of the patent application, wherein 5 to 40% by weight of the total weight of the monomers (1) and (2) is (Cie-C, 4) alkyl methacrylic acid Ester, (ClB-Ca <) alkyl acrylate, or a mixture of these. 3. For example, the polymer of item 1 of the application category, where the average number of atoms in the alkyl group is between 8 and 10. 4. The polymer as claimed in item 3 of the patent scope, in which 5 to 35% by weight of the total weight of the monomers (1) and (2) is (C16-Ce.) Alkyl methacrylate , (Cie-Cae) alkyl acrylate, or a mixture of these. I ti n IT— IIIIII nnn nTf-l-eJ (please read the precautions on the back before f) This paper size is applicable to the national unitary national standard (CNS> A 4 specifications (210 X 297 mm) A8 B8 C8 D8 ( Please read the precautions on the i-face * traveler) 5. For example, the polymer of patent application item 4, wherein the monomer (2) is selected from 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate , 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxymethacrylate Butyl ester and butyl 2-hydroxyacrylate 6. The polymer according to item 1 of the patent application, in which the monomer (1) contains: (i) 0 to 40% by weight of alkyl methacrylate or alkyl Acrylic acid vinegar (wherein the alkyl group pseudo contains 1 to 6 primary atoms), and mixtures thereof; (ii) 30 to 90% by weight of alkyl methacrylate or alkyl acrylate (wherein the alkyl group It contains 7 to 15 atoms) and their mixture; (iii) 0 to 40% by weight of alkyl methacrylate or alkyl acrylate (where Alkyl pseudo contains 16 to 24 large atoms), and mixtures of them; the monomer (2) is printed by the Central Standards Bureau of the Ministry of Economic Affairs and the industrial and consumer cooperatives and the monomer (2) contains less than 10 to 2 wt% of hydroxyalkyl methyl Acrylic acid ester or hydroxyorthoyl acrylate, wherein the alkyl group contains 2 to 6 sulfonate atoms, once substituted by 1 M or more hydroxyl groups, and contains a mixture of them, and the monomer (2) contains Less than 0.5% by weight of the crosslinking agent or precursor material of the crosslinking agent, and the total amount of (i), (ii), (iii), and (2) is equal to 100% by weight of the polymer. This paper scale is suitable for China's Sleepy Family Standard (CNS) Grade A (210 X 297 mm) A8 C8 _ D8 Printed by ββ Industrial and Consumer Cooperative of Central Standards Bureau of the Ministry of Economic Affairs 7. If applying for the polymer in item 6 of the patent scope, And the polymer contains 0 to 25% (i), 45 to 85% (ii), 5 to 35% (iii), and 4 to 8% (2). 8. If applying for a patent The polymer of item 6, where the average number of nitrate atoms is between β and 10. 9. For the polymer of item 6 of the patent application, the monomer ( 2) Pseudo-selected from hydroxy (C »-%) alkyl methacrylate and containing less than 0.2% by weight of cross-linking or cross-linking agent precursor substances. 10. If applying for polymerization in item 9 of the scope Substances, wherein the weight-average molecular weight of the polymer is between 100,000 and 1,000, 000. 11. For example, if the polymer of patent application No. 10 is applied, the polymer contains 5 To 15% (i), 50 to 60% (ii), 25 to 35% (iii), and 5 to 6% (2). 12. For example, the polymer in item 10 of Shen Huan's patent standard has a polydispersity index between 1.5 and 15. 13. For example, if the polymer of patent application item 11 has a polydispersity index between 2 and 4. -3- (Please read the precautions on the back before proceeding); Binding · Ordering · This paper size is applicable to the national standard (CN'S) A 4 specifications (210 X 297 mm>% 04355 A8 B8 C8 D8 14. For example, the polymer in item 11 of the application scope, wherein the monomer (2) is selected from ethyl 2-hydroxymethacrylate. 2-hydroxyethyl acrylate, 2-hydroxymethacrylic acid propylene, and methyl-2- Those with ethyl hydroxymethacrylate, propyl 2-hydroxyacrylate, ethyl 1-methyl-2-hydroxyacrylate, butyl 2-hydroxymethacrylate and butyl 2-hydroxyacrylate 15. If the patent application is covered by The polymer of item 14, wherein the monomer (2) is generally a mixture of 2-hydroxymethacrylate and 1-methyl-2-hydroxymethylpropanoate, and contains less than 0.1% by weight The crosslinking agent or the precursor of the multilinker. 