TWI229009B - Process for alkoxylation of tri and polyalcohols - Google Patents

Abstract

A process for alkoxylation of a tri or polyalcohol, being solid at applied reaction temperature, in the presence of a catalytically effective amount of at least one alkoxylation catalyst is disclosed. The process is a solvent free process and comprises the steps of (i) under effective stirring submitting at least one said tri or polyalcohol to reaction with at least one alkylene oxide, said tri or polyalcohol being coated with a catalytically effective amount of said at least one alkoxylation catalyst, and (ii) under effective stirring charging to in step (i) obtained product and submitting to reaction further amounts of at least one said tri or polyalcohol and at least one alkylene oxide, and optionally (iii) under effective stirring submitting in step (ii) obtained product to reaction with a further amount of at least one alkylene oxide and/or at least one tri or polyalcohol.

Description

1229009 V. Description of the invention (1) Qiaoming is a novel solvent-free alkoxylation method, which is solid at the temperature of alkoxylation: three, and the polyol point is 1 0 0 c or more. Three- and multi-component f limbs, such as those with two-, three-, and three-polyol systems, are used to store the alkylene oxide (alkylene 0; Epoxidation, butadiene oxide, such as ethoxylated styrene, is polymerized into alcohols (such as dioxane hexene oxide and the resulting amidine. The amidine is functionally pre-recovered and Polyhydric alcohols), and functional hydroxy compounds. 〃 Ethyl alcohol and ethoxylation are the most important alkoxylations. Secondary hydroxyl groups are formed. Unexpected side reactions are major unsaturation of ticks. The formation of end groups is driven by the increase of molecular weight and the increase of molecular weight ... and the problem of reduced polymerization rate does not exist. The undesired terminal unsaturation is at the temperature and pressure available in a typical alkoxide plant Make alkane oxidation feasible, high melting solid two, three and multiple Alcohols need to have lower melting points, such as esterification of fatty acids and / or co-solvents (such as organic solvents and / or water). This distinguishes high-melting solid di-, tri-, and polyhydric alcohols from other substrate types typically used for alkoxylation. An important factor in water. Water is a more commonly used solvent for the oxidation of solid di-, tri- or polyhydric alcohols. When di-, tri- or polyhydric alcohols must be at least partially soluble in water, the alcohol does not need to be dissolved in the entire amount in solution Medium. It is thus possible to use the suspension of the alcohol in its own aqueous solution. Usually every 100 parts by weight of two, three or polyhydric alcohols

C: \ 2D-CODE \ 9M2 \ 91121877.ptd Page 6 1229009 V. Description of the invention (2) Use 10 to 50 parts of water. The use of water as a solvent results in the formation of unwanted ethylene glycol and polyethylene glycol from the reaction between water and alkylene oxide. This reaction interferes with the step, and the resulting product is a mixture of ethylene glycol, polyethylene glycol, the polymer and polymer of the alcohol and alkylene oxide, and water, which is not easily separated. Only a limited amount of organic solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, oxidized organic scales of ethylene glycol, and saturated hydrocarbons, are non-reactive to alkylene oxides and are immediately available. Most organic solvents will react with diluted oxygen to dye the resulting product. In addition, the use of organic solvents creates unwanted hazards and requires the product to be refined. For example, during the ethoxylation process of the two, three, or polyhydric alcohols used in the main suspension, the reaction is not immediately liquid at the reaction temperature, and the reaction is performed in the presence of water and other polar solvents, so that the reaction is in a single-phase system.里 发 ^. By-products such as mono-, di-, and tri-ethylene glycol are generated during the process, and rhenium = military origin, azeotrope formation, and strong affinity for the main product. These appear in ethoxylated di-, tri- or polyhydric glycols such as acrylic acid (acrylatione) to produce mono-, di- = K = corresponding acrylics, which are toxic and can cause skin irritation: Its admirable thing is diethylene glycol diacrylate. One possible solution to the problems discussed above is Fangguo Patent No. 2,9,2,478, which discloses that it is substantially insoluble in olefins: oxo-inductive polymer, which can be at temperatures below its melting point and decomposition temperature. In the following, the use of dimethylamine as the solvent for the oxidation of the oxidant is not #. In the next-a disadvantage is that the amine catalyst is inherently unable to catalyze exceeding the low molecular weight :: oxygen $ 7 page 1229009

