TW401431B - Polyoxyalkylene block copolymers and a process for preparing them - Google Patents

Abstract

A block copolymer of a molecular weight from 10,000 to 50,000 containing one or more polyoxyethylene blocks and one or more polyoxy (higher alkylene) blocks wherein the oxyethylene units are present in an amount from 5 to 90 mol% and the oxy (higher alkylene) units are present in an amount from 95 to 10 mol% and wherein at least some of the blocks are linked together by an oxymethylene group can be prepared by reacting one or more dihydroxy terminated polymers selected from poly (ethylene glycol), poly (higher alkylene glycol) and block copolymers thereof in solution with a dihalomethane in the presence of a base at a temperature from 20 to 40 DEG C for from 2 to 36 hours and the resulting block copolymer is separated and dried. Such copolymers can be used as surfactants and surface modifiers.

Description

401431 A7 B7 V. Description of the invention (/) Field of invention __ The present invention relates to a polyoxyalkylene block copolymer and a method for producing the same. Dihydroxy-terminated triblock copolymer < p > b (E) -0H, where E group. These non-ionic interfacial activators. Properties are known to have a general structure Η-(Ε) β stands for oxidized ethylene and P stands for propylene oxide activator. Commercial products such as Plu, 2nicTM interface US-A-4 072 704 are described by gasified polymers and Polyalkylene oxide block copolymerized interfacial activators can be prepared by reacting the alkyl esters of the copolymer with formaldehyde or carbonate-based propylene oxide polymers, etc. Don't block and formaldehyde or carbonic acid interfacial activators. For example * linked The problem that polyoxyethylene and polyethers are trying to solve requires another method that can be adopted, the polygasified alkylene block copolymer and its preparation method, which are particularly expected to be simpler. It makes it possible to prepare higher molecular weight copolymers. Gather more or 1 and inlaid ethoxylate more or 1 with CRE species 1 for clarifying the hair. Lithium-oxygen is connected to the chain by high carbon-tone bond. The inlaid base is reduced to It ’s all in the air, the substrates are buried in the section, and the section starts from Ml 丨 (Please read the precautions on the back before filling out this page) 11 Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Special, or paragraph 1 embedded in carbon The method (i) is to polymerize a plurality of oxygen compounds or insert a kind of polyoxygenase to dissolve the oxypolyalkanease diethyl ether with a single stage of the derivatization catalyst. Many of the intermediates are gathered together in the common chelate fruit. The effect of anti-alkane methylamine halogenated dihydrogenase dicarbon is high and the internal liquid is embedded in it and it should be dissolved in the test. The agent should be used for other purposes. The amount of energy used should be reversed. One sheet of paper should be used by the family and one country. 7 9 2 401431 A7 B7 5. Description of the invention (/) Field of invention __ The present invention It is a polyoxyalkylene block copolymer and its preparation method. Dihydroxy-terminated triblock copolymer < p > b (E) -0H, of which E group. These nonionic interfacial activators are known. General structure Η- (Ε) β stands for oxidized propylene and propylene stands for oxidized propylene activator. Commercial products such as Plu, 2nicTM interface US-A-4 072 704 show the polymer and copolymer of gasified alkane. Polyalkylene oxide block copolymerization interfacial activator prepared by alkyl ester reaction can contain formaldehyde or carbon Ester-based oxypropylene polymers, etc. Don't block and formaldehyde or carbonic acid interface activators. For example, * connected polyoxyethylene and polyether chain need to be solved. Another kind of special expectations can be adopted. Army's production method of polygasified butane block copolymer and its production method. It makes it possible to prepare copolymers with higher molecular weights or more and 1 or more ethylene oxides or 1 containing CRE species. The concatenated monooxygen is connected to the high-tone-tethered base via an alkylene carbon. Some of the inlays are reduced to the air, and the substrates are collected and embedded in the section, starting from Ml 丨 (please read the precautions on the back before filling this page) 11 Central Ministry of Economic Affairs The Zhuhai Bureau Shellfish Consumer Cooperative Co., Ltd. prints a special number, or paragraph 1 containing medium carbon, high-tech (i-formed oxygen compounds gather a total of multiple sections or a type with a section for decane and acetaminophen) This oxygen polyalkanoate diethyl is dissolved at the poly end of the system, and the poly-terminus is selected from the two hydroxyl groups or the thing is gathered together in the common fruit. The effect of anti-alkane methylamine halogenated dihydrogenase Dioxane carbon and high internal solution are embedded in it and the storage test should be reversed to 0. The finished solvent should be used as the other solvent. The amount of energy used should be reversed. A sheet of paper should be prepared. Use Shigong 7 9 2

Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. Charge B7 'V. Description of the invention u) Start at room temperature, so no heating is required. Polyoxyalkylene block copolymers can have higher molecular weights than those made by other methods. The oxidized stilbene embedding group is very similar to the chemical structure of the other groups that form the polymer block. Xiong Mingxi Note 8B sharp Ming The preferred copolymers of the present invention include those in which the polyoxy (high-carbon butane) block is selected from polyoxypropylene and polyoxybutylene blocks. In a specific example of the present invention, the * block copolymer has the following formula to replay the 翚 position-([PrJCfUO-kUEdCHzOK- where P is oxidized propene; E is oxidized propene; η is an integer from 2 to 70, Preferably from 4 to 20; m is an integer from 2 to 250, preferably from 9 to 20; X is an integer from 1 to 100, preferably from 1 to 10; and y is an integer from 1 to 100, preferably from 1 To 50. In another specific example of the present invention, the * block copolymer has the following repeating units-[(E on Er) CH20] z-wherein P is oxypropylene; E is oxyethylene; r is from 2 to 135 An integer, preferably from 75 to 135; s is an integer from 15 to 65, preferably from 30 to 50; and z is an integer from 2 to 50, preferably from 5 to 20. The molecular weight of the block copolymer of the present invention is coagulated. Gel permeation chromatography K poly (oxygen _________ill ------------ This paper is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) (Please read the precautions on the back before (Fill in this page)

Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. Charge B7 'V. Description of the invention u) Start at room temperature, so no heating is required. Polyoxyalkylene block copolymers can have higher molecular weights than those made by other methods. The oxidized stilbene embedding group is very similar to the chemical structure of the other groups that form the polymer block. Xiong Mingxi Note 8B sharp Ming The preferred copolymers of the present invention include those in which the polyoxy (high-carbon butane) block is selected from polyoxypropylene and polyoxybutylene blocks. In a specific example of the present invention, the * block copolymer has the following formula to replay the 翚 position-([PrJCfUO-kUEdCHzOK- where P is oxidized propene; E is oxidized propene; η is an integer from 2 to 70, Preferably from 4 to 20; m is an integer from 2 to 250, preferably from 9 to 20; X is an integer from 1 to 100, preferably from 1 to 10; and y is an integer from 1 to 100, preferably from 1 To 50. In another specific example of the present invention, the * block copolymer has the following repeating units-[(E on Er) CH20] z-wherein P is oxypropylene; E is oxyethylene; r is from 2 to 135 An integer, preferably from 75 to 135; s is an integer from 15 to 65, preferably from 30 to 50; and z is an integer from 2 to 50, preferably from 5 to 20. The molecular weight of the block copolymer of the present invention is coagulated. Gel permeation chromatography K poly (oxygen _________ill ------------ This paper is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) (Please read the precautions on the back before (Fill in this page)

B7 L S5. 1. 2 9 yuan 5. Description of the invention (3) Huaxian B) quasi-measurement, which can range from 10,000 to 500,000, preferably from 50,000 to 250,000. The polymer can be prepared by one or more dihydroxy-terminated polymers selected from the group consisting of poly (ethylene glycol), poly (high carbon dialkylene) and its copolymers in solution in the presence of sickle and two Methane halide reaction. Examples of solvents that can dissolve the reagents include dihalomethanes and other known amidine solutions such as benzene, nitrogen benzene, toluene, or a mixture thereof. Preferably an excess of dihalomethane reagent is used as the solvent. High molecular weight products can be obtained even when the amount of dihalomethane is far more than the amount necessary for coupling with the polymeric antihalogen. Although any dihalomethane or its admixtures such as dihydromethane, dimomethane or diiodomethane can be used, it is preferred that the dihalomethane is dihydromethane. Necessary test conditions can be obtained by incorporating one or more rhenium, such as sodium hydroxide and potassium hydroxide. Examples of dihydroxy-terminated polymer starting materials include commercially available glycosidases (PEGs) and malonases (PPGs). Specific examples include PEG 400, PEG 6000, and PPfi 1000. The numbers connected to the "PEG" or "PPG" names refer to the average molecular weight of the polymer, which is the average number of repeated oxidized ethylene or propylene oxide units in the polymer. Directly proportional. Preferably, the polyendylenediase has a molecular weight ranging from 200 to 10,000. Other «examples of dihydroxy-terminated polymer starting materials printed by the Shell Standard Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs include poly (oxypropylene) (E) and poly (oxypropylene) (P) dihydroxy-terminated EPE triblock Copolymer, commercially available as Pin r on icTM type interfacial activator. Preferred triblock copolymers have molecular weights ranging from 4.000 to 15,000 Fanyuan. The copolymer of the present invention contains both a hydrophilic polyoxyethylene oxyethylene block and a hydrophobic polyoxyethylene (high carbon alkane) block. The balance between the hydrophilicity and hydrophobicity of the copolymer can be adjusted from the paper size to the Chinese national standard (CNS) A4 297 mm) B7 L S5. 1. 2 9 Yuan 5. Description of the invention (3) The precision measurement can range from 10,000 to 50,000, preferably from 50,000 to 250,000. The polymer can be prepared by one or more dihydroxy-terminated polymers selected from the group consisting of poly (ethylene glycol), poly (high carbon dialkylene) and its copolymers in solution in the presence of sickle and two Methane halide reaction. Examples of solvents that can dissolve the reagents include dihalomethanes and other known amidine solutions such as benzene, nitrogen benzene, toluene, or a mixture thereof. Preferably an excess of dihalomethane reagent is used as the solvent. High molecular weight products can be obtained even when the amount of dihalomethane is far more than the amount necessary for coupling with the polymeric antihalogen. Although any dihalomethane or its admixtures such as dihydromethane, dimomethane or diiodomethane can be used, it is preferred that the dihalomethane is dihydromethane. Necessary test conditions can be obtained by incorporating one or more rhenium, such as sodium hydroxide and potassium hydroxide. Examples of dihydroxy-terminated polymer starting materials include commercially available glycosidases (PEGs) and malonases (PPGs). Specific examples include PEG 400, PEG 6000, and PPfi 1000. The numbers connected to the "PEG" or "PPG" names refer to the average molecular weight of the polymer, which is the average number of repeated oxidized ethylene or propylene oxide units in the polymer. Directly proportional. Preferably, the polyendylenediase has a molecular weight ranging from 200 to 10,000. Other «examples of dihydroxy-terminated polymer starting materials printed by the Shell Standard Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs include poly (oxypropylene) (E) and poly (oxypropylene) (P) dihydroxy-terminated EPE triblock Copolymer, commercially available as Pin r on icTM type interfacial activator. Preferred triblock copolymers have molecular weights ranging from 4.000 to 15,000 Fanyuan. The copolymer of the present invention contains both a hydrophilic polyoxyethylene oxyethylene block and a hydrophobic polyoxyethylene (high carbon alkane) block. The balance between the hydrophilicity and hydrophobicity of the copolymer can be adjusted from the paper size to the Chinese paper standard (CNS) (A4, 297 mm)

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. When selecting the starting materials, the most suitable physical and chemical characteristics must be obtained. In addition to being suitable for a variety of interfacial activator applications such as antifoaming agents and dispersing ribbing agents, block copolymers can be used as surface modifiers, for example, to reduce the degree of protein adsorption to polystyrene. Copolymers are suitable for physiologically compatible materials in biological treatment equipment. The following examples illustrate but do not limit the invention. Example 1 An E7βP3OE7βΞ block copolymer (average molecular weight 8,400) with poly (oxyethylene propylene) (E7β) and poly (oxypropylene propylene) (P30) and the presence of dioxane in potassium hydroxide In the following, a multi-block copolymer of K-oxidized methylene was prepared. Digged potassium hydroxide (20g) and dichloromethane (250β1) were mixed in a 1 liter resin pot equipped with a condenser and a mechanical stirrer at room temperature under a nitrogen atmosphere. A triblock copolymer (20 g) dispersed in dichloromethane (50 ml) was added thereto. After stirring the whole for about 2 hours, another gas of methane (500 nl) K was added to reduce the viscosity of the polymer solution. After the solution was passed through diatomaceous earth, the polymer was evaporated by rotary evaporation under vacuum. Polymers were identified by gel permeation chromatography (GPC) plus K. This identification used dimethylformamide (DMF) eluate and Styragel columns, and was calibrated against poly (oxyethylene) standards. With reference to this calibration result, the molecular weight and molecular weight distribution were obtained from GPC media. Mw values ~ 150,00 and Hw / Μη ~ 2 were obtained. Yield > 95%. The method described in Example 1 of the first 12 examples is prepared with the following reagents: this paper is connected with oxidized dynein and is used in the national standard (CNS) A_4 specification (210X297 mm) ----------- -III I-order (please read the precautions on the back before filling this page)

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. When selecting the starting materials, the most suitable physical and chemical characteristics must be obtained. In addition to being suitable for a variety of interfacial activator applications such as antifoaming agents and dispersing ribbing agents, block copolymers can be used as surface modifiers, for example, to reduce the degree of protein adsorption to polystyrene. Copolymers are suitable for physiologically compatible materials in biological treatment equipment. The following examples illustrate but do not limit the invention. Example 1 An E7βP3OE7βΞ block copolymer (average molecular weight 8,400) with poly (oxyethylene propylene) (E7β) and poly (oxypropylene propylene) (P30) and the presence of dioxane in potassium hydroxide In the following, a multi-block copolymer of K-oxidized methylene was prepared. Digged potassium hydroxide (20g) and dichloromethane (250β1) were mixed in a 1 liter resin pot equipped with a condenser and a mechanical stirrer at room temperature under a nitrogen atmosphere. A triblock copolymer (20 g) dispersed in dichloromethane (50 ml) was added thereto. After stirring the whole for about 2 hours, another gas of methane (500 nl) K was added to reduce the viscosity of the polymer solution. After the solution was passed through diatomaceous earth, the polymer was evaporated by rotary evaporation under vacuum. Polymers were identified by gel permeation chromatography (GPC) plus K. This identification used dimethylformamide (DMF) eluate and Styragel columns, and was calibrated against poly (oxyethylene) standards. With reference to this calibration result, the molecular weight and molecular weight distribution were obtained from GPC media. Mw values ~ 150,00 and Hw / Μη ~ 2 were obtained. Yield > 95%. The method described in Example 1 of the first 12 examples is prepared with the following reagents: this paper is connected with oxidized dynein and is used in the national standard (CNS) A_4 specification (210X297 mm) ----------- -III I-Order (please read the precautions on the back before filling this page) 401431 A7 B7

V. Description of the Invention (ί)

Potassium hydroxide Digas methane Ei. AePseE 20g 250ml 20g (in 50m 1 methylene chloride) The polymer was isolated as described in Example 1. "Values ~ 70,000 and | ^ /» ^ ~ 2 "were measured by GPC. Yield> 95%. Fen example 3 According to the method described in Example 1, the following reagents were used to prepare ε βP β β Ε β · Potassium hydroxide diammonium methane 9 P.5 β Ε β 20g 30b1 16g (in 15ml diammonium methane) The polymer was isolated as described in Example 1. The value measured by GPC was ~ 20,000 and > ^ / & gt ^ ~ 2. Yield> 80! 1 !. g Example 4 Polyethylene glycol (PEG 400) with an average molecular weight of 400 and the average molecular weight (please read the precautions on the back before filling this page). Preparation of Polymalonase (PPG 1000) and Digas Methane in Potassium Hydroxide by the Consumers Cooperative of the Central Bureau of the Ministry of Economic Affairs-a multi-block it polymer connected by oxidized methyl formate. Example 1 The method described below uses the following Polymers prepared by reagents: 50 g of potassium hydroxide, dimethylformate 5 0 hi 1 PEG 400 10 g 〆PPG 1000 45 g mol% PEG 400 and 64. 3 no 1 X PPG 1000 ° Description of Example 1 Isolation polymer 0 measured by GPC Mw value ~ 11,000 and ^ < ¥ / 1 ^ ~ 2. Yield >953; The paper size is suitable Chinese National Standard (CNS) A4 size (210 X 297'ί5Τ 83.3.10,000 401431 A7 B7

V. Description of the Invention (ί)

Potassium hydroxide Digas methane Ei. AePseE 20g 250ml 20g (in 50m 1 methylene chloride) The polymer was isolated as described in Example 1. "Values ~ 70,000 and | ^ /» ^ ~ 2 "were measured by GPC. Yield> 95%. Fen example 3 According to the method described in Example 1, the following reagents were used to prepare ε βP β β Ε β · Potassium hydroxide diammonium methane 9 P.5 β Ε β 20g 30b1 16g (in 15ml diammonium methane) The polymer was isolated as described in Example 1. The value measured by GPC was ~ 20,000 and > ^ / & gt ^ ~ 2. Yield> 80! 1 !. g Example 4 Polyethylene glycol (PEG 400) with an average molecular weight of 400 and the average molecular weight (please read the precautions on the back before filling this page). Preparation of Polymalonase (PPG 1000) and Digas Methane in Potassium Hydroxide by the Consumers Cooperative of the Central Bureau of the Ministry of Economic Affairs-a multi-block it polymer connected by oxidized methyl formate. Example 1 The method described below uses the following Polymers prepared by reagents: 50 g of potassium hydroxide, dimethylformate 5 0 hi 1 PEG 400 10 g 〆PPG 1000 45 g mol% PEG 400 and 64. 3 no 1 X PPG 1000 ° Description of Example 1 Isolation polymer 0 measured by GPC Mw value ~ 11,000 and ^ < ¥ / 1 ^ ~ 2. Yield >953; The paper size is suitable China National Standard (CNS) A4 specification (210 X 297 '5T 83.3.10,000 A7 B7 401431 V. Description of the invention (t) Polyethylene glycol (PEG 400) with an average molecular weight of 400 and polypropylene glycol (PPG) with an average molecular weight of 1000 1000) Reacted with dichloroformamidine in the presence of potassium hydride to prepare a 1 M oxidized dynein-embedded multiblock copolymer. The polymer was prepared according to the method described in Example 1 with the following reagents: potassium hydroxide 50 g Dichloromethane 50 · 1 PEG 400 40 g PPG 1000 11. .25g is 90 boU PEG 400 and 10 «olX PPG 1000. The polymer was isolated as described in Spring Example 1. Mw value ~ 50,000 and Mw / Mn measured by GPC ~ 2. Yield > 95X. Fenli fi A M vaporized manicure was prepared by reacting an ErBsEr triblock copolymer having a molecular weight of 4,200 with B-type oxidized butadiene and methylene chloride in the presence of sodium hydroxide. Embedded multi-block copolymer. The copolymer was prepared according to the method described in Example 1 with the following reagents: sodium hydroxide 20 g

10 g of dichloromethane 160 · I E37B11E37 (in 50b1 dioxane). The polymer was isolated as described in Example 1. Mw value ~ 243,000 and Mw / Mn ~ 2 ° Yield > 95X ° g as measured by GPC Example 7 Commercially available Plu "onicTM F108 ErP-Er Ξ block copolymer; and a polyethylene with an average molecular weight of 6000 Second fermentation (PEG 6000) and second gas kebab -9- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Binding Ministry of Economic Affairs Employees of the Central Bureau of Standards #Cooperative Society Printing 83.3.10,000 A7 B7 401431 V. Description of the Invention (t) Polyethylene glycol (PEG 400) with an average molecular weight of 400 and polypropylene glycol (PPG 1000) with an average molecular weight of 1,000 and two atmospheres Formamidine was reacted in the presence of potassium hydride to prepare a monolithic oxidized dynein-embedded multi-block copolymer. The polymer was prepared according to the method described in Example 1 with the following reagents: potassium hydroxide 50 g diammonium methane 50 · 1 PEG 400 40 g PPG 1000 11. 25 g is 90 boU PEG 400 and 10 «olX PPG 1000. Isolate the polymer as described in Spring Example 1. Mw value ~ 50,000 and Mw / Mn ~ 2 measured by GPC. Yield > 95X. Fenfenfi consists of ErBsEr triple embedded with B-type oxidized butadiene and average molecular weight of 4,200. Copolymers prepared by reacting methylene chloride with sodium hydroxide in the presence of one kind of gasifier extending Μ A buried contact multiblock copolymer according to the method of Example 1 copolymer prepared using the following reagents: sodium hydroxide 20g

10 g of dichloromethane 160 · I E37B11E37 (in 50b1 dioxane). The polymer was isolated as described in Example 1. Mw value ~ 243,000 and Mw / Mn ~ 2 ° Yield > 95X ° g as measured by GPC Example 7 Commercially available Plu "onicTM F108 ErP-Er Ξ block copolymer; and a polyethylene with an average molecular weight of 6000 Second fermentation (PEG 6000) and second gas kebab -9- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Binding Ministry of Economic Affairs Employees of the Central Bureau of Standards #Cooperative Society Printing 83.3.10,000 A7 B7 401431 V. Description of the Invention (In the presence of [Sodium Oxide, prepare a multi-block copolymer connected by oxidized dynein. According to the method described in Example 1 Copolymers were prepared using the following reagents: 30 g of sodium hydroxide, 200 m of dichloromethane, 1 ε120P5, β ι 2θ, 15 g (in dichloromethane *), PEG 6000, 15 g (in dichloromethane), * E 1 2 β P 5 β E! 2 β The mixture with PEG 6 0 0 0 was dissolved in 100 a 1 methylene chloride. The polymer was isolated as described in Example 1. The values measured by GPC were ~ 170,500 and Mw / Mn ~ 2. Yield> 95%. (Please read the precautions on the back before filling in the clothing page)

'5J Printed by the Ministry of Economic Affairs and the Central Bureau of Standards and Industry β-Consumer Cooperatives -10- Unprinted paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 83.3.10,000 A7 B7 401431 V. Description of the invention (in " [The reaction was carried out in the presence of sodium oxide to prepare a multi-block copolymer linked by oxidized dyne. According to the method described in Example 1, the copolymer was prepared with the following reagents: sodium hydroxide 30g dichloromethane 200η 1 Ε120Ρ5βΕι2θ 15g (in the second atmosphere In methane *) PEG 6000 15g (in two atmosphere methane)) * Use a mixture of E 1 2 β P 5 β E! 2 β and PEG 6 0 0 0 to dissolve in 100 0 a 1 methylene chloride. According to the example 1Describes isolated polymer. Values measured by GPC ~ 170,500 and Mw / Mn ~ 2. Yield> 95%. (Please read the precautions on the back before filling in the clothing page)

'5J Printed by the Ministry of Economic Affairs and the Central Bureau of Standards, β Industrial Consumer Cooperatives. -10- Not applicable to Chinese Standard (CNS) A4 (210 X 297 mm) for paper sizes. 83.3.10,000

Claims (1)

Patent application No. 84102792, please amend Fan Liguo (November 88) g D8 VI. Patent application scope V i: \ S · · · · ·;, ya,, — — — — — — id segment copolymer 》 It is determined by gel permeation chromatography with molecular units from 50,000 to 50,000, and has the following repeating units of the order-[(P „JCH2〇-) x ([E.] CH2〇) y -Where P is propylene oxide; E is ethylene oxide; η is an integer from 2 to 70; η is an integer from 2 to 250; X is an integer from 1 to 100; and y is a fluorene number from 1 to 100. 2. An embedded Segment copolymers * whose M gel permeation chromatography has a molecular weight from 50, 000 to 500,000, and has the following repeating units in random order-[(ErP.Er) CH2O] z-where P is propylene oxide; E-based ethylene oxide; r is an integer from 2 to 135; s is an integer from 15 to 65; and z is an integer from 2 to 100. 3. One step is to prepare one or more polyethylene oxide blocks and one or more A method for high molecular weight block copolymers of polyoxidized (high carbon butane) blocks, wherein: (a) the molecular weight of the block copolymer is determined by gel permeation chromatography from 10,000 to 500,000; and < b) The method does not require the addition of heat, and the method includes one or more compounds selected from the group consisting of poly (ethylene glycol), poly (high-carbon alkanediol), and dihydroxy terminated polymers formed by block copolymers of Reacts with dihalomethane in the presence of alkali at a temperature from 20 to 40C. The size of this paper is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 丨 o IJ shoulder (please read the precautions on the back before filling this page- * The Consumers Cooperative of the Central Economic and Technical Bureau of the Ministry of Online Economics printed the patent application No. 84102792. Please amend the revised version (November 1988) g D8 VI. Application scope V i: \ S · · · · ·; , — — —; U —id segment copolymers “It is determined by gel permeation chromatography with a molecular weight from 50,000 to 50,000, and has the following repeating units in the order-[(P„ JCH2 〇-) x ([E.] CH2〇) y- where P is propylene oxide; E-based ethylene oxide; η is an integer from 2 to 70; η is an integer from 2 to 250; X is an integer from 1 to 100; and The number of Y series is from 1 to 100. 2. A block copolymer * whose M gel permeation chromatography has a measurement from 50, 000 to 500, 0 A molecular weight of 00 and a random repeat of the following repeating units-[(ErP.Er) CH2〇] z- where P is propylene oxide; E is ethylene oxide; r is an integer from 2 to 135; s is an integer from 15 to 65; and z is an integer from 2 to 100. 3. A method for preparing a high molecular weight block copolymer containing one or more polyoxyethylene blocks and one or more polyoxy (high-carbon butane) blocks, wherein: (a) a block copolymer The molecular weight of M gel permeation chromatography is from 10,000 to 500,000; and < b) method does not require the addition of heat, wherein the method includes one or more selected from the group consisting of poly (ethylene glycol), poly (high-carbon alkanediol), and The group of dihydroxy-terminated polymers formed by its block copolymers reacts with dihalomethane in the presence of alkali at a temperature from 20 to 40C. This paper applies Chinese National Standard (CNS) A4 specifications (210X297 mm). ) O IJ Shoulder (Please read the notes on the back before filling out this page-* Printed by the Consumer Cooperatives of the Central Bureau of Standards and Commerce of the Ministry of Economic Affairs \ AB B8 C8 —_____ D8 _____ VI. Application for patents ranging from 2 to 36 hours, and separation The block copolymer obtained by drying and refining ° 4. The method according to item 3 of the patent application. One or more dibasic terminal triblock copolymers have a molecular weight from 4,000 to 15,000 ° 5. According to the patent application Method 3, one of them Dihydroxy-terminated triblock copolymers of various ethylene glycols and malonase or succinylase · If required, it includes one or more poly (ethylene glycol) and / or poly (malonyl alcohol) dimer The terminal polymer is reacted with dimethylamine in solution in the presence of sickle. 06. According to the method in the scope of the application, the dihalomethane is digas. 7 · According to the scope of the application, the third scope The method, in which the molecular weight of the block copolymer is from 50,000 to 250,000. (Please read the note on the back ^ this page first) (CNS > A4 grid (210X297 mm)