JP5809050B2 - Method for producing quaternary ammonium salt - Google Patents
Method for producing quaternary ammonium salt Download PDFInfo
- Publication number
- JP5809050B2 JP5809050B2 JP2011288553A JP2011288553A JP5809050B2 JP 5809050 B2 JP5809050 B2 JP 5809050B2 JP 2011288553 A JP2011288553 A JP 2011288553A JP 2011288553 A JP2011288553 A JP 2011288553A JP 5809050 B2 JP5809050 B2 JP 5809050B2
- Authority
- JP
- Japan
- Prior art keywords
- quaternary ammonium
- ammonium salt
- group
- tertiary amine
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、第４級アンモニウム塩の製造方法に関する。 The present invention relates to a method for producing a quaternary ammonium salt.
第４級アンモニウム塩は、衣料用洗浄剤や殺菌剤、抗菌剤及び繊維などの柔軟剤や毛髪処理剤、帯電防止剤等に基剤として用いられている。第４級アンモニウム塩は、第３級アミンと４級化剤を必要に応じて溶媒を使用して反応させる方法等により製造される。しかし、製造された第４級アンモニウム塩には、反応中に副生する低級アミンや未反応の4級化剤等の不純物を含有し、この不純物は極少量を含有しても匂いや保存安定性を悪くするという問題があった。 The quaternary ammonium salt is used as a base for garment detergents, bactericides, antibacterial agents, softening agents such as fibers, hair treatment agents, antistatic agents, and the like. The quaternary ammonium salt is produced by a method of reacting a tertiary amine and a quaternizing agent using a solvent as necessary. However, the produced quaternary ammonium salt contains impurities such as lower amines produced as a by-product during the reaction and unreacted quaternizing agent. Even if these impurities are contained in a very small amount, they smell and preserve stably. There was a problem of worsening sex.
そのために、従来では匂いや、色相、保存安定性の改善を目的に、反応後に常圧下あるいは減圧下でのキャリアーガスを用いた除去や減圧下での留去が行われている。例えば、特許文献１では、反応溶媒にエチルアルコールやイソプロピルアルコール等を使用して４級化し、次いで、その反応溶媒と共に不純物を留去することで色相を改善している。特許文献２には、加熱下での留去時間が、泡立ちにより長くなることで匂いが悪化するのを改善する方法として、シリコーン等の消泡剤を添加した後、留去する方法が提案されている。 Therefore, conventionally, for the purpose of improving odor, hue, and storage stability, removal using a carrier gas under normal pressure or reduced pressure and distillation under reduced pressure are performed after the reaction. For example, in Patent Document 1, quaternization is performed using ethyl alcohol, isopropyl alcohol, or the like as a reaction solvent, and then the hue is improved by distilling out impurities together with the reaction solvent. Patent Document 2 proposes a method of distilling off after adding an antifoaming agent such as silicone as a method of improving the odor that is aggravated by elongating the foaming time under heating. ing.
また、特許文献３には、溶媒として非イオン界面活性剤を用いて、第３級アミンをジアルキル硫酸で４級化させる、不純物の副生が少なく、匂いの良好な第４級アンモニウム塩の製造方法が開示されている。また、特許文献４には、第３級アミン化合物と４級化剤とを、溶媒不存在下で反応させる第４級アンモニウム塩の製造方法が開示されている。 Patent Document 3 discloses the production of a quaternary ammonium salt having a good odor and less by-product of impurities by quaternizing a tertiary amine with a dialkyl sulfuric acid using a nonionic surfactant as a solvent. A method is disclosed. Patent Document 4 discloses a method for producing a quaternary ammonium salt in which a tertiary amine compound and a quaternizing agent are reacted in the absence of a solvent.
特許文献１では、製造される第４級アンモニウム塩は低級アルコールとの混合物として得られることから、引火性であるために取り扱い設備の高コスト化、及び商品として低級アルコールによる匂い影響や引火点が検出されて使用できない事がある。また、特許文献２でも、効率的な匂い改善の効果が得られない等の問題があった。更に、従来の第４級アンモニウム塩は、過酷な条件で保存された後の匂いの発生を十分に抑制することは困難であり、特許文献１〜４にはこの課題やその課題の解決手段の具体的な言及はない。 In Patent Document 1, since the quaternary ammonium salt to be produced is obtained as a mixture with a lower alcohol, it is flammable, so the cost of handling equipment is increased, and the odor effect and flash point of the lower alcohol as a product are increased. Detected and cannot be used. Further, Patent Document 2 also has a problem that an effective odor improvement effect cannot be obtained. Furthermore, it is difficult for conventional quaternary ammonium salts to sufficiently suppress the generation of odor after being stored under harsh conditions, and Patent Documents 1 to 4 describe this problem and means for solving the problem. There is no specific mention.
本発明の課題は、製造直後の異臭がなく、過酷な条件で保存された後も異臭の発生を抑制できる高品質な第４級アンモニウム塩が得られる製造方法を提供することである。さらに詳しくは、過酷な条件で保存された後も異臭の発生を抑制できる優れた高品質な第４級アンモニウム塩を、溶媒留去や脱臭操作等の煩雑な精製を行わずに、水溶液の形態で得ることができる製造方法を提供することである。 An object of the present invention is to provide a production method in which a high-quality quaternary ammonium salt is obtained which has no off-flavor immediately after production and can suppress generation of off-flavor even after being stored under severe conditions. More specifically, an excellent high-quality quaternary ammonium salt that can suppress the generation of off-flavor even after being stored under harsh conditions can be obtained in the form of an aqueous solution without complicated purification such as solvent distillation and deodorizing operation. It is providing the manufacturing method which can be obtained by this.
本発明は、下記一般式（１）で表される第３級アミン（１）〔以下、第３級アミン（１）という〕を水中で４級化して下記一般式（２）で表わされる第４級アンモニウム塩（２）〔以下、第４級アンモニウム塩（２）という〕を製造する、第４級アンモニウム塩の製造方法であって、
４級化剤を第３級アミン（１）に対して０．０５モル倍量／分以下の添加速度で反応系に添加する、
第４級アンモニウム塩の製造方法に関する。
In the present invention, a tertiary amine (1) represented by the following general formula (1) [hereinafter referred to as a tertiary amine (1)] is quaternized in water, and is represented by the following general formula (2). A method for producing a quaternary ammonium salt, comprising producing a quaternary ammonium salt (2) [hereinafter referred to as quaternary ammonium salt (2)],
A quaternizing agent is added to the reaction system at an addition rate of 0.05 mol times / min or less with respect to the tertiary amine (1)
The present invention relates to a method for producing a quaternary ammonium salt.
（式中、Ｒ1は、エステル基、アミド基又はエーテル基が挿入されていてもよい、炭素数６〜３０の直鎖又は分岐鎖のアルキル基又はアルケニル基を示す。） (In the formula, R 1 represents a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms into which an ester group, an amide group or an ether group may be inserted.)
（式中、Ｒ1は、エステル基、アミド基又はエーテル基が挿入されていてもよい、炭素数６〜３０の直鎖又は分岐鎖のアルキル基又はアルケニル基を示し、Ｒ2は炭素数１〜３のアルキル基を示し、Ｘ-は陰イオン基を示す。） (In the formula, R 1 represents a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms into which an ester group, an amide group or an ether group may be inserted, and R 2 represents one carbon atom. ˜3 represents an alkyl group, and X − represents an anionic group.)
本発明により、製造直後の異臭がなく、過酷な条件で保存された後も異臭の発生を抑制できる高品質な第４級アンモニウム塩を製造することができる。さらに、この第４級アンモニウム塩は、水溶液の形態で得ることができ、過酷な条件で保存された後も異臭の発生を抑制できることに加え、溶媒による匂いや引火性を有さないことから、取り扱い性に優れ、衣料用洗浄剤、殺菌剤、抗菌剤、繊維用柔軟剤、毛髪処理剤、帯電防止剤等の調製原料として用いる場合に有用である。 According to the present invention, it is possible to produce a high-quality quaternary ammonium salt that has no off-flavor immediately after production and can suppress the generation of off-flavor even after being stored under severe conditions. Furthermore, this quaternary ammonium salt can be obtained in the form of an aqueous solution, and in addition to being able to suppress the generation of off-flavors even after being stored under harsh conditions, it has no odor or flammability due to the solvent, It is excellent in handleability and is useful when used as a raw material for preparation of clothing detergents, bactericides, antibacterial agents, textile softeners, hair treatment agents, antistatic agents and the like.
本発明に用いられる第３級アミン（Ｉ）は、一般式（Ｉ）中のＲ1が、エステル基（−ＣＯＯ−もしくは−ＯＣＯ−）、アミド基（−ＮＨＣＯ−もしくは−ＣＯＮＨ−）、エーテル基（−Ｏ−）が挿入されていてもよい、炭素数６〜３０、好ましくは炭素数８〜２４、より好ましくは炭素数１０〜２２の直鎖又は分岐鎖のアルキル基又はアルケニル基である。Ｒ1は炭素数８〜２４の直鎖又は分岐鎖のアルキル基であることが好ましく、更に炭素数１０〜２２の直鎖又は分岐鎖のアルキル基であることがより好ましく、より更に炭素数１０〜１８の直鎖のアルキル基であることが更に好ましい。 In the tertiary amine (I) used in the present invention, R 1 in the general formula (I) is an ester group (—COO— or —OCO—), an amide group (—NHCO— or —CONH—), an ether A straight or branched alkyl or alkenyl group having 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, more preferably 10 to 22 carbon atoms, to which a group (-O-) may be inserted. . R 1 is preferably a linear or branched alkyl group having 8 to 24 carbon atoms, more preferably a linear or branched alkyl group having 10 to 22 carbon atoms, and even more preferably 10 carbon atoms. More preferably, it is a -18 linear alkyl group.
第４級アンモニウム塩（２）は、第３級アミン（１）を４級化して得られるものであり、一般式（２）中のＲ2は、炭素数１〜３のアルキル基であって、好ましくはメチル基、エチル基、より好ましくはメチル基である。 The quaternary ammonium salt (2) is obtained by quaternizing the tertiary amine (1), and R 2 in the general formula (2) is an alkyl group having 1 to 3 carbon atoms. Preferably a methyl group, an ethyl group, and more preferably a methyl group.
一般式（２）中のＸ-は陰イオン基であって、具体的にはＣｌ-、Ｂｒ-等のハロゲンイオン、メチル硫酸、エチル硫酸等の短鎖アルキル（炭素数１〜３）硫酸イオン、酢酸、酒石酸、乳酸、リンゴ酸、コハク酸等の有機酸の陰イオンが挙げられ、好ましくはＣｌ-、Ｂｒ-等のハロゲンイオン、メチル硫酸、エチル硫酸等の短鎖アルキル（炭素数１〜２）硫酸イオンであり、より好ましくはＣｌ-、メチル硫酸イオン、特に好ましくはＣｌ-（塩化物イオン）である。 X − in the general formula (2) is an anion group, specifically, a halogen ion such as Cl − or Br − , or a short-chain alkyl (carbon number 1 to 3) sulfate ion such as methyl sulfate or ethyl sulfate. Anions of organic acids such as acetic acid, tartaric acid, lactic acid, malic acid and succinic acid, preferably halogen ions such as Cl − and Br − , short chain alkyls such as methyl sulfate and ethyl sulfate (1 to 2) Sulfate ion, more preferably Cl − , methyl sulfate ion, particularly preferably Cl − (chloride ion).
本発明では、水中で第３級アミン（１）を４級化して第４級アンモニウム塩（２）を製造する。また、水の他に、メタノール、エタノール、イソプロピルアルコール等の低級アルコール（炭素数１〜３）、エチレングリコール、プロピレングリコール等のジオール類（炭素数２〜５）、アセトン、アセトニトリルのような有機溶媒を、本反応に影響が無い範囲内で、適宜加えることも可能である。影響のない添加量の範囲としては、例えば、得られた第４級アンモニウム塩水溶液に引火点が発現しない範囲で加えることが出来る。具体的には、エチルアルコールの場合には５質量％以下で添加する事が出来る。本発明では、４級化を水中で行うため、反応溶媒は水を９５質量％以上含有することが好ましく、９５〜１００質量％含有することがより好ましい。 In the present invention, the quaternary ammonium salt (2) is produced by quaternizing the tertiary amine (1) in water. In addition to water, lower alcohols such as methanol, ethanol and isopropyl alcohol (1 to 3 carbon atoms), diols such as ethylene glycol and propylene glycol (2 to 5 carbon atoms), organic solvents such as acetone and acetonitrile. Can be added as appropriate within a range that does not affect the present reaction. As the range of the addition amount having no influence, for example, it can be added within the range where the flash point does not appear in the obtained aqueous solution of quaternary ammonium salt. Specifically, in the case of ethyl alcohol, it can be added at 5% by mass or less. In the present invention, since the quaternization is performed in water, the reaction solvent preferably contains 95% by mass or more of water, and more preferably 95-100% by mass.
水に対する第３級アミン（１）の割合は、得られる第４級アンモニウム塩水溶液の常温における流動性の確保及び効率的な生産性の観点から、４級化剤を最初に導入する前の時点で、２０〜８０質量％であることが好ましく、より好ましくは２５〜７０質量％、更に好ましくは３０〜６０質量％である。この割合は、〔第３級アミン（１）の仕込量／水の仕込量〕×１００により求められるものである。 The ratio of the tertiary amine (1) to the water is the time before the first introduction of the quaternizing agent from the viewpoint of securing the fluidity of the resulting quaternary ammonium salt aqueous solution at room temperature and efficient productivity. It is preferable that it is 20-80 mass%, More preferably, it is 25-70 mass%, More preferably, it is 30-60 mass%. This ratio is obtained by [the amount of tertiary amine (1) charged / the amount of water charged] × 100.
４級化剤は、第３級アミン（１）を第４級アンモニウム塩（２）の構造とするものが適宜選定される。具体的には、塩化メチル、臭化メチル、よう化メチル等のハロゲン化アルキル、炭酸ジメチルや炭酸ジエチル等の炭酸ジアルキル、ジメチル硫酸やジエチル硫酸等のジアルキル硫酸等が挙げられ、好ましくは塩化メチル、炭酸ジメチル、ジメチル硫酸やジエチル硫酸、より好ましくは低コストの観点から塩化メチル、ジメチル硫酸、更に、低コストと４級化反応率の観点から、より好ましくは塩化メチルである。 As the quaternizing agent, one having the tertiary amine (1) as the structure of the quaternary ammonium salt (2) is appropriately selected. Specific examples include alkyl halides such as methyl chloride, methyl bromide and methyl iodide, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, preferably methyl chloride, Dimethyl carbonate, dimethyl sulfate or diethyl sulfate, more preferably methyl chloride and dimethyl sulfate from the viewpoint of low cost, and more preferably methyl chloride from the viewpoint of low cost and quaternization reaction rate.
本発明では、４級化剤を第３級アミン（１）に対して０．０５モル倍／分以下の添加速度で反応系に添加する。低級アミン等の副生物の抑制や仕込みに要する時間の短縮化の観点から、この添加速度は、０．００１５〜０．０４８倍／分が好ましく、０．００４〜０．０４２倍／分がより好ましく、０．００６〜０．０４モル倍／分が更に好ましい。４級化剤を反応系に添加する態様は、一括、連続、分割、間欠など、種々可能であるが、本発明では、いずれの場合でも反応系に導入される４級化剤の添加速度が前記範囲となるように制御する（例えば、分割もしくは間欠で添加する場合は、各添加操作ごとに添加速度を前記範囲とする）ことで、匂いに優れた第４級アンモニウム塩を水系で効率よく製造できるものである。また、連続で添加する場合、添加速度は、前記範囲内において、一定、変動のいずれでもよい。なお、反応系は、第３級アミン（１）及び水を含んで構成される混合物であってよく、更にこれに４級化剤を含んで構成される混合物であってよい。例えば、反応系を、第３級アミン（１）、４級化剤及び水の混合物とみなすことができ、その場合、反応系の量は、これら三者の仕込量の合計とすることができる。 In the present invention, the quaternizing agent is added to the reaction system at an addition rate of 0.05 mol times / min or less with respect to the tertiary amine (1). From the viewpoint of suppressing by-products such as lower amines and shortening the time required for charging, the addition rate is preferably 0.0015 to 0.048 times / minute, more preferably 0.004 to 0.042 times / minute. Preferably, 0.006 to 0.04 mol / min is more preferable. There are various modes of adding the quaternizing agent to the reaction system, such as batch, continuous, divided, intermittent, etc. In the present invention, the addition rate of the quaternizing agent introduced into the reaction system is any case. By controlling to be within the above range (for example, when adding in a divided or intermittent manner, the addition rate is set to the above range for each addition operation), the quaternary ammonium salt excellent in odor is efficiently obtained in an aqueous system. It can be manufactured. In addition, when adding continuously, the addition rate may be constant or variable within the above range. The reaction system may be a mixture including the tertiary amine (1) and water, and may further include a mixture including a quaternizing agent. For example, the reaction system can be regarded as a mixture of a tertiary amine (1), a quaternizing agent and water, in which case the amount of the reaction system can be the sum of these three charges. .
４級化剤の使用量は、第３級アミン（１）に対して０．９５〜２．０モル倍が好ましい。４級化後の未反応第３級アミン含量の低減や４級化剤の副反応、反応後に残存する４級化剤の廃棄等の後処理への負担低減の観点から、４級化剤の使用量は、第３級アミン（１）に対して０．９８〜１．５モル倍がより好ましく、０．９９〜１．３０モル倍が更に好ましく、１．００〜１．１５モル倍がより更に好ましい。 The amount of the quaternizing agent used is preferably 0.95 to 2.0 mol times based on the tertiary amine (1). From the viewpoint of reducing the burden on post-treatment such as reduction of unreacted tertiary amine content after quaternization, side reaction of quaternizing agent, disposal of quaternizing agent remaining after reaction, etc. The amount used is more preferably 0.98 to 1.5 mol times, more preferably 0.99 to 1.30 mol times, and 1.00 to 1.15 mol times with respect to the tertiary amine (1). Even more preferred.
４級化剤を添加する際の反応系の温度（仕込み温度）は、２５〜１１０℃が好ましい。４級化剤と第３級アミン（１）の反応性の観点から、４０〜１００℃が好ましく、４級化の反応熱による過度の温度上昇を抑制する観点から、５０〜９０℃がより好ましい。一般に、この範囲の温度では、第３級アミン（１）は、反応初期では溶解しない状態で水を含む反応系中に存在する。本発明では、不均一系で４級化反応を開始するものであり、４級化剤の添加後、４級化反応が進行するに従って反応系中の第４級アンモニウム塩（２）の割合が増加し、全体として均一系（溶解）へと移行しているものである。 The temperature of the reaction system (preparation temperature) when adding the quaternizing agent is preferably 25 to 110 ° C. 40-100 degreeC is preferable from a reactive viewpoint of a quaternizing agent and tertiary amine (1), and 50-90 degreeC is more preferable from a viewpoint of suppressing the excessive temperature rise by the reaction heat of quaternization. . In general, at a temperature in this range, the tertiary amine (1) is present in a reaction system containing water in a state in which it does not dissolve at the initial stage of the reaction. In the present invention, the quaternization reaction is started in a heterogeneous system, and after the addition of the quaternizing agent, the proportion of the quaternary ammonium salt (2) in the reaction system increases as the quaternization reaction proceeds. As a whole, it has shifted to a homogeneous system (dissolution).
本発明では、目的物である第４級アンモニウム塩（２）の生産効率、４級化反応率、及び色相等の品質の観点から、４級化剤の全量が２０〜６００分、更に２３〜２５０分、より更に２５〜１５０分で反応系に添加されることが好ましい。つまり、４級化剤が最初に反応系に添加されてから、最後に添加されるまでの時間が前記範囲であることが好ましい。 In the present invention, from the viewpoint of the production efficiency of the quaternary ammonium salt (2) which is the target product, the total amount of the quaternizing agent is 20 to 600 minutes, further 23 to 23, from the viewpoint of quality such as quaternization reaction rate and hue. It is preferably added to the reaction system in 250 minutes, and further in 25 to 150 minutes. That is, it is preferable that the time from when the quaternizing agent is first added to the reaction system to when it is finally added is within the above range.
本発明では、４級化剤の全量が反応系に添加された後、所定温度、所定時間の熟成を行い、反応を進行させることが好ましい。熟成温度は２５〜１２０℃が好ましく、速やかに反応を進行させる観点及び反応品の色相等の品質を悪化させない観点から、２５〜１１０℃が更に好ましく、４０〜１００℃がより好ましく、５０〜９０℃が更に好ましい。また、熟成時間は４級化の反応率（原料の第３級アミン（１）の減少量）に基づいて決定することができるが、４級化剤の全量が反応系に添加された後、１０〜１２００分、更に２０〜６００分、より更に３０〜３００分の熟成を行うことが好ましい。 In the present invention, it is preferable that after the entire amount of the quaternizing agent is added to the reaction system, the reaction is allowed to proceed by aging at a predetermined temperature for a predetermined time. The aging temperature is preferably 25 to 120 ° C, more preferably 25 to 110 ° C, more preferably 40 to 100 ° C, and more preferably 50 to 90 ° C from the viewpoint of promptly proceeding the reaction and not deteriorating the quality of the hue of the reaction product. More preferred is ° C. The aging time can be determined based on the quaternization reaction rate (decreasing amount of the raw material tertiary amine (1)), but after the total amount of the quaternizing agent is added to the reaction system, It is preferable to perform aging for 10 to 1200 minutes, further 20 to 600 minutes, and further 30 to 300 minutes.
本発明では、４級化後にアルカリ性下で低沸点化合物の留去を行い、その後に中性に調整することが、第４級アンモニウム塩水溶液の保存安定性や各種製品を製造する際の取り扱い性などの観点で好ましい。４級化反応の終結は、未反応の第３級アミン（１）を滴定等にて定量することにより確認することができる。 In the present invention, the low-boiling point compound is distilled off under alkalinity after quaternization, and then adjusted to neutrality, so that the storage stability of an aqueous quaternary ammonium salt solution and the handleability in producing various products are improved. It is preferable from the viewpoints. The completion of the quaternization reaction can be confirmed by quantifying the unreacted tertiary amine (1) by titration or the like.
ここで、低沸点化合物とは、沸点が１５０℃以下である化合物をいい、具体的には、未反応の４級化剤、水等の反応溶媒、炭素数１〜３の１級、２級又は３級アミン等の低級アミン、匂いに影響する不純物等が挙げられる。 Here, the low boiling point compound refers to a compound having a boiling point of 150 ° C. or lower, specifically, an unreacted quaternizing agent, a reaction solvent such as water, a C 1-3 primary, secondary. Or the lower amines, such as a tertiary amine, the impurity etc. which affect an odor are mentioned.
低沸点化合物の留去時の反応系のｐＨは、低沸点化合物の留去のされ易さ及び得られる第４級アンモニウム塩水溶液中の無機塩量の低減等の観点から、好ましくは７．５〜１３．０、更に好ましくは８．５〜１２．０、より好ましくは８．６〜１１．０である。すなわち、本発明では、第３級アミン（１）を水中で４級化して第４級アンモニウム塩（２）と水とを含有する反応混合物を調製し、該調製物のｐＨを７．５〜１３．０、更に好ましくは８．５〜１２．０、より好ましくは８．６〜１１．０として低沸点化合物の留去を行うことが好ましい。 The pH of the reaction system at the time of distilling off the low boiling point compound is preferably 7.5 from the viewpoint of easiness of distilling off the low boiling point compound and reduction of the amount of inorganic salt in the resulting aqueous quaternary ammonium salt solution. It is -13.0, More preferably, it is 8.5-12.0, More preferably, it is 8.6-11.0. That is, in the present invention, the tertiary amine (1) is quaternized in water to prepare a reaction mixture containing the quaternary ammonium salt (2) and water, and the pH of the preparation is adjusted to 7.5 to The low boiling point compound is preferably distilled off at 13.0, more preferably 8.5 to 12.0, and more preferably 8.6 to 11.0.
低沸点化合物の留去時の反応混合物の温度は、低沸点化合物の留去のされ易さ及び第４級アンモニウム塩水溶液の副反応の低減等から、好ましくは４０〜１２０℃、更に好ましくは５０〜１００℃、より好ましくは６０〜９０℃である。 The temperature of the reaction mixture at the time of distilling off the low boiling point compound is preferably 40 to 120 ° C., more preferably 50, because of the ease of distilling off the low boiling point compound and the reduction of side reactions of the aqueous quaternary ammonium salt solution. It is -100 degreeC, More preferably, it is 60-90 degreeC.
低沸点化合物の留去後は、反応混合物のｐＨを中性近傍、好ましくはｐＨ５．０〜９．５、より好ましくは５．５〜９．０、更に好ましくは６．０〜８．５に調整する。本発明により得られた第４級アンモニウム塩水溶液は、２５℃のｐＨがこれらの範囲にあることが好ましい。 After distilling off the low boiling point compound, the pH of the reaction mixture is close to neutral, preferably pH 5.0 to 9.5, more preferably 5.5 to 9.0, still more preferably 6.0 to 8.5. adjust. The aqueous quaternary ammonium salt obtained by the present invention preferably has a pH of 25 ° C. in these ranges.
低沸点化合物の留去は、消泡剤の存在下に行うことが好ましく、本発明で使用できる消泡剤としては、ジメチルポリシロキサン、部分的にアミノ基やポリオキシアルキレン基等に変性されたジメチルポリシロキサン等のシリコーン化合物、二酸化珪素等が挙げられ、これらの１種以上を用いることができ、また予め乳化したものでもよく、好ましくはジメチルポリシロキサン、部分的にアミノ基やポリオキシアルキレン基等に変性されたジメチルポリシロキサン及びこれらのシリコーンと二酸化珪素との混合物、より好ましくはポリオキシアルキレン基等に変性されたジメチルポリシロキサン及びこれらのシリコーンと二酸化珪素との混合物である。消泡剤を添加混合することで、泡立ちによるトラブルもなく製造がスムーズに行え、更に処理量のアップを図ることができ、大幅な生産性向上が可能となる。 The low-boiling point compound is preferably distilled off in the presence of an antifoaming agent. As the antifoaming agent that can be used in the present invention, dimethylpolysiloxane, partially modified with an amino group or a polyoxyalkylene group, etc. Examples thereof include silicone compounds such as dimethylpolysiloxane, silicon dioxide, and the like. One or more of these may be used, and may be pre-emulsified, preferably dimethylpolysiloxane, partially an amino group or a polyoxyalkylene group. Dimethylpolysiloxane modified to the same, and a mixture of these silicones and silicon dioxide, more preferably dimethylpolysiloxane modified to a polyoxyalkylene group and the like, and a mixture of these silicones and silicon dioxide. By adding and mixing the antifoaming agent, the production can be smoothly performed without any trouble due to foaming, the processing amount can be increased, and the productivity can be greatly improved.
消泡剤の添加量は、反応混合物に対して好ましくは１０〜１，０００ｍｇ／ｋｇ、より好ましくは２５〜５００ｍｇ／ｋｇ、特に好ましくは５０〜２５０ｍｇ／ｋｇである。 The addition amount of the antifoaming agent is preferably 10 to 1,000 mg / kg, more preferably 25 to 500 mg / kg, and particularly preferably 50 to 250 mg / kg with respect to the reaction mixture.
消泡剤の添加時期は、４級化の前または４級化後のどちらでも良いが、４級化時の泡立ちのトラブル回避や処理量のアップによる生産性向上から４級化の前に添加することが好ましい。従って、本発明では、第３級アミン（１）の４級化を消泡剤の存在下で行うことができる。この場合、消泡剤は、反応系、更に第３級アミン（１）と水の合計量に対して前記範囲で用いることが好ましい。 The antifoaming agent may be added before quaternization or after quaternization, but it is added before quaternization in order to avoid problems with foaming during quaternization and to improve productivity by increasing the processing amount. It is preferable to do. Therefore, in the present invention, the quaternization of the tertiary amine (1) can be performed in the presence of an antifoaming agent. In this case, the antifoaming agent is preferably used within the above range with respect to the total amount of the reaction system and the tertiary amine (1) and water.
低沸点化合物の留去は、常圧下または減圧下で行うことが出来る。減圧下で行う場合は、圧力３〜９５ｋＰａが好ましく、より好ましくは６．７〜９０ｋＰａ、特に好ましくは１３〜８０ｋＰａである。 The low boiling point compound can be distilled off under normal pressure or reduced pressure. When performed under reduced pressure, the pressure is preferably 3 to 95 kPa, more preferably 6.7 to 90 kPa, and particularly preferably 13 to 80 kPa.
低沸点化合物の留去において不活性ガスをキャリアガスとして吹き込みを行うことが好ましく、不活性ガスとしては、窒素や蒸気等が挙げられ、好ましくは窒素である。不活性ガスの吹き込み量は、反応混合物に対して０．０５〜５００Ｌ／ｋｇが好ましく、低沸点化合物の留去の効果及び不活性ガスのコスト負担より、より好ましくは０．１〜１００Ｌ／ｋｇ、特に好ましくは０．５〜５０Ｌ／ｋｇである。 In distilling off the low-boiling compound, it is preferable to perform blowing with an inert gas as a carrier gas. Examples of the inert gas include nitrogen and steam, and nitrogen is preferable. The amount of the inert gas blown is preferably 0.05 to 500 L / kg with respect to the reaction mixture, and more preferably 0.1 to 100 L / kg from the effect of distilling off the low boiling point compound and the cost burden of the inert gas. Particularly preferred is 0.5 to 50 L / kg.
低沸点化合物の留去は、バッチ式の槽および薄膜蒸発機等の全ての装置で効果が得られるが、生産コストの観点から好ましくはバッチ式の槽である。 The distillation of the low boiling point compound can be effective in all apparatuses such as a batch tank and a thin film evaporator, but a batch tank is preferable from the viewpoint of production cost.
本発明の製造方法では、第４級アンモニウム塩（２）を２０〜８０質量％、更に２５〜６０質量％、より更に２７〜５０質量％含有する水溶液を得ることができる。 In the production method of the present invention, an aqueous solution containing 20 to 80% by mass, further 25 to 60% by mass, and further 27 to 50% by mass of the quaternary ammonium salt (2) can be obtained.
本発明により製造された第４級アンモニウム塩は、各種洗浄剤（衣料用洗浄剤、身体用洗浄剤、毛髪用洗浄剤等）、毛髪処理剤、柔軟剤等に使用することができる。 The quaternary ammonium salt produced by the present invention can be used for various cleaning agents (clothing cleaning agents, body cleaning agents, hair cleaning agents, etc.), hair treatment agents, softeners, and the like.
実施例及び比較例で製造された第４級アンモニウム塩水溶液の匂い評価を以下の通り行った。 The odor evaluation of the quaternary ammonium salt aqueous solutions produced in Examples and Comparative Examples was performed as follows.
製造直後の水溶液又は６０℃で６ヶ月保存後の水溶液を、１００ｍＬのビーカーに入れ、室温にてパネラー５名による官能評価を行い、下記基準で異臭の抑制を評価した。なお、水溶液の保存は、協同硝子株式会社製の広口規格びんＰＳ−Ｎｏ．１１（胴径５１．５ｍｍ、高さ９５．５ｍｍ、口径３９．５ｍｍ、ガラス製）に水溶液５０ｍＬを入れて密閉、遮光の状態で行った。
Ａ：５名が異臭を感じなかった
Ｂ：４名が異臭を感じなかった
Ｃ：３名が異臭を感じなかった
Ｄ：２名が異臭を感じなかった
Ｅ：０名又は１名が異臭を感じなかった（４名又は５名が異臭を感じた）
An aqueous solution immediately after production or an aqueous solution stored at 60 ° C. for 6 months was put in a 100 mL beaker, sensory evaluation was performed by five panelists at room temperature, and the suppression of off-flavors was evaluated according to the following criteria. The aqueous solution is stored in Kyodou Glass Co., Ltd. Hiroguchi Standard Bottle PS-No. 11 (cylinder diameter 51.5 mm, height 95.5 mm, caliber 39.5 mm, made of glass) was filled with 50 mL of an aqueous solution and sealed and shielded from light.
A: 5 people did not feel a bad odor B: 4 people did not feel a bad odor C: 3 people did not feel a bad odor D: 2 people did not feel a bad odor E: 0 people or 1 person had a bad smell Did not feel (4 or 5 people had a bad smell)
実施例１
攪拌機、温度計、圧力計を具備した０．５Ｌオートクレーブに、ラウリルジメチルアミン（花王株式会社製ファーミン ＤＭ２０９８）８５．４ｇ（０．４０モル）、イオン交換水１７９．７ｇを入れ、窒素置換した。その後、４級化剤の添加条件として、温度を６０℃にした後に、塩化メチルをラウリルジメチルアミンに対して１．０２モル倍（２０．６ｇ）、添加速度０．０３３モル倍／分（添加時間３０．６分）で圧入して、次いで熟成条件として６０〜７０℃で２時間攪拌して反応させた。反応後に、ｐＨ調整として８０℃で炭酸ソーダを添加して、ｐＨ７．５（２５℃）、第４級アンモニウム塩濃度３６．８質量％、反応率９９．４％の第４級アンモニウム塩水溶液２８５ｇを得た。この第４級アンモニウム塩水溶液は、匂い評価Ｂであった。ここで、モル比は、ラウリルジメチルアミンの分子量を２１３．４１、塩化メチルの分子量を５０．４９として算出した。
Example 1
In a 0.5 L autoclave equipped with a stirrer, a thermometer, and a pressure gauge, 85.4 g (0.40 mol) of lauryl dimethylamine (Farmin DM2098 manufactured by Kao Corporation) and 179.7 g of ion-exchanged water were substituted with nitrogen. Then, as the addition conditions of the quaternizing agent, after the temperature was set to 60 ° C., methyl chloride was added 1.02 mol times (20.6 g) to lauryldimethylamine, and the addition rate was 0.033 mol times / min (addition). The reaction was carried out by stirring at 60 to 70 ° C. for 2 hours as aging conditions. After the reaction, sodium carbonate was added at 80 ° C. for pH adjustment, and 285 g of a quaternary ammonium salt aqueous solution having a pH of 7.5 (25 ° C.), a quaternary ammonium salt concentration of 36.8% by mass and a reaction rate of 99.4% Got. This aqueous quaternary ammonium salt had an odor rating B. Here, the molar ratio was calculated by setting the molecular weight of lauryldimethylamine to 213.41 and the molecular weight of methyl chloride to 50.49.
実施例２〜１０、比較例１〜４
実施例１と同様の反応装置を使用し、表１に示す仕込材料、４級化剤の添加条件の温度、４級化剤の添加速度、熟成条件で行った以外は、実施例１と同様の条件で反応を行って、表１に示すｐＨ、４級塩濃度、反応率の第４級アンモニウム塩水溶液を得た。それぞれの第４級アンモニウム塩水溶液の匂い評価を表１に示した。
Examples 2-10, Comparative Examples 1-4
The same reaction apparatus as in Example 1 was used, but the same as in Example 1 except that the charging materials shown in Table 1 were used, the temperature of the addition conditions of the quaternizing agent, the addition rate of the quaternizing agent, and the aging conditions. The reaction was carried out under the following conditions to obtain an aqueous quaternary ammonium salt solution having the pH, quaternary salt concentration, and reaction rate shown in Table 1. The odor evaluation of each quaternary ammonium salt aqueous solution is shown in Table 1.
実施例１１
攪拌機、温度計、圧力計を具備した０．５Ｌオートクレーブに、ラウリルジメチルアミン８５．４ｇ（０．４０モル）、イオン交換水１７７ｇ、ポリエーテル変性シリコーン（消泡剤、東レ・ダウコーニング株製 ＤＯＷ ＣＯＲＮＩＮＧ ＴＯＲＡＹ ＦＺ−２２０３）０．０２９ｇ（反応系に対して１００ｍｇ／ｋｇ）を入れ、窒素置換した。その後、４級化剤の添加条件として、温度を６０℃にした後に、塩化メチルをラウリルジメチルアミンに対して１．０５モル倍（２１．２ｇ）、添加速度０．０３３モル倍／分（添加時間３０．６分）で圧入して、次いで熟成条件として６０〜７０℃で２時間攪拌して反応させた。反応後に、反応混合物を攪拌機、温度計、導入管を具備した４つ口丸底フラスコに移し、８０℃で１７％炭酸ソーダ水溶液０．２８ｇを添加してｐＨ９．７にした。その後、８０℃、常圧下で窒素２Ｌ（第４級アンモニウム塩水溶液に対して７Ｌ／ｋｇ）を３時間で吹き込みして低沸点化合物の留去を行った後に、３５％塩酸水溶液０．２３ｇを加えて６０〜８０℃で１時間混合して、ｐＨ７．１（２５℃）、４級塩濃度３７．０％、反応率９９．４％の第４級アンモニウム塩水溶液２６０ｇを得た。この第４級アンモニウム塩水溶液は、匂い評価Ａであった。さらに、第４級アンモニウム塩水溶液を６０℃で２ヶ月間保存した結果、匂い評価Ａであった（評価方法は、何れも実施例１等と同じ）。
Example 11
In a 0.5 L autoclave equipped with a stirrer, thermometer and pressure gauge, 85.4 g (0.40 mol) of lauryl dimethylamine, 177 g of ion-exchanged water, polyether-modified silicone (antifoaming agent, DOW manufactured by Toray Dow Corning Co., Ltd.) CORNING TORAY FZ-2203) 0.029 g (100 mg / kg with respect to the reaction system) was added, and the atmosphere was replaced with nitrogen. Thereafter, as the addition conditions of the quaternizing agent, after the temperature was set to 60 ° C., methyl chloride was added 1.05 mol times (21.2 g) to lauryldimethylamine, and addition rate 0.033 mol times / min (addition) The reaction was carried out by stirring at 60 to 70 ° C. for 2 hours as aging conditions. After the reaction, the reaction mixture was transferred to a four-necked round bottom flask equipped with a stirrer, a thermometer and an introduction tube, and 0.28 g of 17% sodium carbonate aqueous solution was added at 80 ° C. to pH 9.7. Thereafter, 2 L of nitrogen (7 L / kg with respect to the quaternary ammonium salt aqueous solution) was blown in for 3 hours at 80 ° C. under normal pressure to distill off the low boiling point compound, and then 0.23 g of 35% hydrochloric acid aqueous solution was added. In addition, the mixture was mixed at 60 to 80 ° C. for 1 hour to obtain 260 g of a quaternary ammonium salt aqueous solution having a pH of 7.1 (25 ° C.), a quaternary salt concentration of 37.0%, and a reaction rate of 99.4%. This aqueous quaternary ammonium salt had an odor evaluation A. Further, the quaternary ammonium salt aqueous solution was stored at 60 ° C. for 2 months.
実施例１２
実施例１１と同様の条件で反応して、第４級アンモニウム塩水溶液を得た。反応後に、反応混合物を攪拌機、温度計、導入管を具備した４つ口丸底フラスコに移し、７０℃で炭酸ソーダを添加してｐＨ９．５に調整した。その後、７０℃、６０ｋＰａの減圧下で窒素１Ｌ（第４級アンモニウム塩水溶液に対して３．５Ｌ／ｋｇ）を３時間で吹き込みして低沸点化合物の留去を行った後に、３５％塩酸水溶液加えて６０〜８０℃で１時間混合して、ｐＨ６．８（２５℃）、４級塩濃度３７．３％、反応率９９．４％の第４級アンモニウム塩水溶液２５５ｇを得た。この第４級アンモニウム塩水溶液は、匂い評価Ａであった。さらに、第４級アンモニウム塩水溶液を６０℃で２ヶ月間保存した結果、匂い評価Ａであった（評価方法は、何れも実施例１等と同じ）。
Example 12
Reaction was carried out under the same conditions as in Example 11 to obtain an aqueous quaternary ammonium salt solution. After the reaction, the reaction mixture was transferred to a four-necked round bottom flask equipped with a stirrer, a thermometer, and an introduction tube, and adjusted to pH 9.5 by adding sodium carbonate at 70 ° C. Thereafter, 1 L of nitrogen (3.5 L / kg with respect to the quaternary ammonium salt aqueous solution) was blown in for 3 hours under a reduced pressure of 70 ° C. and 60 kPa to distill off the low boiling point compound, and then a 35% hydrochloric acid aqueous solution. In addition, the mixture was mixed at 60 to 80 ° C. for 1 hour to obtain 255 g of a quaternary ammonium salt aqueous solution having a pH of 6.8 (25 ° C.), a quaternary salt concentration of 37.3% and a reaction rate of 99.4%. This aqueous quaternary ammonium salt had an odor evaluation A. Further, the quaternary ammonium salt aqueous solution was stored at 60 ° C. for 2 months.
Claims (7)
水に対する第３級アミン（１）の割合が、４級化剤を最初に導入する前の時点で、３０〜６０質量％であり、
４級化剤を第３級アミン（１）に対して０．００６〜０．０４モル倍／分の添加速度で反応系に添加する、
第４級アンモニウム塩の製造方法。
（式中、Ｒ1は、エステル基、アミド基又はエーテル基が挿入されていてもよい、炭素数６〜３０の直鎖又は分岐鎖のアルキル基又はアルケニル基を示す。）
（式中、Ｒ1は、エステル基、アミド基又はエーテル基が挿入されていてもよい、炭素数６〜３０の直鎖又は分岐鎖のアルキル基又はアルケニル基を示し、Ｒ2は炭素数１〜３のアルキル基を示し、Ｘ-は陰イオン基を示す。） A quaternary ammonium salt for producing a quaternary ammonium salt (2) represented by the following general formula (2) by quaternizing the tertiary amine (1) represented by the following general formula (1) in water. A manufacturing method of
The proportion of tertiary amine (1) to water is 30-60% by weight before the first introduction of the quaternizing agent,
A quaternizing agent is added to the reaction system at an addition rate of 0.006 to 0.04 mol times / min with respect to the tertiary amine (1).
A method for producing a quaternary ammonium salt.
(In the formula, R 1 represents a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms into which an ester group, an amide group or an ether group may be inserted.)
(In the formula, R 1 represents a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms into which an ester group, an amide group or an ether group may be inserted, and R 2 represents one carbon atom. ˜3 represents an alkyl group, and X − represents an anionic group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011288553A JP5809050B2 (en) | 2011-12-28 | 2011-12-28 | Method for producing quaternary ammonium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011288553A JP5809050B2 (en) | 2011-12-28 | 2011-12-28 | Method for producing quaternary ammonium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013136542A JP2013136542A (en) | 2013-07-11 |
| JP5809050B2 true JP5809050B2 (en) | 2015-11-10 |
Family
ID=48912624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011288553A Active JP5809050B2 (en) | 2011-12-28 | 2011-12-28 | Method for producing quaternary ammonium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5809050B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6725864B2 (en) * | 2015-08-21 | 2020-07-22 | Dic株式会社 | Active energy ray curable composition and film using the same |
| CN108911994A (en) * | 2018-06-11 | 2018-11-30 | 上海华银日用品有限公司 | A kind of environmental protection long chain alkyl ammonium salt solution and its continuous preparation method |
| CN113501760B (en) * | 2021-07-16 | 2024-02-02 | 万华化学集团股份有限公司 | Synthesis method of low-cost long-carbon-chain cationic quaternary ammonium salt |
| CN114031769B (en) * | 2021-11-29 | 2024-03-26 | 广州市慧科高新材料科技有限公司 | Quaternary ammonium salt leveling agent, preparation method thereof, electroplating solution containing quaternary ammonium salt leveling agent and electroplating method |
-
2011
- 2011-12-28 JP JP2011288553A patent/JP5809050B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013136542A (en) | 2013-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5809050B2 (en) | Method for producing quaternary ammonium salt | |
| EP0721936B1 (en) | Liquid softener composition and quaternary ammonium salt | |
| US20070179080A1 (en) | Easy dispersible concentrrate ester quat compositions | |
| US10011807B2 (en) | Fabric softener compositions | |
| JP5681003B2 (en) | Softener composition | |
| JPH04174770A (en) | Concentrated type softening finish | |
| JP5809043B2 (en) | Method for producing quaternary ammonium salt | |
| JP5809051B2 (en) | Method for producing quaternary ammonium salt aqueous solution | |
| US20110229428A1 (en) | Fabric softening compositions and methods | |
| WO1995016766A1 (en) | Viscosity stable concentrated liquid fabric softener compositions | |
| US11299692B2 (en) | Fabric softener active compositions | |
| JP3469974B2 (en) | Liquid softener composition | |
| JP7051538B2 (en) | Fiber treatment agent composition | |
| JP3224191B2 (en) | Liquid softener composition | |
| JP5912508B2 (en) | Softener composition | |
| EP1902083B1 (en) | Oligomeric amidoamines or amidoquats for fabric or hair treatment compositions | |
| JP5815395B2 (en) | Softener composition | |
| EP1171558A1 (en) | Softener compositions having high hydrolytic stability and concentratibility | |
| JP3995767B2 (en) | Method for producing quaternary ammonium salt having good hue | |
| JP4381828B2 (en) | Cationic surfactant composition and method for producing the same | |
| KR101628909B1 (en) | Gemini surfactants, preparing method thereof and fabric softner comprising thereof | |
| KR101502443B1 (en) | Quaternary ammonium cationic surfactant with hydroxyl group, preparation method of thereof and fabric softener composition containing thereof | |
| KR100834483B1 (en) | Method for preparing of cationic surfactants | |
| KR100696704B1 (en) | Preparation of cationic surfactants containing ester group | |
| EP0790295A2 (en) | Fabric softening composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140916 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150422 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150512 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150708 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150908 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150910 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5809050 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |