WO2019196048A1 - 用于生产(甲基)丙烯酸2-二甲氨基乙酯的方法 - Google Patents

用于生产(甲基)丙烯酸2-二甲氨基乙酯的方法 Download PDF

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WO2019196048A1
WO2019196048A1 PCT/CN2018/082774 CN2018082774W WO2019196048A1 WO 2019196048 A1 WO2019196048 A1 WO 2019196048A1 CN 2018082774 W CN2018082774 W CN 2018082774W WO 2019196048 A1 WO2019196048 A1 WO 2019196048A1
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Prior art keywords
dibutyltin oxide
reaction
acrylate
recycled
fresh
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PCT/CN2018/082774
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English (en)
French (fr)
Inventor
法维罗塞德里克
基弗约翰
凌静
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爱森（中国）絮凝剂有限公司
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Priority to FIEP18914519.6T priority Critical patent/FI3778554T3/fi
Priority to JP2020555136A priority patent/JP7163406B2/ja
Priority to US17/041,746 priority patent/US20210114969A1/en
Priority to CN201880069829.3A priority patent/CN111556862B/zh
Priority to PCT/CN2018/082774 priority patent/WO2019196048A1/zh
Priority to EP18914519.6A priority patent/EP3778554B1/en
Priority to CN202010515581.8A priority patent/CN111635326A/zh
Priority to KR1020207028890A priority patent/KR102586500B1/ko
Publication of WO2019196048A1 publication Critical patent/WO2019196048A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/10—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/10—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of a carbon skeleton containing rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to the production of 2-dimethylaminoethyl (meth)acrylate (also known as DMAE (M) A or (M) )Methods.
  • the 2-dimethylaminoethyl (meth)acrylate monomer is typically quaternized, for example quaternized with methyl chloride, dialkyl sulfate or benzyl chloride, and then polymerized to produce a cationic polymer.
  • These polymers are used in many industries such as water treatment, paper making, household and personal care, tertiary oil recovery.
  • the alkyl (meth)acrylate may be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester. Methyl (meth)acrylate is generally preferred.
  • metal alkoxides can be used as transesterification catalysts, such as aluminum (III) isopropoxide, or tetraalkoxides of titanium (IV) acid, such as those described in US Pat. No. 8,067,637 or CN 105330556.
  • acetylacetonate derivatives as catalysts, such as the metal complex zirconium acetylacetonate, aluminum acetylacetonate, zinc acetylacetonate, iron acetylacetonate, for example as described in US 7,071,351 or WO 2001/157645.
  • DBTO is a particularly advantageous catalyst because it is very active at low doses and can be recycled multiple times and minimizes the formation of impurities, which is related to the stoichiometric amount of catalyst associated with the starting material.
  • the derivative catalyst is reversed.
  • DBTO tends to be inactivated during recycling and needs to be replaced periodically, which is expensive and produces toxic waste that is difficult to manage and handle.
  • the reaction product contains more impurities.
  • impurities are Michael adducts of methanol or dimethylaminoethanol reacted with methyl (meth)acrylate, dimethylaminoethyl (meth)acrylate or (meth)acrylic acid.
  • the catalyst activity of the catalyst is sufficient to limit the formation of impurities, the catalyst is separated from the reaction mixture and recycled.
  • the DBTO recovered in the first reaction typically, in the first reaction, fresh DBTO is used as the catalyst. After the reaction, 100% of the DBTO recovered from the first reaction was recycled to the second reaction. After the second reaction, 100% of the DBTO recovered from the second reaction is recycled to the third reaction. However, the DBTO recovered in the third reaction did not have sufficient catalytic activity for the fourth reaction. In other words, if the DBTO is used in the fourth reaction, the quality of 2-dimethylaminoethyl (meth)acrylate is lower because it will contain a large amount of impurities.
  • the problem to be solved by the present invention is to improve the efficiency of the process for producing 2-dimethylaminoethyl (meth)acrylate and the quality of the resulting monomer.
  • the invention is based on two principles.
  • the first principle is to continuously add a composition comprising methyl (meth) acrylate, dimethylaminoethanol to compensate for the volume reduction due to azeotropic distillation and removal of low molecular weight alcohol.
  • the second principle is to add a portion of the fresh DBTO in addition to the recycled DBTO in at least the subsequent batch reaction.
  • the present invention provides a process for the production of 2-dimethylaminoethyl (meth)acrylate comprising at least two consecutive batch reactions in which (meth)acrylic acid is used in each batch reaction Methyl ester, dimethylaminoethanol, a solvent and dibutyltin oxide as a catalyst are added as an initial charge to a stirred reactor equipped with a distillation column, wherein azeotropic distillation is continuously carried out during the reaction, wherein the azeotrope is due to the azeotropy
  • the volume reduction caused by distillation is compensated by continuously adding a composition comprising methyl (meth)acrylate and dimethylaminoethanol to keep the volume in the reactor constant, and the composition may further comprise dibutyltin oxide.
  • the method includes:
  • dibutyltin oxide used as a catalyst is fresh dibutyltin oxide
  • dibutyltin oxide from the first batch reaction is recovered from the reaction mixture of the first batch reaction, and the dibutyltin oxide from the first batch reaction constitutes recycled dibutyltin oxide ;
  • At least a second batch reaction in which at least 65% by weight of the recycled dibutyltin oxide is used together with fresh dibutyltin oxide as a catalyst for the second batch reaction:
  • the mass ratio of recycled dibutyltin oxide to fresh dibutyltin oxide is from 100/0 to 0/100.
  • fresh dibutyltin oxide refers to the first dibutyltin oxide used in the reaction.
  • fresh dibutyltin oxide is not recovered from the previous reaction to produce 2-dimethylaminoethyl (meth)acrylate.
  • new dibutyltin oxide is also used in the present invention and has the same meaning as fresh dibutyltin oxide.
  • the process of the invention comprises at least one subsequent batch reaction wherein at least 65% by weight of the recycled dibutyltin oxide from the previous reaction is used as the reaction together with fresh dibutyltin oxide Catalyst:
  • the mass ratio of recycled dibutyltin oxide to fresh dibutyltin oxide from the previous reaction is 100/0 to 0/100.
  • the process of the invention is a multistage batch reaction comprising recycling a catalyst (DBTO) to a subsequent reaction, adding a quantity of fresh or new catalyst to the recycled catalyst, and using the catalyst in a subsequent reaction .
  • DBTO catalyst
  • composition comprising methyl (meth)acrylate and dimethylaminoethanol during the reaction enables the use of the maximum volume of the reactor, which is advantageous in terms of productivity.
  • the composition may also comprise dibutyltin oxide, which is preferred.
  • This combination of maximum use of the reactor volume of the present invention, recycling of DBTO, and specific ratios of fresh DBTO additions enables improved efficiency of the process for producing 2-dimethylaminoethyl (meth)acrylate and improves such singles.
  • the quality of the body Since 2-dimethylaminoethyl (meth)acrylate contains less impurities, its quality is better.
  • the monomer quality was also more consistent in subsequent batches because the catalyst activity remained constant at the optimum concentration for all batches.
  • Another advantage of the process of the present invention is that the total consumption of catalyst per batch is reduced, and thus the total amount of waste produced per batch is reduced.
  • the method of the invention comprises a total of at least 3, preferably 4, more preferably 5, even more preferably 6, even more preferably 7, even more preferably 8, even more preferably Nine, even more preferably 10, up to 20 batch reactions in which recycled dibutyltin oxide from the previous reaction is used in combination with fresh dibutyltin oxide as a catalyst.
  • the process of the invention comprises at least 2, preferably 3, more preferably 4, even more preferably 5, even more preferably 6 or even more preferably 7, even more preferably 8, even more preferably 9 and up to 19 batch reactions, wherein according to the invention, recycled dibutyltin oxide and fresh dibutyltin from the previous reaction The oxide combination is used as a catalyst.
  • the reaction according to the present invention is carried out in a stirred reactor equipped with a distillation column and a temperature rising device.
  • a solvent, methyl (meth)acrylate, dimethylaminoethanol, and dibutyltin oxide (DBTO) are added to the reactor.
  • the reaction is initiated at elevated temperatures as is known in the art.
  • the methanol produced by the reaction is continuously evaporated together with some solvent and some (meth) acrylate, and is introduced into a distillation column.
  • the recovered solvent is recycled after separation from the alcohol and the (meth) acrylate.
  • the solvent used in the process of the invention is preferably an inert solvent and is typically a C6 to C12 linear, cyclic or branched alkane.
  • a preferred solvent is hexane which forms an azeotrope with a low molecular weight alcohol, especially with methanol.
  • the volume reduction due to evaporation of these products is continuously compensated by continuously adding an equal volume of a composition comprising methyl (meth)acrylate and dimethylaminoethanol.
  • the composition further comprises dibutyltin oxide and a solvent.
  • the composition is the same as the composition originally added to the reactor prior to the start of the reaction.
  • 2-dimethylaminoethyl (meth)acrylate is recovered from the reaction mixture and purified, usually by distillation.
  • DBTO is also recovered and recycled. Those skilled in the art know how to perform these processes.
  • reaction of the process of the invention is carried out in the same reactor, but can also be carried out in separate reactors.
  • the amount of fresh dibutyltin oxide in each subsequent reaction is from 0.1% to 20% by weight, preferably from 0.5% to 15% by weight, based on the recycled dibutyltin oxide, even more preferably 0.5% by weight to 10% by weight.
  • the mass ratio of recycled dibutyltin oxide to fresh dibutyltin oxide added to the initial charge of each subsequent reaction is from 97/3 to 85/15, preferably from 95/5 to 87/ 13, even more preferably 90/10, even more preferably 99/1.
  • each subsequent reaction in a composition that is continuously added to compensate for azeotropic distillation to maintain a constant volume in the reactor, in the case of dibutyltin oxide, recycled dibutyltin
  • the mass ratio of the oxide to the fresh dibutyltin oxide is from 95/5 to 5/95, preferably from 90/10 to 10/90.
  • the dibutyltin oxide added to the initial charge for each subsequent reaction and the composition continuously added to compensate for the azeotropic distillation, the quality of the recycled dibutyltin oxide and fresh dibutyltin oxide The ratio is the same.
  • the preferred mass ratio is preferably from 97/3 to 85/15, preferably from 95/5 to 87/13, even more preferably from 90/10, even more preferably 99/1.
