TWI293313B - Use of trioxepans in the process to make high-solid acrylic, styrenic, and ldpe-type resins - Google Patents

Description

1293313 A7 r~-B7 V. INSTRUCTION DESCRIPTION (彳) The present invention relates to dioxane or substituted anthracene, 2,4-trioxaheptane in the manufacture of acrylic acid (co)polymers High solids acrylic acid is preferred, styrene (co)polymer and/or ethylene (co)polymer (preferably low density polyethylene (LDPE)). High solids acrylic resins are commonly used in coating compositions. As far as environmental considerations are concerned, such coating compositions release less volatile material as little as possible. For this purpose, one or more solvents are preferably present as little as possible. In order to be able to handle the coating composition, particularly when spraying, basically, a low molecular weight acrylic resin composition is used to achieve a low solution viscosity. In practice, this means that a low molecular weight and narrow molecular weight propionate resin is generally used in the coating composition. An example of a method of preparing such a particular high solids coating resin is found in Estonia 96/2762. In this patent, it is proposed to use a specific cyclic ketone peroxygen. Similarly, w〇 〇〇/〇8〇72 proposes the use of a specific dialkyl compound to obtain a high solids acrylic resin. However, there is a need for alternative methods. In these alternative methods, it is preferred to use a peroxide which does not require dilution, so that a high amount of peroxide used does not introduce an undesired solvent, such as a solvent which changes the boiling point of the polymerization medium. In the case of producing a styrene resin, styrene is substantially (co)polymerized by a radical-initiated reaction. This radical is formed by a thermal program in which the stilbene styrene is first polymerized and then forms a group with the third monomer molecule. However, in order to improve reactor output and better control over the molecular weight of the polymerization, one or more complexes are typically used as a source of free radicals. Basically, it is sought to obtain a peroxide of a polymer having a relatively high molecular weight under similar conditions. Such peroxides can be used in larger amounts, which increase the polymerization rate and decrease -4 - This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1293313 A7 B7 V. Description of invention (2) Low tree The molecular weight of Yueluo». Therefore, the polymerization rate can be increased to produce the same polymerization f / as before, so that the reactor space-time yield is improved. Therefore, two g of oxides (peroxides with two peroxy linkages in one molecule) or peroxides that control the cross-linking reaction are considered to be useful or used in conventional styrene polymerization. . However, it is still desirable to have an alternative polymerization system that can further increase the reactor-to-time yield of the reactor. In order to avoid the undesired dyeing of the final resin, the amount of the diluent instead of the peroxide is preferably less than 25% by weight, less than 2% by weight, preferably less than the weight of the final blend. The weight is better. The peroxide blend is most preferably a substantially release agent, as the case may be. There is a need for a peroxide-initiated method for the diluent enthalpy and/or to make the use of peroxides more efficient. 〃本发(4)About the alternative method, in which a novel type of over-rolled material is used. In the inverse of the &, it was found that the molecular polymer yield of the obtained resin can be precisely controlled to be very high' and some methods form a colorless product. More particularly, the invention relates to a process wherein a monomer is polymerized using at least one dioxepane selected from formula I.

Rl\/〇_0 YCH3 R2XyCH3 • R3 (1), wherein R1 is independently selected from hydrogen and a substituted or unsubstituted hydrocarbon group, and the _ in the Ri 3 group may be linked to form a ring structure. In a better case.尺"To the paper scale, the standard for the rich (CNS) A4 specification (the tearing of the director) 1293313 A7 B7 V, invention description &

It is preferably selected from the group consisting of hydrogen and substituted or unsubstituted CrCw alkyl, C3-C2G cycloalkyl, C6-C2Q aryl, C7-C2G aryl and C7-C20 aryl, and these groups may include a straight or branched alkyl group; two of the R1 - 3 groups may be bonded to a (substituted) cycloalkyl group; one or more substituents selected from R1 ^ are each selected from the group consisting of a hydroxyl group and an alkoxy group. , linear or branched alkyl, straight or branched fluorenyl, aryloxy, halogen, ester, carboxyl, nitrile and decylamine. Preferably, ^1 and R3 are selected from lower alkyl groups such as methyl, ethyl and isopropyl, most preferably decyl and ethyl. R2 is selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclohexyl, phenyl, CH3C (C〇CH2-, c2h5oc(o)ch2 -, hoc(ch3)2ch2- and preferably wherein R4 is independently selected from any of the groups defined by R1.3. Another preferred product is

The first type of preferred method according to the present invention is a polymerization process for producing a high solids propionate resin. These methods are of the conventional type, such as: whole, suspension, emulsion or solution, but using at least one of the foregoing peroxides. It is preferred to use a solution polymerization reaction. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1293313 A7 B7 V. INSTRUCTION DESCRIPTION i) The second type of preferred polymerization method according to the present invention is a styrene polymerization method in which at least 40% by weight of the monomer is styrene. Such methods include the manufacture of copolymers (eg, polystyrene acrylonitrile (S AN)) and rubber-modified polymers (eg, methacrylate-butadiene-styrene (MBS)) and high impact polymerization. Styrene (HIPS) resins are known in the art. This process can be carried out by bulk, suspension, emulsion or solution polymerization methods known in the art. Among the second type of methods, the most preferred one is the overall polymerization method and or the suspension/wholesing (wherein the first part of the polymerization is carried out in suspension, after which the reaction mixture is moved to the bulk process). Of these best methods, polystyrene (GPPS) and/or HIPS are generally produced. A third preferred type of preferred polymerization process is a high pressure polymerization process in which ethylene is (co)polymerized at 500 to 4,000 bara. Among these methods, it is expected that the unique properties of the peroxide according to the present invention can make the polymerization extremely efficient and improve the molecular weight control of the resulting polyethylene or ethylene copolymer. Basically, all of these methods have a polymerization temperature of from ordinary temperature to 400 ° C, preferably from 40 to 350 ° C. It is also possible to carry out the polymerization reaction using a temperature change, for example, the initial polymerization temperature is lower than 100 ° C, and then the temperature is raised to higher than 100 ° C to complete the polymerization. In the solvent polymerization method, the polymerization is usually carried out at a reflux temperature of a solvent or a solvent mixture. These variations are known to those skilled in the art, and those skilled in the art have no difficulty in selecting reaction conditions depending on the particular polymerization process and the particular free radical polymerization initiator employed. However, this trioxepane is extremely suitable for high-temperature polymerization (especially at temperatures above 140 ° C, preferably above t65 ° C), at which the conventional peroxide is too reactive. To make the yield poor. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1293313 A7 ____ B7 V. Inventions &) Applicable to the manufacture of (co)monomers coated with resin based on high solids solvent An olefin-based or ethylenically unsaturated monomer such as a substituted or unsubstituted vinyl aromatic monomer, including styrene, jiang-methyl styrene, p-methyl styrene, and halogenated styrene; Vinylbenzene; ethyl hydrazine; ethylenically unsaturated carboxylic acid and derivatives thereof, such as: (meth)acrylic acid, (meth)acrylic acid, (meth)propionic acid, methoxyethyl acrylate, two Methylamino (mercapto) acrylate, isobutyl methacrylate, lauryl methacrylate, stearyl methacrylate, allyl methacrylate, 2-hydroxypropyl (decyl) acrylate, isobutylene amide ( Such as: (meth) butyl acrylate, 2-ethylhexyl (methyl) propionate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and glycidol Base (meth) acrylate, methyl (meth) acrylate (Methyl)ethyl acrylate; ethylenically unsaturated and decylamine, such as: cyanamide, isobutyl carbonitrile and acrylamide; substituted or unsubstituted ethylenically unsaturated monomers, such as : butyl sulphate, isoprene and succinimide; acetamyl esters such as vinyl acetate and acetal propionate and vinyl valerate; ethylenically unsaturated dicarboxylic acids and their derivatives, including mono- and diesters , anhydrides and quinone imines, such as: maleic anhydride, citraconic anhydride, narcanic acid nadine anhydride, itaconic acid, maleic acid, trans-butenedioic acid, aromatic Alkyl, alkyl and aralkyl citricin and cis-butane quinone imine; vinyl halides such as vinyl chloride and chloroacetam; acetophenones such as decyl vinyl ether and positive Butyl vinyl ether; anthracene hydrocarbons such as: ethyl hydrazine, isobutyl hydrazine and 4-methyl pentane; propyl propyl compounds, such as · (2) 晞 @ @ @, such as: diallyl phthalate , (di) allylic ester and tri-propyl propyl cyanurate. Monomer (eg: isobutyric acid, diethylaminoethyl methacrylate, dimethylaminoethyl) 8- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1293313 A7 ____B7 V. Description of invention έ ) methacrylate, tert-butylaminoethyl methacrylate, 3-(2 -Isobutylenoxyethyl)-2,2-spirocyclohexyloxypyrene (oxas〇iidene or the like) can be used to modify the bonding properties of the final coating composition. The system 'needs to contain chemically active groups High solids acrylic resin (usually base or rebel based) to promote molecular weight buildup and formation during the final crosslinking (curing) reaction when the coating composition is applied to the surface to be coated. Typically, melamine or isocyanate is used as the curing agent, and it is basically desirable that the high solid content acrylic resin has a warp content of from about 2 to about 7 wt%. To prepare a polymer having a hydroxyl group content of about 2 to 7% by weight, a sufficient amount of hydroxydecyl acrylate or methacrylate (usually, 20 to 40% by weight of the monomer composition) is used and/or a functional group is used. To the initiator in the resin. Therefore, it is preferred to use a trioxane having a hydroxyl group. However, other functional groups such as carboxylic acids can also be used. Examples of the pyridyl acrylate and isobutyl phthalate which can be used to prepare such a functional compound include 2-hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (methyl) propyl phthalate or the like. The amount of these functional (co)monomers depends on the type of initiator desired for the final resin and the type of initiator used, which is not a problem for those skilled in the art. Preferred comonomers which can be used to make high solids acrylic resins include: (meth) propyl methacrylate, (methyl) propyl methacrylate, ketone, butyl acrylate, Isobutyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, propyl (meth) acrylate, ketone acrylate Propyl ester, phenelzine, p-methyl styrene, (this paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1293313 A7

Methyl)acrylic acid and vinyl acetate. The comonomers which can be used in the conventional styrene polymerization process of the second preferred polymerization type are of the conventional type and include monomers (e.g., (mercapto) propyl phthalate, methyl (ethyl) propionate, propylene Nitrile, vinyl pyridine) and cross-linking comonomers (eg, monoethyl benzene and trimethyl propyl isocyanurate). As mentioned above, rubber is also present in the polymerization process, and styrene is grafted onto the rubber as in the method of producing HIPS, MBS and acrylonitrile-styrene-butadiene rubber (ABS) resins. A third preferred type of comonomer which can be used in the polymerization process is of the conventional type and includes alkenes (e.g., hexene and octene), acetal acetate, and acrylic acid. The amount of initiator used in any of these methods will vary depending on the temperature of the polymerization, the ability to remove the heat of polymerization, the type of monomer used, and the strength used. Usually, 引发1_25% by weight of the initiator based on the total weight of the monomers is used. It is preferred to use 0.001 to 15% by weight of an initiator. Suitable solvents for the solvent polymerization process are, for example, toluene, xylene, tetrahydroanthracene, ethyl acetate, methoxypropyl acetate, n-butyl acetate, oxyhexyl acetate, oxyheptyl acetate, propylene glycol. Methyl ether acetate, butanediol acetate, ethyl ethoxy propionate, acetone, acetamidine, butanone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl Ketone, ethanol, isopropanol, butanol, benzyl alcohol, diethyl ketone alcohol, methoxypropionaldehyde, mineral spirits, other aliphatic, cycloaliphatic and/or aromatic hydrocarbons such as: Solvesso 100®, g For example, Exxate 700®, ethers, ketones, alcohols and mixtures thereof, are customary. It is noted that in the overall GPPS and HIPS processes, ethylbenzene is basically used as a solvent. Mainly based on cost, toxicity, flammability, volatility and chain transfer activity. -10- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1293313 A7 B7 V. Description of invention έ ) Select appropriate Solvent considerations. It is noted that certain trioxepanes are known. Please refer to Kirk & Othmer's, Encyclopedia of Chem. Tech., 3rd Ed, Vol. 17, p. 57, which proposes 1,2,4-trioxocycloheptane of the formula:

W0 98/50354 proposes four related trioxepane compounds, including the products of the formula: 〇-〇 ch3

The use of these compounds and adjuvants in the crosslinking procedure is also presented. The general meaning of the nomenclature used in the method currently proposed for the formation of thermoset plastics or non-thermoplastic elastomers is disclosed in 1.3, such as: W. Hofmann's, Rubber technology handbook (Carl Hanser Verlag, 1989) 0 US 3,517,03 2 Can be formed in this method

The circular trioxygen paper scale of the type 4,4,7,7-tetramethyl-1,2,3-trioxepane is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). ) 1293313 A7 —__B7 V. Description of invention ^ ) Compound. This cyclic trioxide is said to act as a polymerization catalyst. It is not indicated that the contaminant trioxane can be used for this purpose. The trioxepane used in accordance with the present invention can be synthesized in a conventional manner, such as 'substantially, in the presence of a catalyst, by the reaction of H〇C<CH3)Hch2C(CH3)2OOH with hydrazine and subsequent purification steps. . Such a procedure is described in Example 1 of W0 98/50354. Ketones suitable for the synthesis of such peroxides include, for example, acetone, acetophenone, methyl n-amyl ketone, ethyl butyl ketone, ethyl propyl ketone, methyl isoamyl hydrazine, methyl heptyl Ketone, methylhexyl ketone, ethyl amyl ketone, dinonyl ketone, diethyl ketone, dipropyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, A Ketopropyl ketone, methyl tert-butyl ketone, isobutylheptyl ketone, diisobutyl ketone, 2,4-pentanediamine, 2,4-hexanedione, 2,4-heptanedione, 3, 5 -heptanedion, 3,5-octanedione, 5-methyl-2,4-hexanedione, 2,6-dimethyl-3,5-peptanedione, 2,4-octanedione, 5 ,5-Dimethyl-2,4-hexanedione, 6-methyl-2,4-heptanedione, 1-phenyl-1,3-butanedione, 1-phenyl-1,3- Pentanedione, l,3-diphenyl-l,3-propanedione, b-phenyl-2,4-pentanedi-, methylbenzophenone, phenylmethylketone, phenylethylketone, Methyl chloromethyl ketone, methyl bromomethyl ketone and their coupling products. Of course, other ketones having an appropriate r group corresponding to the peroxide of formula I, such as a compound of formula H0RC(0)ROH, and a mixture of two or more different ketones, may also be used. Preferred ketones are acetone, methyl ethyl ketone (any isomer), diethyl ketone (any isomer), oxime acetone (any isomer), methyl ethyl ketone (any isomer), methyl ketone (any different) Structure), methyl ketone (any isomer), ketone (any isomer), ethyl acetonide (any isomer), butyl ethyl ketone (any isomer), ketone ( -12 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1293313 A7 B7 V. Invention description Q) Hetero isomer), Ethyl ketone (any isomer), Cyclohexanone, Acetyl Acetone, ethyl acetate, diacetone alcohol, and mixtures thereof. The peroxide can be prepared, shipped, stored and applied in the form of powders, granules, pellets, ingots, tablets, slabs, slurries and solutions. These blends can be diluted as desired, depending on the particular peroxide and its concentration in the blend. Preferably, the peroxide is used such that at least 5 〇 weight 〇 / 〇 (at least 75% by weight, more preferably more than 85% by weight) or the oxide conjugate is one or more trioxanes according to the invention. Heptane. It is preferred that the peroxide be used in its technical purity grade. The term "high solid content" as used herein means that the solid (nonvolatile matter) content of the resin composition is at least 5% by weight based on the total weight of the resin composition. More preferably, they contain more than 60% by weight. / 〇 (more than 70% by weight of the best) solid. The so-called "low molecular weight" means that the (co)polymer molecular weight is less than 5 〇, 〇〇〇, preferably less than 25,000, more preferably less than 15,000. In the polymerization method, the usual additives may be used in a usual amount. Such additives include chain transfer agents such as sulfur, disulfide and/or CC 14. The high solid content propionate resin obtained according to the present invention is The basic resin composition contains a conventional curing agent and may contain conventional additives such as stabilizers, surfactants, UV-absorbers, catalyst blockers, antioxidants, pigment dispersants, mud additives, rheology Control agents, leveling agents and solvents. Such additives for coating compositions may be present in the process according to the invention 'as long as they do not adversely affect the polymerization process. Paper ruler Choi S @ home fitness standard 297 well multiplexing) -13- 1293313 A7 B7 V. invention is described in (11) styrene (available from Merck, distilled before use) two gas methane (available from Baker)

Solvesso® 100 and Exxate® 700 (from ExxonMobil)

Trigonox® 301 (available from Akzo Nobel, 41% cyclic butanone peroxygen in diluent)

Trigonox® 2 2 (from Akzo Nobel, 1,1 -di(t-butylperoxy)cyclohexane in diluent)

Trigonox ® B (available from Akzo Nobel, di-t-butyl hydroperoxide) All other chemicals supplied by Acros Chemicals were of analytical grade and were used without further purification. The molecular weight (distribution) of the polymer was determined in a conventional manner using a Waters 510 HPLC pump, a general column and a detection device, and this polystyrene # was used as a standard. The degree of polymerization is measured by analyzing the amount of unreacted monomer by gas chromatography in a conventional manner.

Examples 1 - 10 and Comparative Examples A - D In these examples, the propionate was polymerized in a solvent using a sheathed glass reactor having a diameter of 60 mm and a height of 80 mm, equipped with a turbine agitator, Condenser and injection port. Solvent (40 g) was added to the reactor. The temperature was adjusted so that the half-life of the peroxide used in the experiment at this temperature was 15 minutes. When the polymerization temperature is as high as 126 ° C (inclusive), butyl acetate is used as a solvent. The polymerization temperature is from 126 ° C to 165 ° C (inclusive), using Solvesso® 100, Exxate® 700 for polymerization temperatures from 165 to 200 ° C, and ethyl citrate for polymerization temperatures of 220. °C. -14- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1293313 A7 _ B7 1-5. Description of invention (12) Use of nitrogen to obtain anaerobic polymerization conditions. Monomer (40 g butyl acrylate, 28 g hydroxyethyl methacrylate, 20 g styrene, 10 g decyl isobutyrate and 2 g methacrylate) and 30 meq (relative to two 每 per molecule) The hydrazone compound, which is 30 millimoles, was introduced into the reactor using a Watson Marlow pump for 4 hours. This polymerization was then carried out for another hour at the same temperature. The obtained polymer was analyzed in a usual manner. The molecular weight was determined by ΗΡ-SEC using polystyrene as a standard. The solid content (solid) of the obtained resin was measured by gravimetric analysis. · About 1 gram of the resin was accurately weighed, and the sample was dissolved in about 1 gram of toluene, and dried in an oven at an air circulation at 125 ° C for 4 hours. After the sample is cooled, the weight of the remaining material is divided by the original sample weight and the resulting enthalpy is the solid content. The viscosity was measured at 25 ° C using a Brookfield viscometer. The reference product "cyclic-MIAKP" was prepared using the procedure for composition V in WO 96/03397, but isoamyl ketone was used here instead of isobutyl ketone. This compound is considered as a representative example of a novel high solid content acrylic acid polymerization initiator. This cyclic-MIAKP was diluted and contained 67.3% by weight of peroxide. The trioxepane according to the invention according to the invention is in a technically pure form having a peroxide content of more than 95% by weight. Use the following products: -15-

1293313 A7 B7 V. Description of invention (13)

-16- The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1293313 A7 B7 V. Inventive Note (14) The results are as follows: Example Peroxide polymerization temperature Solid (%) Mw Μη D 1 Formula I 180 69.9 4,500 1,750 2.5 2 Formula I 200 70.0 2,400 1,300 1 . 8 3 Formula I 220 69.0 1,700 1,100 1.6 4 Formula II 165 69.2 5,700 2,750 2.0 5 Formula III 180 70.1 3,300 1,800 1.85 6 Formula III 220 69.7 1,700 1,100 1.6 7 Formula IV 180 69.5 4,000 1,950 2.04 8 Formula IV 220 69.3 1,800 1,100 1.57 9 Formula V 220 70.8 1,900 1,200 1.65 10 Formula VI 220 68.2 1,400 1,000 1.4 A Ring-MIAKP 180 70.8 6,000 1,900 3 . 1 B Trigonox® 301 200 71 , 3 2,900 1,500 1.95 C Trigonox® B 220 71.1 2,000 1,200 1.66 D without 220 58.0 Not determined, tacky product These results show that the trioxepane according to the invention is a low molecular weight, high solids content and narrow molecular weight distribution of acrylic acid. A very effective initiator for ester resins. In addition, these products can be used without the use of a diluent. The reason why the colored resins were obtained in Examples 7 and 8 was unknown, and the other resins were pale to more pronounced yellow.

Real 4 columns 1 1 and ratio &gt; Cars 4 columns E glass ampoules (2.5 ml) filled with about 1.3 g of initiator / styrene blend -17 - This paper scale applies to China National Standard (CNS) A4 specifications ( 210X 297 mm) 1293313 A7 B7 V. Inventive Note (15) (0.75 milliequivalents of initiator, equivalent to 0.75 millimoles per gram of styrene and 0.375 millimoles in Example 7 and Example C, respectively 100 grams of styrene) was placed in dry ice to cool the mixture to about -7 0 °C. The air above the frozen mixture is scrubbed with nitrogen and the ampoules are sealed. The ampoule was placed in a 120 ° C oil bath to polymerize the contents. Remove the ampoules after 2, 4, 6 and 8 hours. After removal from the oil bath, it was cleaned, broken, transferred to a 100 ml Erlenmeyer flask, and the contents were dissolved in 20 ml of dichloromethane for at least 48 hours. Each 2500 grams of this methylene chloride contained 25 grams of n-butylbenzene and 6.25 grams of butylated hydroxytoluene as separate internal standards and antioxidants for subsequent GC analysis. After dissolution, the styrene is converted to polystyrene, and the molecular weight of the polystyrene is determined by GC and GPC techniques in a conventional manner. The following table lists the conversion of styrene and the weight average molecular weight of the resin after 2, 4, 6 and 8 hours of polymerization. Example Peroxide Conversion (%) Mw*10'3(D) 2 4 6 8 2 4 6 8 11 Formula V 36.2 69.3· 94.4 99.4 320 375 455 445 E Trigonox® 22 78 97.5 99.5 99.7 315 370 365 355

Example 1 2 and Comparative Example F Example 1 2 and F were repeated for Examples 1 and E, but the polymerization was carried out at 140 °C. Peroxide conversion for the example ^ K%) Mw*10*3(D) 1.5 4 6 8 1.5 4 6 8 12 Formula V ~ 75.5 84.3 97* 98.8 195 202 200** 195 F Trigonox® 22 77 79.6** 90 97 176 180** 192 193 -18- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1293313 A7 B7 V. Invention description (16 ) Estimated by data after 3 hours (96%) **= Estimated 値 can be seen from Examples 1 1, 2 2, E and F: Compared to conventional peroxides (eg Trigonox® 2 2 ), the products according to the invention enable polystyrene at the same conversion rate The yield of acetamidine is extremely high and has a desired higher molecular weight. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1293

——^090122495 (The above columns are from this bureau) Invention #中 96Λ17日修正 Supplement i Ά4 C4 Chinese manual replacement page (October 1996) Patent specification, Lin! Name Method for the manufacture of high solids acrylic, styrene, and LDPE type resins using trioxane heptanes

USE OF TRIOXEPANS IN THE PROCESS TO MAKE fflGH-SOLID ACRYLIC, STYRENIC, AND LDPE-TYPE RESINS Name Nationality 1 · Andreas Homante ANDREAS HERMAN HOGT 2 · John Mejer JOHN MEIJER People's residence, residence, and righteousness (name f Nationality 5, name 1 · 203, Odden Zasser Street, Indidi City, The Netherlands 2) No. 18, R. Heilizhe Street, Duffet, The Netherlands, Dutch company Axor Nobel AKZO NOBEL NV Netherlands

76 Weber Road, Yahan, The Netherlands 1 Peter Kniriris Shakwick PIETER CORNELIS SCHALKWIJK 2. Gault Ferdin GUNTER FETT Paper ruler "财 _gi^-) A4»(210X297^)

Claims (1)

A BCD 129 No. Patent Application No. 1 Chinese Patent Application Substitute (October 96) VI. Patent Application A polymerization method in which at least one heptarginator is used to carry out one or more monomers (1) of trioxane. One of 1-3 L in the middle Γ?, one selected from the group consisting of hydrogen and a substituted or unsubstituted hydrocarbon group, may be linked to form a ring structure. 2. For the method of claim 1, γ+ /, 中,R are respectively selected from hydrogen and substituted or unsubstituted Cl-C2G alkyl, Parkan 3 120% alkyl, C6-Go square , cvc^alkyl and (: a wide aryl group, these groups may be (iv) (d) Μ 烷基 alkyl 'heart group can be linked to a cycloalkyl group; to each of the three selected one or more The groups are respectively selected from the group consisting of a mercapto group, an alkoxy group, a carboxylic acid, a linear or branched chain group, an aryloxy group, a halogen group, an ester group, a carboxyl group, a nitrile group and a decylamine group. The method of the invention, wherein R 1 and R 3 are selected from the group consisting of C 2 decyl, and R 2 is selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, isobutyl, second butyl, pentyl, isopentyl , cyclohexyl, phenyl, (:1130:(;〇;)〇^2-, C2H50C(0)CHr, HOC(CH3)2CH2+ 73111-961017.DOC This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1293313 VI. Patent application scope ;, R R knife 4 freely apply for the RU3 ^ = He group, or RW is connected to the substituted or unsubstituted method of the third paragraph of the patent scope, where hR3 is selected, B Base and isopropyl. Soil = the method of any of the items U4 of the patent application, wherein the solid content is an acrylate resin. y 6 as in the method of any of the above-mentioned patents, the method of formulating a monomer mixture containing at least 40% by weight of styrene in a pot to form a styrenic resin 0, as in any one of the claims U4 , wherein ethylene is free radically polymerized or copolymerized at a pressure of from 500 to 4,000 bar. 73111-961017.DOC This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)