1229009 V. Description of the invention (4) Oxidation catalyst coating, and the reaction is based on the negative reaction of the alcohol and the alkylene alkane compound is liquid at the applied reaction temperature, and ii) is added under effective stirring The product obtained in step (i) is sent to a larger amount of at least one of the di-, tri- or polyhydric alcohol and at least one alkylene alcohol and the alkylene oxide system to produce a liquid alkoxylated alcohol oligomer or polymerization ^ ( b) added in mole ratio, the oligomer or polymer is liquid under the applied reaction / JEL degree, and as the case may be, iU) under effective stirring, the product obtained in step (li) is sent to The amount of at least one alkylene oxide and / or at least one di-, tri-, or polyhydric alcohol: the amount of the alcohol produced; or the alcohol system to produce a heart lice alcohol oligomer or polymer having at least 0.5 alkoxy units (C). The effective stirring is preferably performed with a diameter of 90%, ^ 9090% sil96_99% # ^ ^ is stored in the initial step of the method of the present invention, the second gas: 二 reaction temperature The distribution of the resulting products of the two, three, and polyhydric alcohols is shown below. > 'The agitator affects the progress of the reaction =: (ii) and / or the optional step (Ui) added in the second, third or night vultures can be used in various of the present invention, ^ coating one effective You are reminded to visit Ling gv 〃, and appropriately and separately ^ oligosity oxidation catalyst. The upper right can be added to other and better specific examples of: p-oxidation catalyst: effective catalysis of alkane Select the reaction mixture in step (iii). Step (11) and / or various specific examples of the method according to the present invention include

1229009 V. Description of the invention (5) Alkoxylated alcohol polymer or polymer Γ, jealous declaration from the bucket, people, u, thing (a) and the task or difficult compound produced in step (ii) ⑻ has at least 0.5, such as 〇2, 2-5, alkoxy units, with ··· υ · 5-10 agglomerates or polymers (c) have emulsifying alcohol as small as 0 main ) 0 · 5, such as 0-5 0 _! 〇Λ or 2-20 alkoxy units. 3U, 1-30

The step (i) of this method is in a specific example of I 2 々 夕 — #, ▲ In the specific example of the car, the second, first or night 70 turns used and the naturalization used are exhausted ^ pa is recognized by A person. 4 The mole ratio of Qiuhua milk is between 0.5 and 10, for example between 2 and 5, so ^ Λ ^ In the same preferred specific example, ㈣ (: · ,: early A batch of steps. The -alcohol and the alkylene oxide used; (ii) 糸: two, three or more used for example between 2 and 5, and between 0 and 5 and 10 "⑴" is preferably to produce a Γ with an interval between .5 gates, steps 10, 2 and 20, 2 and 30, or 1 and 30, such as a mole of polymer or polymer. Ratio, the oxidized alcohol oligomerization system is better and each step is performed at a temperature of 50-250 t. Each step is 12 0-180 ° C. Order 'for example 80-20 0 ° C or in step (i) Step (^) and / or optional step one, two, or polyhydric alcohols are used in a preferred embodiment (1 1 1). The two, three, or polyhydric alcohols with a dazzling point of at least H0 are in Dipentaerythritol, tripentaerythritol, trihydroxypyrene at atmospheric pressure Ethylene glycol, pentaerythritol, dimethyltrimethylolpropane, sorbitol or sugar, 哕 ttrimethylol is preferably pentaerythritol or dipentaerythritol. ^ One, two or more in step (i), Step (i0 and / or optional step Γ ·· alkylene oxide is divided into C1 U in the preferred embodiment of the present invention) 2 ~ horse ethylene oxide, ring

1229009 V. Description of the invention (6) Propane, butylene oxide 'butadiene oxide, styrene, and the best combination is ethylene oxide, cyclopropane or gasification. The two compounds, or a mixture thereof, or a preferable alkoxylation catalyst thereof include specific examples selected from test compounds. The calcination and oxidation catalysts used in step (^, oxal compound and organic or inorganic step (⑴) are the best and are: ^ ^ ^ ^ ^ ^ ^ .b 4. (alkoxide), Λ7Γ ^ ^ ^ (meth〇xide), and / or soil test: milk. Catalysts can be exemplified by sodium hydroxide, formic acid, potassium hydroxide, hydroxide chain, and methyl methoxide. The chemical contacts: oxygen potassium, The final product of methoxyl produced by the method of the present invention = catalyst is better and is respectively; J0; 〇〇! -〇. 05% ^ 0. 001-0. 〇〇5% 5 step (11) and optional steps (Iii) The sub-steps are: the step (0), the best specific method of the method (1), the step (i and the optional step (111) bis: 2: 2; in the: step or-pentaerythritol 'and The steps are the specific examples of oxybenzene and / or propylene oxide. The further description of oxygen :, j, I believe that one person who is familiar with this skill can only explain 祚 = Ming. Therefore, the following better specific and The content is intended to be illustrative and not to limit the present disclosure in any manner; and 2 is an instruction to coat quaternary, pentaerythritol, and dipentaerythrium with a burn-oxidation catalyst = J3 to 6 The method of the present invention is disclosed, in which the method is described, and Example 7 is an example of ethoxylated with various degrees of ethoxylation, which is based on commercially known 9l] 2l877.ptd 11 pages 1229009

The pentaerythritol was ethoxylated in the presence of water as a co-solvent. Example 1 x Potassium hydroxide (alkoxylation catalyst) was coated with pentaerythritol. After ΓΓ: production of milliliter: potassium oxide aqueous solution, the concentration of which is equivalent to that in the optimal production. Gangel pentaerythritol was added to the t-liquid t / 'sub to make the mixture uniformly mixed. It is then dried at 120 to steam the water. Finally, the obtained product is ground into a powder. /, Example 2 Dipentaerythritol was coated with potassium oxynitride (alumina oxidation catalyst). 600 ml of a potassium hydroxide aqueous solution was prepared at a concentration equivalent to 0.002% KOH in the final alkoxylation product. 600 g of dipentaerythritol was added to the solution, and the mixture was uniformly mixed. Then it was dried at 20 ° C to prepare water. Finally, the obtained product is ground into a powder. Example 3 An ethoxylated pentaerythritol having an average degree of ethoxylation of 5 mole ethylene oxide / mole pentaerythritol was prepared in 2 steps, using 0.02% KOH as the alkoxylation catalyst in the final product . Step (i)

A scale of 200 grams was coated with a pentaerythritol according to Example 1 in a suitably equipped 2 liter laboratory pressure cooker (including a 90% to 95% dipstick with a diameter of the pressure cooker). Under effective stirring for 2 hours, 131 g of ethylene oxide was added to pentaerythritol and reacted with it at a temperature of 0-10-180. The pressure during this reaction was 2000_600 kPa.

C: \ 2D-CX) DE \ 9M2 \ 91121877.ptd Page 12 1229009 V. The degree of ethoxylation determined by the description of the invention (8) * Yield,% Step (ii) " 7 2 grams in step (1) The obtained product is equipped with a 2 liter laboratory pressure cooker that is compatible with step (1) (1.) (i.〇4 ^ oh / 10〇V ^) ^ ψ (η ^ ^ ^ Andanes and 181.8 grams of pentaerythritol were added to the product of this one step (〗), and the pressure between 160-18 (rc temperature is 20 0-600kPa. "Han I 3 reaction period • 5. 12 94. 9 Degree of ethoxylation determined by diethyl ether * Yield,% The content of alcohol and triethylene glycol is shown in Table 1. Monoethylene glycol in the final product is shown in Table 1. * Mole ethylene oxide / Mole pentaerythritol. Examples 4 In 3 steps: prepare an ethoxylated pentaerythritol with an average degree of ethoxylation of 5 moles of ethoxylate / mole pentaerythritol, using 0.02% K0H as the alkoxylation catalyst in the final product Step (i) Weigh 200 grams of pentaerythritol coated according to the example} iKOH in a suitably equipped 2 liter laboratory pressure cooker (including a 90-95% stirrer with a diameter of the pressure cooker) ^ in Under effective stirring for 2 hours, 131 g of ethylene oxide was added to the pentaerythritol and reacted with it at a temperature of 1600-1800 t. The pressure during the reaction was 2000-600 k P a.

C: \ 2D-C0DE \ 9M2 \ 91121877.ptd Page 13 1229009 V. Description of the invention (9) 2. 04 99. 7 Degree of ethoxylation determined * Yield,% Step (ii) Attack 1 8 · 2 g of the product obtained in step (i) was equipped with the same 2 liter laboratory pressure cooker as in step (丨), and 0.61 g of a K0Η aqueous solution (1.04 g of KοΗ) was used as an alkoxylation catalyst. (100 ml). Under effective stirring for 5 hours, 126 grams of ethylene oxide and 181.8 grams of pentaerythritol were added to the product of step (i), and reacted at a temperature of 16-18 (rc.) During the reaction. The pressure is 2 0-6 OOkPa. The degree of ethoxylation determined * 2 15 Yield '% 99 5 Step (iii) * Section 1 9 · 4 g of the product obtained in step (ii) is provided in the equipment 2 liter laboratory pressure cooker same as steps (丨) and (1 1), and 0.37 g of KOH aqueous solution (1.04 g ... Mix. Under effective stirring for 2.5 hours, 700 grams of ethylene oxide is added to the product of step (ii) and reacted at a temperature of 160-180 t. During the reaction The pressure is 2000-600 kPa. The determined degree of ethoxylation * 512 I # '% 94. 9 The content of monoethylene glycol, diethylene glycol and triethylene glycol in the final product is not as shown in the table. —. * Mole Ethylene Oxide / Mole Pentaerythritol. Example 5

C: \ 2D-CODE \ 9M2 \ 91121877.ptd Page 14 1229009 V. Description of the invention (ίο) Prepare 2 steps with an average ethoxylated beauty agent such as μ 〇 # ^, Youding / 〇 lice explosion degree is丨 3 Molar Ethylene Oxide /

Moore ^ Ethyl quaternary ethoxylation-check rfe rm e -b JzL monopentaerythritol, 0.02 2% K0Η as alkoxylation catalyst in the final product. Step (i) Scale 2 93 grams of a 2 liter laboratory pressure cooker (including a stirrer having a diameter of 90-95% of a pressure cooker diameter) coated with KOH in accordance with Example 2 was appropriately equipped with dipentaerythritol. With effective stirring for 3 hours, 259 grams of ethylene oxide was added to dipentaerythritol and reacted with it at a temperature of 160 to 180 ° C. The pressure during the reaction was 20 to 60 Ok Pa.

Degree of ethoxylation determined * 5.0 Yield,% 98.7 Step (ii) Weigh 23 grams of the product obtained in step (i) in a 2 liter laboratory pressure cooker identical to that in step (i), and 1.52 g of an aqueous KOH solution (1.04 g of KOH / 100 ml) as an alkoxylation catalyst was mixed. With an effective disturbance of 3 hours, 534 g of ethylene oxide and 230 g of dipentaerythritol were added to the product of step (i) and reacted at a temperature of 1 60 to 1 80 ° C. The pressure during this reaction is 200-600 kPa.

The degree of ethoxylation determined * 13.03 Yield,% 97.2 The contents of monoethylene glycol, diethylene glycol and triethylene glycol in the final product are shown in Table 1.氺 Mol Ethylene Oxide / Mole Dipentaerythritol. Example 6

1229009 V. Description of the invention (11) An ethoxylated dipentaerythritol having an average degree of ethoxylation of 9 molole dipentaerythritol is prepared in 3 steps, and the contention is: u / 7L / By using 0.02% K0 烷 as an alkoxylation catalyst. ~ A Make step (i) 2 3 3 grams of two quarters coated with Κ Ο Η in Example 2, when equipped with a 2 liter laboratory pressure cooker (including a 9 0 -9 5% diameter Blender). With effective stirring for 3 hours, "" 25% of ethylene oxide was added to dipentaerythritol, and reacted with it at a severity of 160-18 rc. The pressure during the reaction was 200-600 kPa. % Degree of ethoxylation determined * 5.0 Yield,% 98.7 Step (ii) Scale 1 8 · 2 g of product obtained in step (i) in a 2 liter laboratory equipped with the same as in step (丨) Pressure cooker and mix it with 0.67 g of KOH aqueous solution (1.04 g KOH / 100 ml) as an alkoxylation catalyst. Under effective stirring for 3.5 hours, 158 g of ethylene oxide and 81 8 grams of dipentaerythritol are added to the product of step (i) and reacted at a temperature of 160-180. The pressure during the reaction is 2 00-6 0 0 kPa. The degree of ethoxylation determined * 4.8 Yield,% 97. 6 Step (iii) Scale 3 5 7 · 4 g of the product obtained in step (ii) is equipped with a 2 liter laboratory pressure cooker which is the same as in step (丨) and step (ii), and 〇28g of KOH aqueous solution (1.04g KOH / 100ml) was used as a burning oxidation catalyst.

III

Page 16 1229009 V. Description of the invention (12) 4. With 5 hours of effective stirring, add 140 grams of ethylene oxide to the product of step (11), and the temperature is between 16 0 and 180 ° C. Reaction at temperature. The pressure during this reaction was 200-600 kPa. 9. 02 93.2 Degree of ethoxylation determined by ethylene glycol spear * Yield,% The content of ethylene glycol is significant. Monoethylene glycol in the final product is not shown in Table 1. * Mole ethylene oxide / Mole pentaerythritol. Example 7 * An ethoxylated dipentaerythritol having an average degree of ethoxylation of 5 moles of ethylene oxide / mole pentaerythritol was prepared in 2 steps, and 0.002% of KOH was used as the burn-oxidation contact in the final product. Media. Step (i) ^ 2 93 grams of 2 liters of laboratory pressure pins (approximately having a diameter of a pressure cooker =: 95%) coated with dipentaerythritol according to Example 2 in a suitably equipped 2 liter laboratory pressure pin . With effective stirring for 3.5 hours, 260 g of% oxyethane was added to dipentaerythritol and reacted with it at a temperature of 1600-1800 ° C. The pressure during this reaction was 2000-600 kPa. Determined degree of ethoxylation * 97.7% yield,% 'The product obtained in step (ii) # 1 8 · #step (1) is equipped with the same 2 / ^ test as in step (i) until Pressure steel. Under effective mixing for 4.5 hours, 162 g of oxoxane and 1 8 1 · 8 g of two coated with KOH according to Example 2

1229009 V. Description of the invention (13) Pentaerythritol is added to the product of step (i) and reacted at a temperature of 160-180 ° C. The pressure during this reaction was 2 00-6 0 OkPa. Determined degree of ethoxylation * 5.1 Yield,% 99.3 The content of monoethylene glycol, diethylene glycol, and triethylene glycol in the final product is significantly different. * Mole ethylene oxide / Mole dipentaerythritol. Example 7-The ratio of ethoxylated pentaerythritol to acetic acid with an average degree of ethoxylation of 5 moles / mole pentaerythritol

As # «π ^ i ^ In the final product, use 0.1% 2K0H as the emulsifying catalyst and water as the co-solvent scale. 136 grams of pentaerythritol water was used in the appropriate equipment. The powder K0Η and 70 g of the distillate were stirred and heated to 150 to 1,000 pounds. In a nitrogen environment, add mixed grams of ethylene oxide to the obtained solution, and under stirring for 3.5 hours, 220

91121877.ptd Page 18 20/3 of 00-4000 mmHg and react at UOt temperature and Table 1 1 knife 1229009

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Chinese Invention Patent Specification Three and Polyols Oxidation Method Name Name Ming Faming Inventor III. Please apply prc fo] English Name (Chinese)

Name (English) " WT Name of Residence (Domestic) (Chinese) Name (Name) (English)-National Residence, Domicile (Office) Name of Representative (Chinese) Name of Representative (English) C yal poly nd a • 1 tr of on lati Zrmi rz Lozkiyki awkiki skasny sllmwsew wei • corbin ieazkoni kiwis WKacig kis • chkiwzb Lursk zulsszk ksammi eczanumi Hepijanto HrpyJaTO 1 · 2 · 3 · 4 · 1 · 2 · 3 · 4 ·

No. No. No. j one 05 JfoTo Ke ίο Ke j I Te Te Te Te f I Qi Qi Qi Wu f f Lan j Nanana Nana jf Poeieere City Municipality Municipality Reirereire > 5 Bullfighting and bullfighting • Twist-barley wheat dagger IIII 4 Er Er Er Shu Qi Qi Qi Qi Zi II Dede De Puke Kai Kai Tate Lan Lan Lan Ye \ Pobo Bobo Bobo 1 · 2 · 3 · 4 · I

Claims (1)

1229009 -^ No. 91121877 Application patent scope nl, a kind of alkane oxidation method of two or more alcohols, which has a melting point of at least A10 (rc, / female hydrazine alcohol) in the atmosphere to oxidize the presence of oxidation catalyst under pressure; effective catalysis The amount of at least one kind of method, 廿 in the next into the lamp 'wherein, 沬 沬 沬 并 括 括 water) method, including the following steps: / only shell on the system without solvent ^ under effective stirring, make at least one selected from _: ?, Tripentaerythritol, trimethylolethane, ditrimethylol, dipentaerythryl: via fluorenyl propane, sorbitol, or strict sugar: terephthalate, di-, di-, and dilute oxygen reactions, multiple materials Oxygen ::; coating, and the reaction is based on the alcohol in Moore = 11) with effective stirring, added in step (n and more of at least one record Xi-Wu Ke _ 2 paid product And make it wide, $-★, evening species ^ one or evening 70 _ and at least one alkylene oxide inverse: the alkylene oxide system is generated to produce-a liquid oxidized alcohol oligomer at a temperature of f Polymer or polymer (b): and, as the case may be, iU) under effective stirring, the product obtained in step (ii) and more Amount of-alkylene oxide and / or at least-three or more fluorene reaction, the dilute oxygen and / or the > tri- or polyhydric alcohol system to produce a burned oxidized alcohol having at least 0.5 alkoxy units The polymer or polymer (c) is added in an amount. 2. The method according to item 1 of the scope of patent application, wherein the effective stirring is performed using a blender having a diameter of at least 90% of the diameter of the corresponding reactor. 3. The method of claim 1 or 2, wherein, in step (u) (:: \ Total file \ 91 \ 91121877 \ 91121877 (replacement) -l.Ptc Page 21 1229009 丄 ^ ΛM 91121877 〃, the tri- or polyhydric alcohol alkoxylation catalyst added in the amendment of the scope of patent application. Main Distribute an effective catalytic amount of the at least one 4. The burning oxidation catalyst such as the scope of the patent application] is added in step 1 ('Effective catalytic amount 5 as from-Shaoxiang C11). • Xishenlong Patent The first or the second range of the scope is ancient and earth. The ternary added in step ⑴υ is the at least one kind of alkoxylation catalyst selected. "糸 Main cloth-effective catalytic amount 6 The alkoxylation reaction of the 1st or 2nd is strong, among which the effective catalytic amount of the catalyst is added in the step (iii) used by the Haier. A2: The method of item 1 or 2 of the patent scope, where ， Alcohol Thai polymer or polymer (a) has at least 0.5 alkoxy units Or polymer (b) has at least 0.5 alkoxy units ^ 9. If the method of claim 1 or 2 of the scope of patent application, The intermediate polymer or polymer (c) has at least 0.5 alkoxy units. 10. The method according to item 1 or 2 of the scope of the patent application, wherein Niu Bang r. Mole ratio of alcohol to the alkylene oxide used 1 ^ between 0.5 and 10 (inclusive) in a single batch step. Force 11 · If the method of item 1 or 2 of the patent application, Among them, + ^ is used in the three or polyhydric alcohols used and the alkylene gas /: (1) is performed between 2 and 5 (inclusive)., K examples are referred to 1 2 The method according to item 1 or 2, wherein + is performed by using the three or more polyols and the alkylene oxides used (1 1) between 0.5, and 10 (inclusive) Continuous steps. The ratio is (:: \ General file \ 91 \ 91121877 \ 91121877 (replacement) -l.Ptc Page 22 1229009 MM 91121S77 VI. Application for patent scope 1 3. If the method of applying for the first or second scope of patent scope is used Second or guest-/, T 'step (1 1) between Jiqing 7 = Mole ratio of the alkylene oxide used is 1 4 · If the patent application step (iii) is used to generate a star / entry Method, in which the step of oxidizing the alcohol oligomer or the oxygen burning unit between 5 and 5 ° is selected. 5. If the application is dedicated to: Batch steps performed in the example. Step (iii) ) Is to produce a method with the right eighth or item, wherein the selected step of the alcohol polymer or polymer m: alkoxy units between the alkoxy units such as the application of the second patent application 1 ::? Step (ii) and / or the 'eight methods of item', in which step ⑴ and 进行 are performed. V step (1 1 1) 7 knives are at a temperature of 5 0-2 5 0 ° C 1 7 · If you apply for step (ii) of the patent application and / or choose the method of Xiban or 2 items, in which step (i), the next step is carried out., ^ 步 (1 1 1) are respectively at a temperature of 8 0-2 0 0 〇C 18 · Rushen Step (ii) and / or the method of the item 2 or 2 in the patent specification, wherein step (i) and OC are performed. Step (111) is at a temperature of 120-180 1 9 respectively. The method of step (i), step (ii), and $ or 2, wherein the alkylene oxides used in the ethylene oxide, propylene oxide, and the step-step (1 ii) are respectively oxygenated And / or phenylethyl oxide, butadiene oxide, butadiene oxide, cyclohexene 20. If the scope of the patent application is the method of alkoxylation catalyst at least one insertion + Z members, in which the organic used Acid compound or at least one kind of organic or none 1229009 ----- ^ 1 ^ 91121877__Yueyuebai Amendment VI. Patent Application ^ " --------- Organic base compound. The method according to item i or 2, wherein the alkoxylation catalyst is at least one kind of alkali metal hydroxide, alkali metal substance, or soil test metal hydroxide. Xiao Jia Emulsification 乂 V: Patent Application Scope No. 1 or 2 Method 'In which, the two = 21, step (ii) and the selected step (iii) are used to oxidize the catalyst system ", sodium gas or methoxyl Sodium, potassium hydroxide or potassium methoxide, and / or lithium oxynitride or thallium lithium oxide. 〆 · 23 · The method according to item i or 2 of the scope of patent application, wherein step (1), step (ii) And the alkoxylation catalyst used in step (iii) is calculated based on the final product, and is present in the amounts of 0 · 0 0 and 0 · 1%, respectively. · 24 · If the method of the first or second scope of the patent application, wherein the alkoxylation catalyst in the step (1), step (ii) and the selected step (iii) is calculated based on the final product, respectively 0. 00 bu 0. 05% of the amount. 25. The method according to item 1 or 2 of the scope of patent application, wherein the alkoxylation catalyst in step (1), step (ii) and selected step (iii) is calculated based on the final product, which is based on 0 · 00 卜 0 · 0 0 5% exists. 26. The method of claim 1 or 2, wherein the tertiary or polyhydric alcohol used in step (i), step (ii) and selected step (iii) is pentaerythritol or dipentaerythritol. 2 7 · The method according to item 1 or 2 of the scope of patent application, wherein the alkylene oxide used in step (i), step (ii) and optional step (iii) is ethylene oxide and / or propylene oxide . 2 8 · The method of claim 1 or 2 in the scope of patent application, wherein C: \ _ t \ 9l \ 9U2l877 \ 91121877 (replacement) -l.ptc Page 24 1229009 _ Case No. 91121877_ year month day amendment_ VI. The amount of water in any solvent in the patent application method is less than 10% . 29. The method of claim 1 or 2 in which the amount of water in any solvent present in the method is less than 5%. 30. The method of claim 1 or 2, wherein the amount of water in any solvent present in the method is less than 1%. (:: \ Total file \ 91 \ 9] 121877 \ 91121877 (Replace) -1.ptc Page 25