  • the invention also provides 2-dimethylaminoethyl (meth)acrylate obtained according to the process of the invention.
  • the obtained monomeric 2-dimethylaminoethyl (meth)acrylate has a good quality because it contains less impurities.
  • the monomer quality as the batch is increased is also improved because it is more uniform than the method in which no fresh catalyst is added and there is no compensatory volume reduction (quality decreases significantly with batch increase). This is because the method of the present invention enables a more uniform effect as the catalyst is increased in batches.
  • the invention also provides a mixture of 2-dimethylaminoethyl (meth)acrylate recovered from the reaction mixture obtained according to the process of the invention after the separation step.
  • the 2-dimethylaminoethyl (meth)acrylate mixture contains less impurities and is of better quality.
  • the present invention also provides 2-dimethylaminoethyl (meth)acrylate of the present invention in a quaternized form.
  • the quaternization is carried out, for example, with dimethyl sulfate, diethyl sulfate, benzyl chloride or methyl chloride or a mixture thereof, and preferably with methyl chloride to convert the tertiary amine to a quaternary ammonium.
  • the present invention also provides a polymer prepared from the quaternized form of 2-dimethylaminoethyl (meth)acrylate of the present invention.
  • Any polymerization method such as gel polymerization, liquid phase polymerization or emulsion polymerization can be used. Any form of polymer can be obtained, such as powders, emulsions, dispersions, solutions.
  • the polymers of the invention are preferably water soluble, but may also be water swellable.
  • Additional monomers can be used in combination with the quaternized form of 2-dimethylaminoethyl (meth)acrylate to produce the polymers of the present invention.
  • These monomers can be selected from the following list:
  • Nonionic monomers acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-vinylpyrrolidone, N-vinylformamide, N-ethylene Imidazole, polyethylene glycol methacrylate, diacetone acrylamide, N-isopropyl acrylamide, 2-hydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate Ester, 2,3-dihydroxypropyl methacrylate, N-tert-butyl acrylamide,
  • anionic monomers unsalted, partially salted or fully salted acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), methacrylic acid, itaconic acid, maleic acid, sulphur Acid allyl ester,
  • Cationic monomers diallyldimethylammonium chloride (DADMAC), acrylamidodialkylaminopropyl, methacrylamidodialkylaminopropyl, and acidified or quaternary ammonium salts thereof.
  • DADMAC diallyldimethylammonium chloride
  • acrylamidodialkylaminopropyl acrylamidodialkylaminopropyl
  • methacrylamidodialkylaminopropyl acrylamidodialkylaminopropyl
  • acidified or quaternary ammonium salts thereof acidified or quaternary ammonium salts thereof.
  • a polyethylenically unsaturated monomer having at least two unsaturated functional groups for example, a vinyl group, an allyl group, an acrylic group, and an epoxy functional group
  • unsaturated functional groups for example, a vinyl group, an allyl group, an acrylic group, and an epoxy functional group
  • MCA methylene bis acrylamide
  • triallylamine for example, triallylamine
  • tetraallyl ammonium chloride or macroinitiators
  • macroinitiators such as polyperoxides, polyazo compounds, and transfer polymerization agents such as polythiol polymers.
  • the polymer according to the invention is not limited in terms of molecular weight.
  • the polymer preferably has a weight average molecular weight of from 5,000 g/mol to 100,000 g/mol, or a weight average molecular weight of from 100,000 g/mol to 1,000,000 g/mol, or a weight average molecular weight of from 1,000,000 g/mol to 30,000,000 g/mol.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC).
  • the invention also provides the polymer of the invention in water treatment, sludge dewatering, papermaking process, agriculture, cosmetics and cleaning composition, textile process, oil and gas recovery process such as enhanced oil recovery, fracturing, mining operations such as tailings treatment use.
  • the first batch was carried out with fresh DBTO.
  • the 12 liter jacketed reactor was equipped with a stirrer, a packed column with 10 theoretical plates, a reflux condenser and a decanter. To the reactor were charged 950 g of hexane, 6520 g of methyl acrylate and 3380 g of dimethylaminoethanol.
  • the reaction mixture was heated to 80 ° C with an external heater. During the reaction, the feedstock and catalyst are continuously added to the reactor to compensate for the reduced volume.
  • the continuous feed consisted of 105.2 g of hexane, 722 g of methyl acrylate, and 374 g of dimethylaminoethanol.
  • reaction mixture was then transferred to a still pot equipped with a rectification column. 5160 g of 2-dimethylaminoethyl acrylate as a distillate was recovered, corresponding to a yield of 95%.
  • the 2-dimethylaminoethyl acrylate was analyzed by GC-FID to a purity of 99.9%.
  • DBTO is retained in the kettle as a high boiler and used as a recycled DBTO in the following examples:
  • the continuous feed consisted of 105.2 g of hexane, 722 g of methyl acrylate, 374 g of dimethylaminoethanol and 12.1 g of recycled DBTO (corresponding to 10% by weight of recycled DBTO from the previous batch).
  • DBTO recycled DBTO
  • a certain amount of fresh DBTO was added, and the weight % of 12.1 g of recycled DBTO was mentioned in Table 1.
  • DBTO Waste The total amount of fresh DBTO used during the entire batch divided by the number of batches.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

一种以多级分批反应生产(甲基)丙烯酸2-二甲氨基乙酯的方法，包括使催化剂(DBTO)再循环到后续反应中、向再循环的催化剂中添加一定量的新鲜催化剂、在后续反应中使用所述催化剂，并且其中由于共沸蒸馏而引起的体积减小通过连续添加包含(甲基)丙烯酸甲酯和二甲氨基乙醇的组合物进行补偿，从而在反应期间保持反应器中的体积恒定。

Description

用于生产(甲基)丙烯酸2-二甲氨基乙酯的方法 技术领域
本发明涉及用于生产(甲基)丙烯酸2-二甲氨基乙酯(也称为DMAE(M)A或(M)
Figure PCTCN2018082774-appb-000001
)的方法。
背景技术
通常使(甲基)丙烯酸2-二甲氨基乙酯单体季铵化，例如用甲基氯、硫酸二烷基酯或苄基氯季铵化，然后聚合以产生阳离子聚合物。这些聚合物被用于许多行业，例如水处理、造纸、家庭和个人护理、三次采油。
用有机锡化合物催化酯交换反应是公知的。在所关注的(甲基)丙烯酸酯中，(甲基)丙烯酸2-二甲氨基乙酯通过用锡氧化物衍生物(例如，二丁基锡氧化物(DBTO))作为催化剂的(甲基)丙烯酸烷基酯和二甲氨基乙醇的酯交换反应获得。催化剂的作用是使平衡移动至产生更多的(甲基)丙烯酸2-二甲氨基乙酯和减少杂质形成。
(甲基)丙烯酸烷基酯可以是(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯。(甲基)丙烯酸甲酯通常是优选的。
还已知的是，可以使用其他金属醇盐作为酯交换催化剂，例如异丙醇铝(III)，或者钛(IV)酸四烷醇盐，例如US 8,067,637或CN 105330556中所述的。还使用乙酰丙酮化物衍生物作为催化剂，例如金属络合物乙酰丙酮锆、乙酰丙酮铝、乙酰丙酮锌、乙酰丙酮铁，例如US 7,071,351或WO 2001/157645中所述的。DBTO是一种特别有利的催化剂，因为它在低剂量下的活性非常高，可以再循环多次并且使杂质形成最小化，这与需要与起始材料相关的化学计算量的催化剂的钛酸酯衍生物催化剂相反。
尽管有这样的优点，但是DBTO往往会在再循环时失活并且需要定期更换，这是很昂贵的，并且产生难以管理和处理的有毒废物。
当DBTO开始失活时，反应产物含有更多的杂质。通常，在用DBTO作为催化剂的(甲基)丙烯酸甲酯和二甲氨基乙醇的反应中，存在作为副产物产生的杂质，这降低了(甲基)丙烯酸2-二甲氨基乙酯的品质。这些杂质是甲醇或二甲氨基乙醇与(甲基)丙烯酸甲酯、(甲基)丙烯酸二甲氨基乙酯或(甲基)丙烯酸反应的Michael加合物。
为了限制杂质如由低分子量醇(甲醇)形成的Michael加合物的形成，已知在溶剂中进行反应。这使得能够在连续共沸蒸馏期间消除低分子量醇。这种方法的缺点是反应器中的体积不断减小使得该方法的生产效率较低。
在反应结束时，如果催化剂的催化剂活性足以限制杂质的形成，则将催化剂从反应混合物中分离出来并进行再循环。
通常，在第一反应中，使用新鲜DBTO作为催化剂。在该反应之后，使从第一反应中回收的DBTO的100％再循环到第二反应中。在第二反应之后，使从第二反应中回收的DBTO的100％再循环到第三反应中。但是在第三反应中回收的DBTO没有足够的催化活性以用于第四反应。换句话说，如果在第四反应中使用该DBTO，则(甲基)丙烯酸2-二甲氨基乙酯的品质较低，因为其会含有大量的杂质。
发明内容
本发明要解决的问题是改善生产(甲基)丙烯酸2-二甲氨基乙酯的方法的效率和所得单体的品质。
出乎意料地发现，这可以通过反应器体积的更有效使用和催化剂的更有效使用来完成。本发明基于两个原则。第一个原则是连续添加包含(甲基)丙烯酸甲酯、二甲氨基乙醇的组合物，以补偿由于共沸蒸馏和低分子量醇的移除而引起的体积减小。第二个原则是在至少后续分批反应中除了再循环的DBTO之外还添加一部分新鲜DBTO。
本发明提供了一种用于生产(甲基)丙烯酸2-二甲氨基乙酯的方法，其包括至少两个连续的分批反应，其中在每个分批反应中，将(甲基)丙烯酸甲酯、二甲氨基乙醇、溶剂和作为催化剂的二丁基锡氧化 物作为初始进料添加到配备有蒸馏塔的搅拌反应器中，其中在反应期间连续地进行共沸蒸馏，其中由于所述共沸蒸馏而引起的体积减小通过连续添加包含(甲基)丙烯酸甲酯和二甲氨基乙醇的组合物进行补偿，从而使反应器中的体积保持恒定，该组合物还可以包含二丁基锡氧化物，所述方法包括：
-第一分批反应，其中用作催化剂的二丁基锡氧化物是新鲜二丁基锡氧化物；
-分离步骤，其中从第一分批反应的反应混合物中回收来自第一分批反应的二丁基锡氧化物，并且所述来自第一分批反应的二丁基锡氧化物构成再循环的二丁基锡氧化物；
-至少第二分批反应，其中再循环的二丁基锡氧化物的至少65重量％与新鲜二丁基锡氧化物一起用作第二分批反应的催化剂：
○其中基于来自第一分批反应的再循环的二丁基锡氧化物，新鲜二丁基锡氧化物的量为0.1重量％至35重量％，
○其中初始进料中添加的再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比为220/1至80/20，
○其中连续添加以补偿共沸蒸馏的组合物中，在包含二丁基锡氧化物的情况下，再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比为100/0至0/100。
根据定义，新鲜二丁基锡氧化物是指首次用于反应的二丁基锡氧化物。换句话说，新鲜二丁基锡氧化物不是从产生(甲基)丙烯酸2-二甲氨基乙酯的前一反应中回收的。术语新的二丁基锡氧化物也在本发明中使用，并且与新鲜二丁基锡氧化物具有相同的含义。
在一个优选实施方案中，本发明的方法包括至少一个后续的分批反应，其中来自前一反应的再循环的二丁基锡氧化物的至少65重量％与新鲜二丁基锡氧化物一起用作所述反应的催化剂：
○其中基于来自前一反应的再循环的二丁基锡氧化物，新鲜二丁基锡氧化物的量为0.1重量％至35重量％，
○其中初始进料中添加的来自前一反应的再循环的二丁基 锡氧化物与新鲜二丁基锡氧化物的质量比为220/1至80/20，
○其中连续添加以补偿共沸蒸馏的组合物中，在包含二丁基锡氧化物的情况下，来自前一反应的再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比为100/0至0/100。
本发明的方法是多级分批反应，其包括使催化剂(DBTO)再循环到后续反应中，向再循环的催化剂中添加一定量的新鲜或新的催化剂，以及在后续反应中使用所述催化剂。
在反应期间连续添加包含(甲基)丙烯酸甲酯和二甲氨基乙醇的组合物使得能够使用反应器的最大体积，这在生产率方面是有利的。该组合物还可以包含二丁基锡氧化物，这是优选的。
本发明的反应器体积的这种最大使用、DBTO的再循环和特定比例的新鲜DBTO添加的组合使得能够改善生产(甲基)丙烯酸2-二甲氨基乙酯的方法的效率并改善这种单体的品质。因为(甲基)丙烯酸2-二甲氨基乙酯含有较少的杂质，其品质更好。在后续的批次中，单体品质也更为一致，因为对于所有批次，催化剂活性在最佳浓度下均保持恒定。本发明的方法的另一个优点是每批次的催化剂总消耗量减少，并因此每批次产生的废物总量减少。
在本发明的一个优选实施方案中，本发明的方法包括总共至少3个，优选4个，更优选5个，甚至更优选6个，甚至更优选7个，甚至更优选8个，甚至更优选9个，甚至更优选10个，多至20个分批反应，其中根据本发明，来自前一反应的再循环的二丁基锡氧化物与新鲜二丁基锡氧化物组合用作催化剂。
换言之，这意味着，在涉及仅使用新鲜催化剂的本发明的方法的第一反应之后，本发明的方法包括至少2个，优选3个，更优选4个，甚至更优选5个，甚至更优选6个，甚至更优选7个，甚至更优选8个，甚至更优选9个，多至19个分批反应，其中根据本发明，来自前一反应的再循环的二丁基锡氧化物与新鲜二丁基锡氧化物组合用作催化剂。
根据本发明的反应在配备有蒸馏塔和升温装置的搅拌反应器中 进行。通常，将溶剂、(甲基)丙烯酸甲酯、二甲氨基乙醇和二丁基锡氧化物(DBTO)添加到反应器中。如本领域已知的，在温度升高的情况下引发反应。由反应产生的甲醇与一些溶剂和一些(甲基)丙烯酸酯一起连续蒸发，并被导入蒸馏塔中。优选地，在从醇和(甲基)丙烯酸酯中分离之后使回收的溶剂进行再循环。
本发明的方法中使用的溶剂优选为惰性溶剂，并且典型地为C6至C12的线性、环状或支化烷烃。优选的溶剂为与低分子量醇(尤其是与甲醇)形成共沸混合物的己烷。
根据本发明，由于这些产物蒸发而引起的体积减小通过连续添加等体积的包含(甲基)丙烯酸甲酯和二甲氨基乙醇的组合物来连续补偿。在一个优选实施方案中，该组合物还包含二丁基锡氧化物和溶剂。在一个更优选实施方案中，组合物与反应开始之前最初添加到反应器中的组合物相同。
本领域技术人员知道如何进行该反应并且可以参考文献US2012/0123148。本发明的方法不需要特定的附加方式来进行反应以通过用二丁基锡氧化物(DBTO)作为催化剂的(甲基)丙烯酸甲酯和二甲氨基乙醇的酯交换来获得(甲基)丙烯酸2-二甲氨基乙酯。该反应的化学品比例、温度和其他参数是公知的。
在每个分批反应结束时，从反应混合物中回收(甲基)丙烯酸2-二甲氨基乙酯，并进行纯化，通常通过蒸馏进行纯化。如本发明所述，DBTO也被回收并进行再循环。本领域技术人员知道如何进行这些过程。
在一个优选实施方案中，本发明的方法的反应在同一反应器中进行，但也可以在不同的反应器中进行。
在一个优选实施方案中，在根据本发明的第二分批反应和/或后续的分批反应中，从前一反应回收的再循环的二丁基锡氧化物的至少80重量％，优选至少85重量％，更优选至少90重量％与新鲜二丁基锡氧化物一起用作后续反应的催化剂。
在一个优选实施方案中，每个后续反应中的新鲜二丁基锡氧化物 的量为基于再循环的二丁基锡氧化物的0.1重量％至20重量％，优选0.5重量％至15重量％，甚至更优选0.5重量％至10重量％。
在一个优选实施方案中，每个后续反应的初始进料中添加的再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比为97/3至85/15，优选95/5至87/13，甚至更优选90/10，甚至更优选99/1。
在一个优选实施方案中，在每个后续反应中，在连续添加以补偿共沸蒸馏从而保持反应器中的体积恒定的组合物中，在包含二丁基锡氧化物的情况下，再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比为95/5至5/95，优选90/10至10/90。
在一个优选实施方案中，对于每个后续反应的初始进料中添加的二丁基锡氧化物和连续添加以补偿共沸蒸馏的组合物，再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比是相同的。在这种情况下，优选的质量比优选为97/3至85/15，优选95/5至87/13，甚至更优选90/10，甚至更优选99/1。
本发明还提供了根据本发明的方法获得的(甲基)丙烯酸2-二甲氨基乙酯。所获得的单体(甲基)丙烯酸2-二甲氨基乙酯具有较好的品质，因为其含有较少的杂质。与没有添加新鲜催化剂并且没有补偿体积减小的方法(品质随着批次增加显著下降)相比，随着批次增加的单体品质也得到改善，因为其更为均匀。这是因为本发明的方法使得随着批次增加催化剂的作用能够更均匀。
本发明还提供了在分离步骤之后从根据本发明的方法获得的反应混合物中回收的(甲基)丙烯酸2-二甲氨基乙酯混合物。所述(甲基)丙烯酸2-二甲氨基乙酯混合物含有较少的杂质，并且品质较好。
本发明还提供了季铵化形式的本发明的(甲基)丙烯酸2-二甲氨基乙酯。季铵化例如用硫酸二甲酯、硫酸二乙酯、苄基氯或甲基氯或其混合物，并且优选用甲基氯进行以将叔胺转化成季铵。
本发明还提供了用季铵化形式的本发明的(甲基)丙烯酸2-二甲氨基乙酯制备的聚合物。可以使用任何聚合方法，例如凝胶聚合、液相聚合或乳液聚合。可以获得任何形式的聚合物，例如粉末、乳液、分 散体、溶液。本发明的聚合物优选是水溶性的，但也可以是水可溶胀的。
可以与季铵化形式的(甲基)丙烯酸2-二甲氨基乙酯组合使用另外的单体以生产本发明的聚合物。这些单体可以选自以下列表：
-非离子单体：丙烯酰胺、甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、N-乙烯基吡咯烷酮、N-乙烯基甲酰胺、N-乙烯基咪唑、聚乙二醇的甲基丙烯酸酯、双丙酮丙烯酰胺、N-异丙基丙烯酰胺、丙烯酸2-羟乙酯、丙烯酸2,3-二羟丙酯、甲基丙烯酸2-羟乙酯、甲基丙烯酸2,3-二羟丙酯、N-叔丁基丙烯酰胺，
-阴离子单体：未成盐的、部分成盐的或完全成盐的丙烯酸、2-丙烯酰胺基-2-甲基丙磺酸(ATBS)、甲基丙烯酸、衣康酸、马来酸、磺酸烯丙酯，
-阳离子单体：二烯丙基二甲基氯化铵(DADMAC)、丙烯酰胺基二烷基氨基丙基、甲基丙烯酰胺基二烷基氨基丙基、及其酸化盐或季铵盐。
-结构剂：具有至少两个不饱和官能团(例如乙烯基、烯丙基、丙烯酸类和环氧官能团)的多烯键式不饱和单体，并且可以提及例如亚甲基双丙烯酰胺(MBA)、三烯丙基胺、四烯丙基氯化铵，或者大分子引发剂如多过氧化物、多偶氮化合物和转移聚合剂如聚硫醇聚合物。
根据本发明的聚合物在分子量方面不受限制。所述聚合物的重均分子量优选为5,000g/mol至100,000g/mol，或者重均分子量为100,000g/mol至1,000,000g/mol，或者重均分子量为1,000,000g/mol至30,000,000g/mol。重均分子量通过凝胶渗透色谱(GPC)来测量。
本发明还提供了本发明的聚合物在水处理、污泥脱水、造纸工艺、农业、化妆品和清洁组合物、纺织工艺、油气回收工艺如强化采油、压裂、采矿作业如尾矿处理中的用途。
具体实施方式
现在将通过以下实施例更详细地说明本发明。
实施例
所有实施例的共同点：第一批次用新鲜DBTO进行。
12升夹套反应器配备有搅拌器、具有10个理论塔板的填充塔、回流冷凝器和倾析器。向反应器中加入950g己烷、6520g丙烯酸甲酯和3380g二甲氨基乙醇。
加入121g新鲜DBTO。为了避免聚合反应，还向反应器中加入10g吩噻嗪。
用外部加热器将反应混合物加热至80℃。在反应期间，向反应器中连续添加原料和催化剂以补偿减小的体积。连续进料由105.2g己烷、722g丙烯酸甲酯、374g二甲氨基乙醇构成。
30分钟之后，DBTO活化并且产生己烷/甲醇/丙烯酸甲酯的共沸混合物进入蒸馏塔中。使馏出物与水混合并沉降。有机相被送回反应器。
加热10小时之后，回收1210g甲醇，反应结束。
然后将反应混合物转移至配备有精馏塔的蒸馏釜中。回收作为馏出物的5160g丙烯酸2-二甲氨基乙酯，相当于产率为95％。
通过GC-FID分析丙烯酸2-二甲氨基乙酯，其纯度为99.9％。
蒸馏之后，DBTO作为高沸点化合物保留在釜中，并作为再循环的DBTO在以下实施例中使用：
实施例1至5：
在之前描述的12升反应器中，向反应器中加入与上述第一批次反应相同量的丙烯酸甲酯、二甲氨基乙醇和己烷。在后续批次中重复使用来自前一批次的再循环的DBTO的100重量％，相当于121g。
最初将108.9g再循环的DBTO加入到反应器中，这相当于来自前一批次的再循环DBTO的90％重量。此外，最初将一定量的新鲜DBTO加入到反应器中，表1中提到了关于108.9g再循环的DBTO的重量％。
在反应期间，向反应器中连续添加原料和催化剂以补偿减小的体 积。连续进料由105.2g己烷、722g丙烯酸甲酯、374g二甲氨基乙醇和12.1g再循环的DBTO(相当于来自前一批次的再循环的DBTO的10％重量)构成。此外，加入一定量的新鲜DBTO，表1中提到了关于12.1g再循环的DBTO的重量％。
反应结束并用精馏塔纯化之后，通过GC-FID分析最终的丙烯酸二甲氨基乙酯。当最终的丙烯酸二甲氨基乙酯的纯度降至低于99.8％时，再循环的DBTO被认为没有足够的活性。
对比例：
使用与实施例1至5相同的过程，不同之处在于，没有向反应器中添加一定量的新鲜的DBTO(仅添加再循环的DBTO)，并且在反应期间没有进行原料和催化剂的连续进料以补偿因共沸蒸馏而损失的体积。
结果归纳在表1至表2中。
表1
Figure PCTCN2018082774-appb-000002
表2
Figure PCTCN2018082774-appb-000003
DBTO废物：在全部批次期间使用的总的新鲜DBTO量除以该批次数。
结果表明，根据本发明的方法允许催化剂的更有效使用，这归因于每批次的总催化剂消耗显著降低，并因此减少了每批产生的总废物量。结果，生产满意的单体品质的最大批次数增加。由于在整个反应过程中均使用反应器的完整体积，因此生产量也有所增加。总体来看，与现有方法相比，该方法具有显著改善。

Claims (17)

  1. 一种用于生产(甲基)丙烯酸2-二甲氨基乙酯的方法，包括至少两个连续的分批反应，其中在每个分批反应中，将(甲基)丙烯酸甲酯、二甲氨基乙醇、溶剂和作为催化剂的二丁基锡氧化物作为初始进料添加到配备有蒸馏塔的搅拌反应器中，其中在反应期间连续地进行共沸蒸馏，其中由于所述共沸蒸馏而引起的体积减小通过连续添加包含(甲基)丙烯酸甲酯和二甲氨基乙醇的组合物进行补偿，从而保持所述反应器中的体积恒定，该组合物还可以包含二丁基锡氧化物，所述方法包括：
    -第一分批反应，其中用作催化剂的二丁基锡氧化物是新鲜二丁基锡氧化物；
    -分离步骤，其中从所述第一分批反应的反应混合物中回收来自第一分批反应的二丁基锡氧化物，并且所述来自第一分批反应的二丁基锡氧化物构成再循环的二丁基锡氧化物；
    -至少第二分批反应，其中所述再循环的二丁基锡氧化物的至少65重量％与新鲜二丁基锡氧化物一起用作第二分批反应的催化剂：
    ○其中基于所述来自所述第一分批反应的再循环的二丁基锡氧化物，新鲜二丁基锡氧化物的量为0.1重量％至35重量％，
    ○其中初始进料中添加的再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比为220/1至80/20，
    ○其中连续添加以补偿所述共沸蒸馏的所述组合物中，在包含二丁基锡氧化物的情况下，再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比为100/0至0/100。
  2. 根据权利要求1所述的方法，其中所述方法包括至少一个后续的分批反应，其中来自前一反应的所述再循环的二丁基锡氧化物的至少65重量％与新鲜二丁基锡氧化物一起用作所述反应的催化剂：
    ○其中基于来自前一反应的所述再循环的二丁基锡氧化物，新鲜二丁基锡氧化物的量为0.1重量％至35重量％，
    ○其中初始进料中添加的来自所述前一反应的再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比为220/1至80/20，
    ○其中连续添加以补偿所述共沸蒸馏的所述组合物中，在包含二丁基锡氧化物的情况下，来自所述前一反应的再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比为100/0至0/100。
  3. 根据前述权利要求中任一项所述的方法，其中所述方法包括总共至少3个，优选4个，更优选5个，甚至更优选6个，甚至更优选7个，甚至更优选8个，甚至更优选9个，甚至更优选10个，多至20个分批反应，其中根据权利要求1所述，在每个分批反应中，来自前一反应的所述再循环的二丁基锡氧化物与新鲜二丁基锡氧化物组合用作催化剂。
  4. 根据前述权利要求中任一项所述的方法，其中所述溶剂为C6至C12的线性、环状或支化烷烃。
  5. 根据前述权利要求中任一项所述的方法，其中所述方法的所述连续的分批反应在同一反应器中进行。
  6. 根据前述权利要求中任一项所述的方法，其中在所述反应期间连续添加以补偿由于所述共沸蒸馏引起的体积减小的所述组合物包含(甲基)丙烯酸甲酯、二甲氨基乙醇、二丁基锡氧化物和溶剂。
  7. 根据前述权利要求中任一项所述的方法，其中在所述反应期间连续添加以补偿由于所述共沸蒸馏引起的体积减小的所述组合物的组成与在所述反应开始之前最初添加到所述反应器中的组合物的组成相同。
  8. 根据前述权利要求中任一项所述的方法，其中所述第二分批反应和/或后续的分批反应中，回收来自所述前一反应的再循环的二丁基锡氧化物的至少80重量％，优选至少85重量％，更优选至少90重量％与新鲜二丁基锡氧化物一起用作后续反应的催化剂。
  9. 根据前述权利要求中任一项所述的方法，其中每个后续反应中的新鲜二丁基锡氧化物的量为基于所述再循环的二丁基锡氧化物的0.1重量％至20重量％，优选0.5重量％至15重量％，甚至更优选 0.5重量％至10重量％。
  10. 根据前述权利要求中任一项所述的方法，其中在每个后续的分批反应中，每个后续反应的初始进料中添加的再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比为97/3至85/15，优选95/5至87/13，甚至更优选90/10，甚至更优选99/1。
  11. 根据前述权利要求中任一项所述的方法，其中在连续添加以补偿所述共沸蒸馏从而保持所述反应器中的体积恒定的所述组合物中，在包含二丁基锡氧化物的情况下，再循环的二丁基锡氧化物与新鲜二丁基锡氧化物的质量比为95/5至5/95，优选90/10至10/90。
  12. 一种根据权利要求1至11中任一项所述的方法获得的(甲基)丙烯酸2-二甲氨基乙酯。
  13. 一种在分离步骤之后从根据权利要求1至11中任一项所述的方法获得的反应混合物中回收的(甲基)丙烯酸2-二甲氨基乙酯混合物。
  14. 一种季铵化形式的根据权利要求12所述的(甲基)丙烯酸2-二甲氨基乙酯或根据权利要求13所述的(甲基)丙烯酸2-二甲氨基乙酯混合物。
  15. 一种用根据权利要求14所述的季铵化形式的(甲基)丙烯酸2-二甲氨基乙酯制备的聚合物。
  16. 根据权利要求15所述的聚合物，其通过使根据权利要求14所述的季铵化形式的(甲基)丙烯酸2-二甲氨基乙酯和选自以下列表的至少一种单体聚合而获得：
    -非离子单体：丙烯酰胺、甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、N-乙烯基吡咯烷酮、N-乙烯基甲酰胺、N-乙烯基咪唑、聚乙二醇的甲基丙烯酸酯、双丙酮丙烯酰胺、N-异丙基丙烯酰胺、丙烯酸2-羟乙酯、丙烯酸2,3-二羟丙酯、甲基丙烯酸2-羟乙酯、甲基丙烯酸2,3-二羟丙酯、N-叔丁基丙烯酰胺，
    -阴离子单体：未成盐的、部分成盐的或完全成盐的丙烯酸、2-丙烯酰胺基-2-甲基丙磺酸(ATBS)、甲基丙烯酸、衣康酸、马来酸、 磺酸烯丙酯，
    -阳离子单体：二烯丙基二甲基氯化铵(DADMAC)、丙烯酰胺基二烷基氨基丙基、甲基丙烯酰胺基二烷基氨基丙基、及其酸化盐或季铵盐。
    -结构剂：具有至少两个不饱和官能团(例如乙烯基、烯丙基、丙烯酸类和环氧官能团)的多烯键式不饱和单体，例如亚甲基双丙烯酰胺(MBA)、三烯丙基胺、四烯丙基氯化铵，或者大分子引发剂如多过氧化物、多偶氮化合物和转移聚合剂如聚硫醇聚合物。
  17. 根据权利要求15或16所述的聚合物在水处理、污泥脱水、造纸工艺、农业、化妆品和清洁组合物、纺织工艺、油气回收工艺如强化采油、压裂、采矿作业如尾矿处理中的用途。
PCT/CN2018/082774 2018-04-12 2018-04-12 用于生产(甲基)丙烯酸2-二甲氨基乙酯的方法 WO2019196048A1 (zh)

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