16. For example, the polymer of item 15 of the patent application, where (i) Meng is 10% methyl methacrylate and (ii) is pseudo 5 % Of isodecyl methacrylate, (iii) is assumed to account for 30% of cetyl methacrylate-arachidyl ester, and (2) has a content of 5%. (Please read first The precautions before proceeding f) — Installation, Ordering, " The Central Standards Bureau of the Ministry of Economic Affairs, Cooperative Printing and Manufacturing Co., Ltd. Du Printed 17. The polymer as claimed in item 11 of which the weight average molecular weight of the polymer is between 300,000 to 800,000, and in the alkyl part of the acrylic or methacrylic ester backbone polymer, the average number of atoms in the backbone is between 8 and 10. 18. If the scope of the patent application is item 6 Polymer, in which (i) one or more monomers pseudo-selected from methyl methacrylate, butyl methacrylate, and isobutyl methacrylate, (ii) from methacrylic acid Xin Brew _ 4 _ This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 public goods)% A8 B8 C8 D8 Printed by the Ministry of Economic Affairs Central Standards Bureau Negative Consumers Cooperative (2-ethylhexyl methacrylate), A One or more threshing monomers of isodecyl propionate, dodecyl methacrylate, pentadecyl methacrylate, and lauryl methacrylate-myristyl ester, (iii) methacrylic acid Cetyl ester-stearyl aldehyde ester, and cetyl methacrylate-eicosanyl ester One or more of the monomers, and (2) is selected from ethyl 2-hydroxymethacrylate, ethyl 2-hydroxyacrylate, propyl 2-hydroxymethacrylate, 1-methyl-2-hydroxymethyl One or more monomers of ethyl acrylate, 2-hydroxypropyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate, and 2-hydroxybutyl acrylate. 19. The polymer as claimed in item 18 of the patent application, wherein the weight-average molecular weight of the polymer is between 100,000 and 1,000.000. 20. For example, the polymer of claim 18, where (i) 10% methyl methacrylate, (ii) 55% isodecyl methacrylate, and (iii) 30% pseudo Of methacrylic acid + hexaalkyl ester-stearyl acrylate, and (2) is a 5% mixture of 2-hydroxymethacrylate and 1-methyl-2-hydroxyethylmethacrylate . 21. For example, the polymer in the 18th patent application country, where (i) is 20% butyl methacrylate, (ii) is 45% isodecyl methacrylate, and (iii) is pseudo 30% of the escape is from a monomer of cetyl methacrylate-stearyl methacrylate and cetyl methacrylate-eicosanyl ester, and (2) is 5% of 2-hydroxy Propyl methacrylate and 1-methyl-2-hydroxyl (please read the precautions on the back before re-packing. • Thread · This paper size is applicable to China Unitary Standards (CNS) A4 specifications (210 X 297 Public goods)% 〇4 printed on 5 A8 B8 C8 D8 Ministry of Economic Affairs Central Standards Bureau employee consumer cooperatives formed by the formation of a mixture of ethyl methacrylate. 22. Such as the application of the patent Fan Ji 18th of the polymer, of which (I) 20% isobutyl methacrylate, (ii) 45% isodecyl methacrylate, (iii) 30% hexadecyl methacrylate-stearin Acetate and hexadecyl methacrylate-eicosyl ester is a monomer, and (2) is 5% 2-propyl methacrylate and butyl methyl-2-hydroxymethacrylate Ester 23. The polymer as claimed in item 18 of the patent scope, where (i) is 15% of a monomer selected from the group consisting of butyl methacrylate and isobutyl methacrylate, (ii) pseudo It is 80% of lotus from a monomer of lauryl methacrylate-myristyl methacrylate and dodecyl methacrylate-pentadecanyl methacrylate, the amount of (iii) is 0 °, and (2) is like 5) A mixture of propyl 2-hydroxymethacrylate and 1-methyl-2-hydroxyethyl methacrylate. 24. The polymer according to item 18 of the patent application, where (i) is pseudo Is 5 to 10% of methyl methacrylate, (ii) is 85 to 90% selected from lauryl methacrylate-myristyl, isodecyl methacrylate, and dodecyl methacrylate_ A monomer in pentadecyl ester, (iii) is 0 to 5% hexadecyl methacryloyl methacrylate, and (2) is 5% pseudopropyl 2-hydroxymethacrylate It is a mixture of ester and 1-methyl-2-hydroxyethyl methacrylate. (Please read the precautions on the back before proceeding to $) Packing · Ordering · ik. This paper size is subject to the Central Park National Standard (CNS) 4 Specifications (210 X 297 mm) C8 D8 25.-A condensate for lubricating oil, containing 30 to 70% by weight of the patented scope of the first polymer. 26.-A shrinkage product for lubricating oils, containing 30 to 70% by weight of the polymer in claim 6 of the patent scope. 27. As claimed in the patent contraction No. 26 building shrinkage, where the polymer contains 10% methacrylic acid, 55% isodecyl methacrylate, i 30% hexadecane methacrylate Ester-Eicosyl Ester, 5% of the mixture formed by 2-hydroxymethacrylic acid propyl ester and dimethyl-2-hydroxymethacrylic acid ethyl ester, and its weight average molecular weight is between 100,000 and 1 · Those between ∣〇, 〇〇〇. (Please read the precautions on the back side first-install and order. Ά. Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs.