JP2819491B2 - Preparation of alkaline earth metal sulfide mixtures of salicylic acids and phenols - Google Patents
Preparation of alkaline earth metal sulfide mixtures of salicylic acids and phenolsInfo
- Publication number
- JP2819491B2 JP2819491B2 JP9539493A JP9539493A JP2819491B2 JP 2819491 B2 JP2819491 B2 JP 2819491B2 JP 9539493 A JP9539493 A JP 9539493A JP 9539493 A JP9539493 A JP 9539493A JP 2819491 B2 JP2819491 B2 JP 2819491B2
- Authority
- JP
- Japan
- Prior art keywords
- alkaline earth
- earth metal
- reaction
- mol
- phenols
- 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.)
- Expired - Lifetime
Links
- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims description 84
- 150000002989 phenols Chemical class 0.000 title claims description 45
- 239000000203 mixture Substances 0.000 title claims description 44
- -1 alkaline earth metal sulfide Chemical class 0.000 title claims description 20
- 150000003870 salicylic acids Chemical class 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 72
- 239000003153 chemical reaction reagent Substances 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000004821 distillation Methods 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000005486 sulfidation Methods 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 108
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 71
- 239000007795 chemical reaction product Substances 0.000 description 52
- 239000000047 product Substances 0.000 description 35
- 229910052757 nitrogen Inorganic materials 0.000 description 33
- 239000012467 final product Substances 0.000 description 27
- 239000007788 liquid Chemical group 0.000 description 26
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 21
- 238000006473 carboxylation reaction Methods 0.000 description 20
- 239000003921 oil Substances 0.000 description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- 238000007259 addition reaction Methods 0.000 description 15
- 239000010687 lubricating oil Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 15
- 238000001914 filtration Methods 0.000 description 14
- 238000005987 sulfurization reaction Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 239000003085 diluting agent Substances 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000021523 carboxylation Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229960001860 salicylate Drugs 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 241000219198 Brassica Species 0.000 description 3
- 235000003351 Brassica cretica Nutrition 0.000 description 3
- 235000003343 Brassica rupestris Nutrition 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 235000010460 mustard Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- ILJOIOLSOMYKNF-UHFFFAOYSA-N 2,3-didodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCCCCC ILJOIOLSOMYKNF-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000005956 Cosmos caudatus Nutrition 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、潤滑油および燃料油に
添加する清浄剤として極めて有用な、サリチル酸類およ
びフェノール類のアルカリ土類金属塩硫化混合物の製法
に関するものであり、さらに詳細には、製品の色相改善
および回収フェノールの白濁を防止し得る改良された上
記製法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for preparing a sulfurized mixture of an alkaline earth metal salt of salicylic acids and phenols, which is extremely useful as a detergent added to lubricating oils and fuel oils. The present invention relates to an improved method for improving the hue of a product and preventing clouding of recovered phenol.
【０００２】[0002]
【従来の技術】本発明者らは、アルカリ土類金属酸化
物、水酸化物またはそれらの混合物（以下、「アルカリ
土類金属試薬」という。）、アルキルフェノールおよび
二価アルコールを混合反応させ、その後水と二価アルコ
ールを留去し、得られたアルカリ土類金属フェネートに
二酸化炭素処理を施すことによりヒドロキシアルキル安
息香酸塩（サリシレート）を形成し、それに元素硫黄を
反応させることによりヒドロキシアルキル安息香酸およ
びアルキルフェノールのアルカリ土類金属塩硫化混合物
ならびにその製造法を得ることに成功した（特開昭６４
−２９３５４）。この方法は、アルカリ金属を使用する
必要がなく、アルカリ土類金属フェネートから直接アル
カリ土類金属ヒドロキシアルキル安息香酸塩を形成する
ことにより製造工程を著しく単純化した点に特色があ
る。また、特願平４−２７５０２６では、ヒドロキシア
ルキル安息香酸塩を形成後、硫化をする際にアルカリ土
類金属試薬と二価アルコールを再び添加して硫化金属付
加反応を行うことにより生成するヒドロキシアルキル安
息香酸およびアルキルフェノールのアルカリ土類金属塩
硫化混合物の塩基価を向上し、さらに色相を明るくし
た。これら２つの方法は、フェノール類の存在はアルキ
ルサリチル酸の生成を妨害するという従来からの考えを
覆すもので、これにより、アルキルフェノールを溶媒と
して使用することが可能となり特殊な溶媒や添加物を必
要とせず、希釈油として使用する鉱油を除けば全て反応
に直接用いられるもののみを原料として用いている。し
たがって、使用原料の種類を必要最小限にとどめている
点で優れている。2. Description of the Related Art The present inventors have made an alkaline earth metal oxide, a hydroxide or a mixture thereof (hereinafter referred to as "alkaline earth metal reagent"), an alkylphenol and a dihydric alcohol mixed and reacted. Water and dihydric alcohol are distilled off, and the obtained alkaline earth metal phenate is subjected to carbon dioxide treatment to form a hydroxyalkyl benzoate (salicylate), which is then reacted with elemental sulfur to obtain a hydroxyalkyl benzoic acid. Of alkaline earth metal salts of phenols and alkylphenols and a process for producing the same (JP-A-64
-29354). This method is characterized in that it does not require the use of an alkali metal and significantly simplifies the manufacturing process by forming the alkaline earth metal hydroxyalkyl benzoate directly from the alkaline earth metal phenate. Further, Japanese Patent Application No. 4-275,026 discloses that a hydroxyalkyl benzoate is formed, and then, at the time of sulfurization, a hydroxyalkyl formed by adding an alkaline earth metal reagent and a dihydric alcohol again to carry out a metal sulfide addition reaction. The base value of the alkaline earth metal salt sulfide mixture of benzoic acid and alkylphenol was improved, and the hue was further increased. These two methods reverse the conventional belief that the presence of phenols interferes with the production of alkylsalicylic acid, which allows the use of alkylphenols as solvents and requires special solvents and additives. Instead, only those directly used in the reaction were used as raw materials except for the mineral oil used as the diluent oil. Therefore, it is excellent in that the types of raw materials used are kept to the minimum necessary.
【０００３】また、本発明者らは特願平５−２０５８１
で、硫化反応時にエチレングリコールを添加することに
より、得られる製品の色相が著しく明るくなることを見
いだしている。Further, the present inventors have disclosed in Japanese Patent Application No. 5-205581.
It has been found that the addition of ethylene glycol during the sulfidation reaction significantly increases the hue of the resulting product.
【０００４】[0004]
【発明が解決しようとする課題】しかし、特開昭６４−
２９３５４の方法は、得られる製品の色相が著しく暗い
という欠点が、特願平４−２７５０２６の方法は、得ら
れる製品の色相は明るくなるが、工程数（炭酸化反応工
程）が増えるため、製造時間が長くなり、各種ユーティ
リティーにかかるコストが大きくなるといった欠点が、
また特願平５−２０５８１では、製品の色相は明るくな
るが、硫化反応を常圧または加圧の密閉系で行うと、そ
の後のフェノール類回収の際に回収フェノール類が白濁
してしまうという欠点があった。回収フェノール類は、
循環して再利用することが好ましく、再利用できないと
フェノール類を多量に使用するため原料コストが莫大に
かかってしまう。この回収フェノール類が白濁する理由
は詳かではないが、サリチル酸類およびフェノール類の
アルカリ土類金属塩硫化混合物を製造する際に、硫化を
二価アルコールの存在下に製造段階の後期に行うためで
あり、ポリスルフィド等の副生物が回収フェノール類中
に混入するためと考えられる。白濁したフェノール類
は、フェノール類としての商品価値が低いことは勿論、
フェネートやサリシレートの製造に再使用する原料とし
ても、望ましくない副反応が生じることが予想され、ま
た最終製品の油溶性低下の原因となるため適当でない。However, Japanese Unexamined Patent Publication No.
The method of No. 29354 is disadvantageous in that the color of the obtained product is extremely dark, and the method of Japanese Patent Application No. 4-75026 is lighter in the color of the obtained product but increases the number of steps (carbonation reaction step). Disadvantages such as longer time and higher costs for various utilities,
In Japanese Patent Application No. 5-20581, the hue of the product becomes bright, but if the sulfidation reaction is carried out in a closed system under normal pressure or pressure, the recovered phenol will become cloudy in the subsequent recovery of phenol. was there. The recovered phenols are
It is preferable to circulate and reuse, and if it cannot be recycled, a large amount of phenols are used, so that the raw material cost is enormous. The reason why the recovered phenols become cloudy is not clear, but when producing an alkaline earth metal salt sulfide mixture of salicylic acids and phenols, sulfidation is carried out later in the production stage in the presence of a dihydric alcohol. It is considered that by-products such as polysulfide are mixed in the recovered phenols. Cloudy phenols, of course, have low commercial value as phenols,
Raw materials that are reused in the production of phenates and salicylates are not suitable because undesirable side reactions are expected to occur and cause a reduction in oil solubility of the final product.
【０００５】本発明の目的は、工程数、使用原料を必要
最小限にとどめながら、製品が明るい色相を有し、かつ
回収フェノール類が濁らずに再使用可能であり、そして
酸中和能力の高いサリチル酸類およびフェノール類のア
ルカリ土類金属塩硫化混合物を製造する方法を提供する
ことにある。[0005] It is an object of the present invention to minimize the number of steps and raw materials used, to obtain a product having a bright hue, to be able to reuse recycled phenols without becoming cloudy, and to have an acid neutralizing ability. It is an object of the present invention to provide a method for producing a high-sulfurized mixture of salicylic acids and phenols of an alkaline earth metal salt.
【０００６】[0006]
【課題を解決するための手段】そこで、本発明者らはこ
れらの課題を解決するために鋭意検討を重ねた結果、硫
化反応を反応温度１６０℃以上、常圧または加圧の開放
系にて二価アルコールを特定量存在させる条件下で行う
ことにより、工程数を増やすことなく製品の色相を明る
くし、かつ回収フェノール類が濁らずに再使用可能とな
ることを見いだし、本発明を完成したものである。The inventors of the present invention have conducted intensive studies to solve these problems, and as a result, have found that the sulfidation reaction can be carried out at a reaction temperature of 160 ° C. or higher and in an open system under normal pressure or pressure. By conducting the reaction under the condition that a specific amount of dihydric alcohol is present, the hue of the product is brightened without increasing the number of steps, and it has been found that the recovered phenols can be reused without becoming cloudy, and the present invention has been completed. Things.
【０００７】すなわち、本発明の要旨は、フェノール
類、二価アルコール類、アルカリ土類金属試薬よりなる
反応原料混合物またはこれらに水を加えたものを反応さ
せ、次いで水および二価アルコールを留去して得られた
蒸留塔底物に二酸化炭素を反応させ、得られた生成物に
二価アルコール類および元素硫黄を添加して硫化反応を
行うことからなるサリチル酸類およびフェノール類のア
ルカリ土類金属塩硫化混合物の製法において、（ａ）硫
化反応の際、反応温度を１６０℃以上、加圧開放系で反
応を行い、添加する二価アルコール類をアルカリ土類金
属試薬１モル当たり２．０モル以上とするか、あるいは
（ｂ）硫化反応の際、反応温度を１６０℃以上、常圧開
放系で反応を行い、添加する二価アルコール類をアルカ
リ土類金属試薬１モル当たり０．５モル以上とすること
を特徴とするサリチル酸類およびフェノール類のアルカ
リ土類金属塩硫化混合物の製法に存する。That is, the gist of the present invention is to provide a reaction raw material mixture comprising phenols, dihydric alcohols and alkaline earth metal reagents or a reaction mixture obtained by adding water thereto, and then distilling off water and the dihydric alcohol. Alkaline earth metals such as salicylic acids and phenols, which are obtained by reacting carbon dioxide with the bottom of the distillation column obtained by the reaction and adding a dihydric alcohol and elemental sulfur to the obtained product to carry out a sulfurization reaction. In the method for producing a salt-sulfide mixture, (a) at the time of the sulfurization reaction, the reaction temperature is 160 ° C. or higher, the reaction is carried out in a pressurized and open system, and the dihydric alcohol to be added is 2.0 mol per mol of the alkaline earth metal reagent Or (b) in the case of the sulfurization reaction, the reaction temperature is 160 ° C. or higher, the reaction is carried out in an open system under normal pressure, and the dihydric alcohol to be added is converted into one alkaline earth metal reagent. Consists in preparation of the alkaline earth metal salt or the alcohol is unsaturated salicylic acids and phenols, characterized in that the per 0.5 mol or more.
【０００８】本発明に使用されるフェノール類は、炭素
数４〜３６個、好ましくは炭素数８〜３２個の炭化水素
側鎖、例えばアルキル基、アルケニル基、アラルキル基
等を有するモノまたはジ置換フェノール類を挙げること
ができる。具体的には、ブチル、アミル、オクチル、ノ
ニル、ドデシル、セチル、エチルヘキシル、トリアコン
チル等の炭化水素基、あるいは流動パラフィン、ワック
ス、オレフィン重合体（ポリエチレン、ポリプロピレ
ン、ポリブテン等）の石油炭化水素から誘導される基を
有するフェノール類が単独、あるいはこれらの混合物に
て使用される。通常約１３０℃、好ましくは約１２０℃
で液状となり得るものが望ましい。これらフェノール類
の具体例としては、ブチルフェノール、オクチルフェノ
ール、ノニルフェノール、ドデシルフェノール、セチル
フェノール、ポリブテンでアルキル化したアルキルフェ
ノール、ジノニルフェノール、ジドデシルフェノールな
どが挙げられる。The phenol used in the present invention is a mono- or di-substituted phenol having a hydrocarbon side chain having 4 to 36 carbon atoms, preferably 8 to 32 carbon atoms, such as an alkyl group, an alkenyl group and an aralkyl group. Phenols can be mentioned. Specifically, it is derived from hydrocarbon groups such as butyl, amyl, octyl, nonyl, dodecyl, cetyl, ethylhexyl, and triacontyl, or liquid paraffins, waxes, and petroleum hydrocarbons such as olefin polymers (polyethylene, polypropylene, polybutene, etc.). Phenols having one or more groups are used alone or in a mixture thereof. Usually about 130 ° C, preferably about 120 ° C
It is desirable that the material can be in a liquid state. Specific examples of these phenols include butylphenol, octylphenol, nonylphenol, dodecylphenol, cetylphenol, alkylphenol alkylated with polybutene, dinonylphenol, didodecylphenol and the like.
【０００９】アルカリ土類金属試薬としては、通常アル
カリ土類金属の酸化物、あるいは水酸化物ないしはそれ
らの混合物が用いられる。例えばカルシウム、バリウ
ム、ストロンチウム、マグネシウム等の酸化物あるいは
水酸化物ないしはそれらの混合物が用いられる。フェノ
ール類に対するアルカリ土類金属試薬の使用量は、使用
フェノール１当量当たり約０．９９当量以下、好ましく
は０．０１〜０．９８当量である。As the alkaline earth metal reagent, an oxide or hydroxide of an alkaline earth metal or a mixture thereof is usually used. For example, oxides or hydroxides of calcium, barium, strontium, magnesium and the like, or mixtures thereof are used. The amount of the alkaline earth metal reagent used relative to the phenol is about 0.99 equivalent or less, preferably 0.01 to 0.98 equivalent, per equivalent of the phenol used.
【００１０】フェノール類に対するアルカリ土類金属試
薬の量が多過ぎると中間体がゲル化してそれ以上反応が
進まないため、目的とする良好な生成物が得られない。
また、少な過ぎると原料に対する製品の収率が低下する
ばかりか、フェノール類の回収に費やすユーティリティ
や時間が大となり、経済的に不利である。If the amount of the alkaline earth metal reagent relative to the phenol is too large, the intermediate gels and the reaction does not proceed any further, so that the desired good product cannot be obtained.
On the other hand, if the amount is too small, not only does the yield of the product relative to the raw material decrease, but the utility and time spent for recovering phenols increase, which is economically disadvantageous.
【００１１】次に、二価アルコールとしては、比較的低
沸点かつ低粘度で反応性に富むものが使用される。二価
アルコールは、炭素数が２〜６を有することが好まし
く、特に、エチレングリコール、プロピレングリコール
等が好ましい。二価アルコールはフェノール類とアルカ
リ土類金属試薬との反応による油溶性物質への転化を助
け、一部は生成物中に取り込まれる。Next, a dihydric alcohol having a relatively low boiling point, a low viscosity and a high reactivity is used. The dihydric alcohol preferably has 2 to 6 carbon atoms, particularly preferably ethylene glycol and propylene glycol. Dihydric alcohols assist in the conversion of phenols and alkaline earth metal reagents to oil-soluble materials by reaction, some of which are incorporated into the product.
【００１２】本発明法においては、金属付加反応は、反
応促進効果のある水を添加して行っても、添加しないで
行っても良く、水を添加して行う場合、二価アルコール
の使用量はアルカリ土類金属試薬１モル当たり約０．１
５〜３．０モル、特に約０．３〜１．５モルが好まし
い。また水を添加しないで行う場合、二価アルコールの
使用量はアルカリ土類金属試薬１モル当たり、約１．０
〜３．０モル、特に約１．２〜２．０モルが好ましい。In the method of the present invention, the metal addition reaction may or may not be carried out with the addition of water having a reaction promoting effect. Is about 0.1 per mole of alkaline earth metal reagent
5-3.0 moles, especially about 0.3-1.5 moles, are preferred. When the reaction is carried out without adding water, the amount of the dihydric alcohol used is about 1.0 per mole of the alkaline earth metal reagent.
~ 3.0 moles, especially about 1.2-2.0 moles are preferred.
【００１３】二価アルコールの使用量が少なすぎると反
応原料、特にアルカリ土類金属試薬のアルカリ土類金属
フェネートへの転化率が低下する。それにより不溶解分
が増加し、ろ過が困難になるばかりでなく、後のカルボ
キシル化工程で、カルボキシル化率が低下し、ヒドロキ
シベンゾエート生成量が減少する。また、多すぎるとフ
ェノール類への金属付加反応は円滑に進行するが、反応
生成物から過剰の二価アルコールを蒸留留去する時間お
よびユーティリティーが過大にかかってしまう。If the amount of the dihydric alcohol used is too small, the conversion of the starting materials for the reaction, particularly the alkaline earth metal reagent to the alkaline earth metal phenate decreases. This increases the amount of insolubles and makes filtration difficult, and in the subsequent carboxylation step, the carboxylation rate decreases and the amount of hydroxybenzoate produced decreases. If the amount is too large, the metal addition reaction to the phenol proceeds smoothly, but the time and utility for distilling off excess dihydric alcohol from the reaction product are excessively long.
【００１４】また、後記する硫化反応時に使用する二価
アルコールの使用量は、反応を加圧開放系で行う場合、
アルカリ土類金属試薬１モル当たり２．０〜１０モル、
好ましくは２．０〜５．０モル、反応を常圧開放系で行
う場合、アルカリ土類金属試薬１モル当たり０．５〜１
０モル、好ましくは１．０〜５．０モルとする。二価ア
ルコールの使用量が多すぎると、反応生成物から過剰の
二価アルコールを蒸留留去する時間およびユーティリテ
ーが過大にかかってしまう。また、上記した範囲より二
価アルコールの使用量が少ないと、回収フェノールの白
濁を防止するという効果が得られなくなる。ここで開放
系とは、ある一定の圧力を保持するのに反応の進行によ
り変化する反応器内の圧力をガスの出し入れにより調節
する系を言う。The amount of the dihydric alcohol used in the sulfurization reaction described below is determined when the reaction is carried out in a pressure-open system.
2.0 to 10 mol per mol of alkaline earth metal reagent,
2.0 to 5.0 mol, preferably 0.5 to 1 mol per mol of alkaline earth metal reagent when the reaction is carried out in an open system under normal pressure.
0 mol, preferably 1.0 to 5.0 mol. If the amount of the dihydric alcohol used is too large, the time and utility for distilling off excess dihydric alcohol from the reaction product will be excessive. If the amount of the dihydric alcohol used is less than the above range, the effect of preventing the recovered phenol from becoming cloudy cannot be obtained. Here, the open system refers to a system in which the pressure in the reactor, which changes with the progress of the reaction while maintaining a certain pressure, is adjusted by taking in and out of gas.
【００１５】フェノール類へのアルカリ土類金属試薬の
金属付加反応工程において反応を促進するために反応系
中に水を添加する場合は、蒸留水はもちろん缶水や工業
用水、金属付加反応で生成する水などが使用でき、その
品質に特に制限はなく、冷水、温水、水蒸気等どのよう
な状態の水でも使用できる。金属付加反応促進のために
用いる水の反応器への添加は水単独で行ってもよいし、
一部あるいは全部をフェノール類や二価アルコールなど
ほかの原料との混合物として添加してもよい。反応器へ
の水の添加時期は特に制限はなく、水以外の全反応原料
が混合される前でも後でも良いが、全反応原料混合後約
１時間以内に添加するのが好ましい。When water is added to the reaction system to promote the reaction in the metal addition reaction of an alkaline earth metal reagent to phenols, not only distilled water but also still water, industrial water, and metal addition reaction are used. The quality of the water is not particularly limited, and water in any state such as cold water, hot water, and steam can be used. Water used for promoting the metal addition reaction may be added to the reactor alone with water,
Some or all of them may be added as a mixture with other raw materials such as phenols and dihydric alcohols. The timing of adding water to the reactor is not particularly limited, and may be before or after all of the reaction materials other than water are mixed, but it is preferable to add the water within about one hour after mixing all of the reaction materials.
【００１６】反応系中への金属付加反応促進のために用
いる水の添加量は使用するアルカリ土類金属試薬１モル
当たり約０．０１〜１０モル、望ましくは０．１〜２．
０モルである。外部から水を反応系中に添加して金属付
加反応を行うと、水を添加しない以外は同一の条件で反
応を行う場合に比べて反応が円滑に進行する。反応系中
へ添加する水が少なすぎるとその効果は減少してしま
う。また逆に多すぎれば反応後の蒸留工程が簡略化され
るという利点が失われる。The amount of water used for promoting the metal addition reaction into the reaction system is about 0.01 to 10 mol, preferably 0.1 to 2.0 mol per mol of the alkaline earth metal reagent used.
0 mol. When a metal addition reaction is carried out by adding water from the outside to the reaction system, the reaction proceeds smoothly as compared with the case where the reaction is carried out under the same conditions except that water is not added. If too little water is added to the reaction system, the effect will be reduced. Conversely, if the amount is too large, the advantage that the distillation step after the reaction is simplified is lost.
【００１７】硫黄の使用量は、極少量から大多量の広い
範囲にわたって使用できる。通常の使用量は、アルカリ
土類金属試薬１モル当たり０．１〜４．０モル、好まし
くは０．２〜３．０モル、さらに好ましくは０．２〜
１．５モルを用いる。硫黄の使用量を低減するにつれ製
品の粘度は低下するが、使用量が少なすぎると製品中の
硫化物が減少し、油溶性が低下してしまう。また多すぎ
ると製品の塩基性が低下するため塩基価の高い製品が得
にくくなるばかりでなく、製品の粘度が著しく高くなっ
てしまう。The amount of sulfur can be used in a wide range from a very small amount to a large amount. The usual use amount is 0.1 to 4.0 mol, preferably 0.2 to 3.0 mol, more preferably 0.2 to 4.0 mol per mol of the alkaline earth metal reagent.
Use 1.5 moles. As the amount of sulfur used is reduced, the viscosity of the product decreases, but if the amount is too small, the sulfide in the product is reduced and the oil solubility is reduced. On the other hand, if the content is too large, the basicity of the product is lowered, so that not only is it difficult to obtain a product having a high base number, but also the viscosity of the product becomes extremely high.
【００１８】硫化反応の際使用する不活性ガスとして
は、窒素、ヘリウムなどが挙げられるが、好ましくは窒
素ガスを用いる。As the inert gas used in the sulfurization reaction, nitrogen, helium and the like can be mentioned, but nitrogen gas is preferably used.
【００１９】本発明において、反応物、反応中間体、あ
るいは製品等の取扱いを容易にするために適当な粘度を
有する希釈剤もしくは溶剤（以下、「希釈剤」とい
う。）を加えることができる。たとえば硫化反応を終え
たのちの反応生成物中から過剰の未反応フェノール類を
蒸留で回収する際、高沸点で、かつ適当な粘度を有する
希釈剤の存在下で行うことによって反応塔底物を液状の
望ましい状態で得ることができる。なお、通常は未反応
フェノール類の留出に伴って希釈剤の一部も留出する。
したがって、回収フェノール類を繰り返し反応に供する
という目的の為には希釈剤としては反応に直接悪影響を
与えないものが望ましい。また希釈剤の存在下に反応を
行ってもよい。好ましい希釈剤の例としては、パラフィ
ン系、ナフテン系、芳香族系、あるいは混合系の基油な
どの適当な粘度の石油留分、例えば沸点約２２０〜５５
０℃で粘度が１００℃で約０．５〜４０ｃＳｔの潤滑油
留分を挙げることができる。その他の有機溶媒でも疎水
性、かつ、親油性を示し、反応時や製品の用途面におい
て無害であれば希釈剤として用いることができる。In the present invention, a diluent or a solvent (hereinafter, referred to as "diluent") having an appropriate viscosity can be added to facilitate handling of a reactant, a reaction intermediate, or a product. For example, when recovering excess unreacted phenols from the reaction product after the sulfurization reaction by distillation, the reaction bottoms are obtained by performing the reaction at a high boiling point and in the presence of a diluent having an appropriate viscosity. It can be obtained in a desirable liquid state. Note that, usually, a part of the diluent is also distilled off as the unreacted phenols are distilled off.
Therefore, for the purpose of repeatedly subjecting the recovered phenols to the reaction, a diluent that does not directly affect the reaction is desirable. The reaction may be performed in the presence of a diluent. Examples of preferred diluents include petroleum fractions of suitable viscosity such as paraffinic, naphthenic, aromatic or mixed base oils, e.g.
A lubricating oil fraction having a viscosity of about 0.5 to 40 cSt at 100C at 0 ° C can be mentioned. Other organic solvents also exhibit hydrophobicity and lipophilicity, and can be used as a diluent if they are harmless at the time of reaction or in the application of the product.
【００２０】本発明におけるサリチル酸類およびフェノ
ール類のアルカリ土類金属塩硫化混合物の主なる製造工
程および運転条件は下記のとおりである。The main production steps and operating conditions of the alkaline earth metal salt sulfide mixture of salicylic acids and phenols in the present invention are as follows.
【００２１】（イ）金属付加工程 所定量のフェノール類、二価アルコール類、アルカリ土
類金属試薬、および必要により希釈剤および／または前
記所定量の水からなる反応原料混合物を反応温度６０〜
２００℃、好ましくは約９０〜１９０℃の範囲で反応さ
せる。その際、反応は約０．０１〜１０atmの減圧、常
圧、もしくは加圧の条件下にて行う。上記金属付加反応
工程において生成する水および添加した水は次のカルボ
キシル化工程前に全量の約９９．９％以上、好ましくは
全量を、二価アルコールは系内に残存する量がアルカリ
土類金属試薬１モル当たり通常約０．６モル以下、好ま
しくは約０．３モル以下になるように留去する。水およ
び二価アルコールが系内に多量に残存すると次のカルボ
キシル化工程で、カルボキシル化率が低下し、ヒドロキ
シベンゾエート生成量が減少する。本反応は通常約１〜
９時間の範囲内でほぼ終了する。(A) Metal Addition Step A reaction raw material mixture comprising a predetermined amount of a phenol, a dihydric alcohol, an alkaline earth metal reagent, and, if necessary, a diluent and / or the predetermined amount of water is reacted at a reaction temperature of 60 to 60%.
The reaction is carried out at 200C, preferably in the range of about 90-190C. At this time, the reaction is carried out under reduced pressure, normal pressure, or pressurized condition of about 0.01 to 10 atm. The water generated in the above metal addition reaction step and the added water are about 99.9% or more, preferably the whole amount, of the total amount before the next carboxylation step, and the dihydric alcohol is an alkaline earth metal in the amount remaining in the system. The solvent is distilled off so as to be usually about 0.6 mol or less, preferably about 0.3 mol or less, per 1 mol of the reagent. If a large amount of water and dihydric alcohol remain in the system, the carboxylation rate decreases in the next carboxylation step, and the amount of hydroxybenzoate produced decreases. This reaction is usually carried out
It almost finishes within 9 hours.
【００２２】（ロ）カルボキシル化工程 本工程は、前記の金属付加反応生成物をカルボキシル化
し、ヒドロキシベンゾエート成分を得る工程である。す
なわち、前記の金属付加反応生成物を反応温度約１５０
〜２４０℃、好ましくは約１６０〜２３０℃、反応圧力
は、約０．０５〜１００atm、好ましくは約０．１〜５
０atmの減圧、常圧もしくは加圧条件下で二酸化炭素と
反応させる。本反応は通常約１〜１０時間の範囲内でほ
ぼ終了する。(B) Carboxylation Step This step is a step of carboxylating the metal addition reaction product to obtain a hydroxybenzoate component. That is, the above-mentioned metal addition reaction product is reacted at a reaction temperature of about 150.
To 240 ° C, preferably about 160 to 230 ° C, and the reaction pressure is about 0.05 to 100 atm, preferably about 0.1 to 5 atm.
It is reacted with carbon dioxide under reduced pressure, normal pressure or pressurized condition of 0 atm. This reaction is generally completed within about 1 to 10 hours.
【００２３】（ハ）硫化工程 この硫化工程は最終製品の性質、特に油溶性、粘度特
性、貯蔵安定性などの物性を改善する工程で、この硫化
反応を常圧または加圧の開放系にて二価アルコールを特
定量、すなわち加圧開放系ではアルカリ土類金属試薬１
モル当たり二価アルコール２．０モル以上、そして常圧
開放系ではアルカリ土類金属試薬１モル当たり二価アル
コール０．５モル以上、存在させる条件下で行うことに
より、製品の色相が明るくなり、さらに回収フェノール
類の白濁現象が防止できる。前記のカルボキシル化工程
生成物を反応温度１６０℃以上、好ましくは１６０〜２
００℃、圧力１．０〜１０atmにて反応を行う。好まし
くは不活性ガス雰囲気下に行うのがよい。本反応は通常
約１〜２０時間でほぼ終了する。反応温度が高過ぎる
と、カルボキシル化工程で生成したヒドロキシベンゾエ
ートのカルボキシル基が脱カルボキシル化してしまう。
また、低過ぎると、製品の色相は明るくなるが、回収フ
ェノール類の白濁現象は改善されなくなる。また、白濁
現象は改善されても、製品の粘度が高くなってしまう。
粘度の低い製品を得るためには１６０℃以上の温度条件
とすることが好ましい。(Iii) Sulfidation step This sulfidation step is a step for improving the properties of the final product, in particular, properties such as oil solubility, viscosity characteristics and storage stability. A specific amount of dihydric alcohol, that is, alkaline earth metal reagent 1
When the reaction is carried out under the condition of 2.0 mol or more of dihydric alcohol per mol and 0.5 mol or more of dihydric alcohol per 1 mol of alkaline earth metal reagent in the normal pressure open system, the hue of the product becomes bright, Further, the clouding phenomenon of the recovered phenols can be prevented. The product of the carboxylation step is reacted at a reaction temperature of 160 ° C. or higher, preferably 160 to 2
The reaction is performed at 00 ° C. and a pressure of 1.0 to 10 atm. Preferably, the reaction is performed in an inert gas atmosphere. This reaction is generally completed in about 1 to 20 hours. If the reaction temperature is too high, the carboxyl group of hydroxybenzoate generated in the carboxylation step will be decarboxylated.
If it is too low, the hue of the product will be bright, but the clouding phenomenon of the recovered phenols will not be improved. Further, even if the cloudiness phenomenon is improved, the viscosity of the product increases.
In order to obtain a product having a low viscosity, the temperature is preferably set to 160 ° C. or higher.
【００２４】硫化反応後の反応生成物にアルカリ土類金
属試薬と二価アルコールとを添加し、さらに上記のよう
な金属付加反応を繰り返して行うことも可能である。そ
の際、金属付加反応後に下記（ニ）のような二酸化炭素
処理工程を繰り返して行うことも可能で、二酸化炭素処
理することにより、最終製品の性質、特に油溶性、粘度
特性、貯蔵安定性などを改善することができる。これに
より生成物の塩基価を上げることが可能となる。It is also possible to add an alkaline earth metal reagent and a dihydric alcohol to the reaction product after the sulfurization reaction, and to repeat the above metal addition reaction. At this time, it is also possible to repeat the carbon dioxide treatment step as described in the following (d) after the metal addition reaction, and the carbon dioxide treatment allows the properties of the final product, particularly oil solubility, viscosity characteristics, storage stability, etc. Can be improved. This makes it possible to increase the base number of the product.
【００２５】（ニ）二酸化炭素処理工程 前記のごとく複数回金属付加反応を行う場合、金属付加
反応後に、反応温度約１５０〜２４０℃、好ましくは約
１６０〜２３０℃、反応圧力は約０．０５〜１００at
m、好ましくは０．１〜５０atmの減圧、常圧、加圧条件
下で二酸化炭素と反応させる。(D) Carbon dioxide treatment step When the metal addition reaction is performed a plurality of times as described above, after the metal addition reaction, the reaction temperature is about 150 to 240 ° C, preferably about 160 to 230 ° C, and the reaction pressure is about 0.05. ~ 100at
m, preferably 0.1 to 50 atm, under reduced pressure, normal pressure and pressurized conditions.
【００２６】硫化反応後の反応生成物中の未反応フェノ
ール類は経済上などの面から、これらの１部もしくは大
部分を回収することが好ましく、この回収フェノール類
は原料として再使用され得る。ここで、未反応フェノー
ル類の蒸留を高沸点の鉱油など、通常の希釈剤の存在下
で行うと、蒸留残留物は液状の好ましい状態で得ること
ができる。残存する少量の不溶解性物質は、フェノール
類の回収前、あるいは回収後にろ過または遠心分離など
の操作により除去することができる。Unreacted phenols in the reaction product after the sulfurization reaction are preferably recovered in part or in large part from the viewpoint of economy and the like, and the recovered phenols can be reused as a raw material. Here, if the unreacted phenol is distilled in the presence of a normal diluent such as a high-boiling mineral oil, the distillation residue can be obtained in a preferable liquid state. A small amount of the remaining insoluble substance can be removed by an operation such as filtration or centrifugation before or after the recovery of the phenols.
【００２７】本発明方法の反応生成物の正確な構造の詳
細は不明であるが、反応生成物を加水分解し、加水分解
物をヘキサンのような溶剤で抽出して得られる油層にサ
リチル酸類とフェノール類の両者が検出されることから
原料フェノール類は、その一部が二酸化炭素との反応に
よりサリシレートに転化したものと考えられる。また、
反応生成物はフェノール類およびサリチル酸類の合計グ
ラム当量当たり理論量以上のアルカリ土類金属元素を含
有することから生成物は、塩基性アルカリ土類金属サリ
シレートもしくは塩基性硫化アルカリ土類金属サリシレ
ートと塩基性硫化アルカリ土類金属フェネートの骨格を
有するものと考えられる。一方、反応生成物はサリシレ
ート骨格のみよりなる分子とフェネート骨格のみよりな
る分子との混合物であるのか、１分子中にサリシレート
骨格とフェネート骨格との両者を有する化合物なのか、
または両者を含んだ混合物なのか詳細は不明であり、ま
た反応したアルカリ土類金属元素、反応した硫黄および
反応した二価アルコールとサリシレート骨格とフェネー
ト骨格との結合様式については詳細不明であり、さらに
反応した二酸化炭素のうちサリシレートへの転化に費や
された以外の二酸化炭素の生成物中における結合様式は
詳細不明である。いずれにせよ本発明の反応生成物は、
塩基性アルカリ土類金属フェネートと塩基性アルカリ土
類金属サリシレートの硫化混合物である。The exact structure of the reaction product of the process of the present invention is not known in detail, but the reaction product is hydrolyzed, and the hydrolyzate is extracted with a solvent such as hexane. Since both phenols are detected, it is considered that a part of the starting phenol was converted into salicylate by reaction with carbon dioxide. Also,
Since the reaction product contains a theoretical amount or more of alkaline earth metal element per gram equivalent of phenols and salicylic acids, the product is a basic alkaline earth metal salicylate or a basic alkaline earth metal salicylate and a base. It is considered to have a skeleton of a sulfided alkaline earth metal phenate. On the other hand, whether the reaction product is a mixture of a molecule consisting of only a salicylate skeleton and a molecule consisting of only a phenate skeleton, or a compound having both a salicylate skeleton and a phenate skeleton in one molecule,
It is unknown whether it is a mixture containing the two or a mixture containing both, and the details of the reacted alkaline earth metal element, the reacted sulfur and the bonding mode between the reacted dihydric alcohol, the salicylate skeleton, and the phenate skeleton are unknown. The mode of binding in the product of carbon dioxide other than that spent on the conversion to salicylate of the reacted carbon dioxide is unknown. In any case, the reaction product of the present invention
It is a sulfurized mixture of a basic alkaline earth metal phenate and a basic alkaline earth metal salicylate.
【００２８】[0028]
【実施例】以下、本発明を実施例によりさらに具体的に
説明するが、これらは単に例示であって本発明を制限す
るものではない。以下の実施例ならびに比較例におい
て、圧力は特記しない限りゲージ圧である。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but these are merely examples and do not limit the present invention. In the following Examples and Comparative Examples, pressures are gauge pressures unless otherwise specified.
【００２９】実施例１ 撹拌器、冷却管、窒素ガス導入管および温度計を装着し
た５lオートクレーブに純度９４．４％のドデシルフェ
ノール２９１７．８ｇ（１０．５モル）、純度９５．８
％の酸化カルシウム１７５．７ｇ（３．０モル）を送入
し、撹拌した。この懸濁液にエチレングリコール２５
１．５ｇ（４．０５モル）にイオン交換水５．４ｇ
（０．３モル）を混合した溶液を、窒素気流中２．０at
m の加圧下、１３０℃、３０分で全量添加し、終了後こ
れを３．０atm まで窒素で加圧し、１３０℃で３時間反
応させた。その後、該反応系を徐々に減圧しながら、添
加した水、生成水、添加した大部分のエチレングリコー
ル、および少量のドデシルフェノール（５１０．５ｇ）
を留去して、カラシ色の液状の蒸留残留物２８３０．９
ｇが得られた。その際の塔底物の温度は１７３℃、留出
物温度は１３９℃（２mmHg）であった。Example 1 2917.8 g (10.5 mol) of 94.4% pure dodecylphenol was placed in a 5-liter autoclave equipped with a stirrer, a cooling pipe, a nitrogen gas introducing pipe and a thermometer, and 95.8 in purity.
% Calcium oxide (175.7 g, 3.0 mol) was fed in and stirred. Add ethylene glycol 25 to this suspension.
1.5 g (4.05 mol) of 5.4 g of ion-exchanged water
(0.3 mol) in a nitrogen stream at 2.0 at.
The whole amount was added at 130 ° C. for 30 minutes under a pressure of m 2, and after completion, the mixture was pressurized with nitrogen to 3.0 atm and reacted at 130 ° C. for 3 hours. Then, while gradually reducing the pressure of the reaction system, added water, produced water, most of the added ethylene glycol, and a small amount of dodecylphenol (510.5 g)
Is distilled off to obtain a mustard-colored liquid distillation residue of 2830.9.
g was obtained. At that time, the temperature of the bottom product was 173 ° C., and the distillate temperature was 139 ° C. (2 mmHg).
【００３０】次に該蒸留残留物２８３０．９ｇに１７８
℃、３mmHgの状態から二酸化炭素を吹き込み５．０atm
まで昇圧し、昇圧後その状態のまま４時間保持して、暗
い灰黄赤色の液状反応生成物２９４０ｇを得た。Next, 178 was added to 2830.9 g of the distillation residue.
Injection of carbon dioxide from 3mmHg at 5.0 ℃
The pressure was maintained until the pressure was increased, and the state was maintained for 4 hours to obtain 2940 g of a dark gray-yellow liquid reaction product.
【００３１】次に、このカルボキシル化反応生成物を１
l オートクレーブに４９０．０ｇ移し、硫黄１７．７ｇ
（０．５５モル、アルカリ土類金属試薬１モル当たり
１．１モル）を１０５℃で添加し、次いで１５０℃まで
昇温し、窒素で２．０atm まで加圧した後、エチレング
リコール６２．１ｇ（１．０モル、アルカリ土類金属試
薬１モル当たり２．０モル）を３０分で全量添加し、次
いで１６５℃まで昇温し、その後窒素で５．０atm まで
加圧し開放系（反応容器の圧力が５atm を越えると５at
m になるまで減圧し、５atm を下回ると５atm まで加圧
する系）で４時間撹拌した。Next, this carboxylation reaction product is
l Transfer 490.0 g to autoclave and 17.7 g of sulfur
(0.55 mol, 1.1 mol per mol of alkaline earth metal reagent) at 105 ° C., then heated to 150 ° C., pressurized to 2.0 atm with nitrogen, and then 62.1 g of ethylene glycol (1.0 mol, 2.0 mol per mol of alkaline earth metal reagent) was added in 30 minutes, then the temperature was raised to 165 ° C., and then the pressure was increased to 5.0 atm with nitrogen to open the system (reaction vessel). 5at if pressure exceeds 5atm
m, and pressurized to 5 atm when the pressure falls below 5 atm) and stirred for 4 hours.
【００３２】次に、該反応生成物に１５０ニュートラル
油（１００℃の粘度が５．２７cStのパラフィン系潤滑
油、以下の例においても、用いた１５０ニュートラル油
はこれと同じである）１６５．５ｇを添加し、撹拌した
後、１l三口梨型フラスコに６４９．５ｇ移しとり、大
部分のエチレングリコールとドデシルフェノールおよび
少量の潤滑油留分３５５．９ｇを留去して、蒸留残留物
２８６．８ｇを得た。その際の最終留出物温度は２００
℃（２．５mmHg）であった。この後、蒸留残留物中に含
まれる極少量の不溶解物をろ過により除去し、極暗い黄
赤色透明粘稠な液状の最終製品２８４．８ｇを得た。こ
の最終製品の一般的性状を表１に示す。回収フェノール
類の濁りは目視にて判定した（以下の例も同様）。Next, 165.5 g of 150 neutral oil (paraffinic lubricating oil having a viscosity of 5.27 cSt at 100 ° C., and in the following examples, the same 150 neutral oil was used) was added to the reaction product. Was added and stirred, and then transferred to a 1 l three-necked pear-shaped flask with 649.5 g, and most of ethylene glycol, dodecylphenol and a small amount of lubricating oil fraction 355.9 g were distilled off, and 286.8 g of a distillation residue was obtained. I got The final distillate temperature at that time was 200
° C (2.5 mmHg). Thereafter, a very small amount of insolubles contained in the distillation residue was removed by filtration to obtain 284.8 g of a very dark yellow-red transparent viscous liquid final product. Table 1 shows general properties of the final product. Turbidity of the recovered phenols was visually determined (the same applies to the following examples).
【００３３】なお、色相はASTM D1500に従って測定した
（以下の例も同様）。すなわち、試料１５容量部を白灯
油８５容量部に溶解させ、それをＡＳＴＭ比色管に移
し、ＡＳＴＭ比色計にて測定した。このときの色相が８
以上となる場合は、再度その灯油溶液１５容量部を８５
容量部の白灯油に溶解させ、色相を測定する。それでも
なお色相が８以上の場合は８以内になるまで同様の操作
により測定を繰り返す。The hue was measured according to ASTM D1500 (the same applies to the following examples). That is, 15 parts by volume of the sample was dissolved in 85 parts by volume of white kerosene, transferred to an ASTM colorimetric tube, and measured with an ASTM colorimeter. The hue at this time is 8
In such cases, the kerosene solution 15 parts by volume is again
Dissolve in a volume of white kerosene and measure the hue. If the hue is still 8 or more, the measurement is repeated by the same operation until the hue is within 8.
【００３４】また、この反応生成物２．００ｇを分液ロ
ートにとり、６０ｍｌのエーテルに溶解させ、１Ｎの硫
酸１５ｍｌを添加して加水分解し（振とう機にて６０分
撹拌）、十分水洗後エーテル層を分離し、次いでエーテ
ルをロータリーエバポレーターにて除去したところ、褐
色の液状物１．８０ｇを得た。この液状物の酸価は２７
ｍｇＫＯＨ／ｇであった（以下の例においても酸価の測
定は、上記と全く同じ手法で行った）。Further, 2.00 g of the reaction product is taken in a separating funnel, dissolved in 60 ml of ether, hydrolyzed by adding 15 ml of 1N sulfuric acid (stirred for 60 minutes with a shaker), and thoroughly washed with water. The ether layer was separated, and the ether was removed with a rotary evaporator to obtain 1.80 g of a brown liquid. The acid value of this liquid is 27
mgKOH / g (in the following examples, the acid value was measured in exactly the same manner as described above).
【００３５】比較例１ 撹拌器、冷却管、窒素ガス導入管および温度計を装着し
た５l オートクレーブに純度９４．４％のドデシルフェ
ノール２５０１．０ｇ（９．０モル）、１５０ニュート
ラル油３３６．６ｇ、純度９３．２％の酸化カルシウム
１８０．６ｇ（３．０モル）を送入し、撹拌した。この
懸濁液にエチレングリコール２５１．５ｇ（４．０５モ
ル）にイオン交換水５．４ｇ（０．３モル）を混合した
溶液を、窒素気流中１．５atm の加圧下、１３０℃、３
０分で全量添加し、終了後これを３．０atm まで窒素で
加圧し、１３０℃で３時間反応させた。その後、該反応
系を徐々に減圧しながら、添加した水、生成水、添加し
た大部分のエチレングリコール、および少量のドデシル
フェノール（６７２．１ｇ）を留去して、カラシ色の液
状の蒸留残留物２６００．０ｇが得られた。その際の塔
底物の温度は１７８℃、留出物温度は１３６℃（１mmH
g）であった。Comparative Example 1 2501.0 g (9.0 mol) of 94.4% pure dodecylphenol, 336.6 g of 150 neutral oil were placed in a 5-liter autoclave equipped with a stirrer, a cooling pipe, a nitrogen gas introducing pipe and a thermometer. 180.6 g (3.0 mol) of calcium oxide having a purity of 93.2% was fed and stirred. A solution obtained by mixing 251.5 g (4.05 mol) of ethylene glycol with 5.4 g (0.3 mol) of ion-exchanged water was added to this suspension at 130 ° C. under a pressure of 1.5 atm in a nitrogen stream.
The whole amount was added in 0 minutes, and after completion, the mixture was pressurized with nitrogen to 3.0 atm and reacted at 130 ° C. for 3 hours. Then, while gradually reducing the pressure of the reaction system, the added water, generated water, most of the added ethylene glycol, and a small amount of dodecylphenol (672.1 g) were distilled off, and a mustard liquid distillation residue was removed. 2600.0 g of the product were obtained. At that time, the temperature of the bottom product was 178 ° C, and the distillate temperature was 136 ° C (1 mmH
g).
【００３６】次に該蒸留残留物２６００．０ｇに１７８
℃、１mmHgの状態から攪拌しながら二酸化炭素を１．３
５l／minの流速で３０分吹き込み、その後さらに二酸化
炭素で５．０atm まで昇圧し、昇圧後その状態のまま４
時間保持して、暗い灰黄赤色の液状反応生成物２７２
０．０ｇを得た。Next, 178 was added to 2600.0 g of the distillation residue.
1.3 ° C. while stirring at 1 ° C. and 1 mmHg.
Blow at a flow rate of 5 l / min for 30 minutes, and then further raise the pressure to 5.0 atm with carbon dioxide.
After holding for a while, a dark gray-yellow liquid reaction product 272 is obtained.
0.0 g was obtained.
【００３７】次に、このカルボキシル化反応生成物を１
l オートクレーブに４５１．０ｇ移し、硫黄１７．６ｇ
（０．５５モル、アルカリ土類金属試薬１モル当たり
１．１モル）を１０５℃で添加し、次いで１５０℃まで
昇温し、窒素で２atm まで加圧し、エチレングリコール
４６．３ｇ（０．７５モル、アルカリ土類金属試薬１モ
ル当たり１．５モル）を３０分で全量添加し、次いで１
６５℃まで昇温し、その後窒素で５．０atm まで加圧
し、開放系（反応容器の圧力が５atm を越えると５atm
になるまで減圧し、５atm を下回ると５atm まで加圧す
る系、以下の例においても開放系という語は、このよう
な系を示す）で４時間撹拌した。Next, this carboxylation reaction product is
l Transfer to the autoclave 451.0g, sulfur 17.6g
(0.55 mol, 1.1 mol per mol of alkaline earth metal reagent) at 105 ° C., then raise the temperature to 150 ° C., pressurize to 2 atm with nitrogen, and add 46.3 g (0.75 mol) of ethylene glycol. Mol, 1.5 mol per mol of alkaline earth metal reagent) in 30 minutes.
The temperature was raised to 65 ° C, then pressurized to 5.0 atm with nitrogen, and opened (5 atm when the pressure in the reaction vessel exceeded 5 atm).
And then pressurized to 5 atm below 5 atm (the term open system in the following examples also indicates such a system) for 4 hours.
【００３８】次に、該反応生成物に１５０ニュートラル
油１０８．８ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに５３０．９ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分２
４７．６ｇを留去して、蒸留残留物２７３．６８ｇを得
た。その際の最終留出物温度は１９８℃（１．５mmHg）
であった。この後、蒸留残留物中に含まれる極少量の不
溶解物をろ過により除去し、極暗い黄赤色透明粘稠な液
状の最終製品２７０．２ｇを得た。この最終製品の一般
的性状を表１に示す。Next, 108.8 g of 150 neutral oil was added to the reaction product, and after stirring, 530.9 g was transferred to a 1-liter three-necked pear-shaped flask, and most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 2
47.6 g was distilled off to obtain 273.68 g of a distillation residue. The final distillate temperature at that time is 198 ° C (1.5 mmHg)
Met. Thereafter, a very small amount of insolubles contained in the distillation residue was removed by filtration to obtain 270.2 g of an extremely dark yellow-red transparent viscous liquid final product. Table 1 shows general properties of the final product.
【００３９】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３８ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of the reaction product obtained in the same manner as in Example 1 was 38 mgKOH / g.
【００４０】この比較例１は、実施例１と比して二価ア
ルコールをアルカリ土類金属試薬１モル当たり１．５モ
ルと少なくした例である。表１を見ればわかるように色
相は実施例１とほぼ同じだが、回収フェノールに濁りを
生じている。Comparative Example 1 is an example in which the dihydric alcohol was reduced to 1.5 mol per mol of the alkaline earth metal reagent as compared with Example 1. As can be seen from Table 1, the hue is almost the same as in Example 1, but the recovered phenol is turbid.
【００４１】比較例２ 撹拌器、冷却管、窒素ガス導入管および温度計を装着し
た５lオートクレーブに純度９４．４％のドデシルフェ
ノール２６６７．７ｇ（９．６モル）、１５０ニュート
ラル油３３６．６ｇ、純度９５．８％の酸化カルシウム
１７５．７ｇ（３．０モル）を送入し、撹拌した。この
懸濁液にエチレングリコール２５１．５ｇ（４．０５モ
ル）にイオン交換水５．４ｇ（０．３モル）を混合した
溶液を、窒素気流中２．０atm の加圧下、１３０℃、３
０分で全量添加し、終了後これを３．０atm まで窒素で
加圧し、１３０℃で３時間反応させた。その後、該反応
系を徐々に減圧しながら、添加した水、生成水、添加し
た大部分のエチレングリコール、および少量のドデシル
フェノール（６７６．９ｇ）を留去して、カラシ色の液
状の蒸留残留物２７１２．０ｇが得られた。その際の塔
底物の温度は１７８℃、留出物温度は１３８℃（３mmH
g）であった。Comparative Example 2 2667.7 g (9.6 mol) of 94.4% pure dodecylphenol, 336.6 g of 150 neutral oil were placed in a 5-liter autoclave equipped with a stirrer, a cooling pipe, a nitrogen gas introducing pipe and a thermometer. 175.7 g (3.0 mol) of calcium oxide having a purity of 95.8% was fed and stirred. A solution obtained by mixing 251.5 g (4.05 mol) of ethylene glycol with 5.4 g (0.3 mol) of ion-exchanged water was added to this suspension at 130 ° C. under a pressure of 2.0 atm in a nitrogen stream.
The whole amount was added in 0 minutes, and after completion, the mixture was pressurized with nitrogen to 3.0 atm and reacted at 130 ° C. for 3 hours. Thereafter, while gradually reducing the pressure of the reaction system, the added water, generated water, most of the added ethylene glycol, and a small amount of dodecylphenol (676.9 g) were distilled off, and a mustard liquid distillation residue was obtained. 2712.0 g of the product were obtained. At that time, the temperature of the bottom product was 178 ° C, and the distillate temperature was 138 ° C (3 mmH
g).
【００４２】次に該蒸留残留物２８２０．５ｇに１７８
℃、３mmHgの状態から攪拌しながら二酸化炭素を１．３
５l／minの流速で３０分吹き込み、その後さらに二酸化
炭素で５．０atm まで昇圧し、昇圧後その状態のまま４
時間保持して、暗い灰黄赤色の液状反応生成物２８２
０．５ｇを得た。Next, 178 was added to 2820.5 g of the distillation residue.
1.3 ° C. while stirring at a temperature of 3 mmHg.
Blow at a flow rate of 5 l / min for 30 minutes, and then further raise the pressure to 5.0 atm with carbon dioxide.
Hold for a dark gray-yellow liquid reaction product 282
0.5 g was obtained.
【００４３】次に、このカルボキシル化反応生成物を１
l オートクレーブに４７３．４ｇ移し、硫黄１６．２ｇ
（０．５０モル、アルカリ土類金属試薬１モル当たり
１．０モル）を１０５℃で添加し、次いで１７０℃まで
昇温し、窒素で３atm まで加圧し、エチレングリコール
６２．４ｇ（１．０モル、アルカリ土類金属試薬１モル
当たり２．０モル）を３０分で全量添加し、次いで１７
０℃まで昇温し、その後窒素で５．０atm まで加圧し、
密閉系で４時間撹拌した。反応終了後の圧力は、６．７
atmとなった。Next, this carboxylation reaction product was
l Transfer 473.4 g to the autoclave and add 16.2 g of sulfur
(0.50 mol, 1.0 mol per mol of alkaline earth metal reagent) at 105 ° C., then raise the temperature to 170 ° C., pressurize to 3 atm with nitrogen, and add 62.4 g (1.0 Mol, 2.0 mol per mol of alkaline earth metal reagent) in 30 minutes.
The temperature was raised to 0 ° C, then pressurized to 5.0 atm with nitrogen,
The mixture was stirred in a closed system for 4 hours. The pressure after completion of the reaction was 6.7.
It became atm.
【００４４】次に、該反応生成物に１５０ニュートラル
油１１０．８ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに６５９．０ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分２
９３．３ｇを留去して、蒸留残留物２９２．２ｇを得
た。その際の最終留出物温度は１８５℃（３mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２８８．１ｇを得た。この最終製品の一般的性
状を表１に示す。Next, 110.8 g of 150 neutral oil was added to the reaction product, and after stirring, 659.0 g of the mixture was transferred to a 1-liter three-necked pear-shaped flask, and most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 2
93.3 g were distilled off to obtain 292.2 g of a distillation residue. The final distillate temperature at that time was 185 ° C. (3 mmHg). Thereafter, a very small amount of insolubles contained in the distillation residue was removed by filtration to obtain 288.1 g of a very dark yellow-red transparent viscous liquid final product. Table 1 shows general properties of the final product.
【００４５】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３３ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of the reaction product obtained in the same manner as in Example 1 was 33 mgKOH / g.
【００４６】この比較例２は、実施例１と比して、硫化
反応を加圧密閉系で行った例である。表１を見ればわか
るように色相は実施例１と同じだが、回収フェノールに
濁りを生じている。Comparative Example 2 is an example in which the sulfurization reaction was performed in a pressurized closed system as compared with Example 1. As can be seen from Table 1, the hue is the same as in Example 1, but the recovered phenol is turbid.
【００４７】実施例２ 実施例１で得たカルボキシル化反応生成物４９０．０ｇ
を１lオートクレーブに移し、硫黄１７．７ｇ（０．５
５モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１０３℃で添加し、次いで１５０℃まで昇温し、
窒素で３atm まで加圧し、エチレングリコール６２．１
ｇ（１．０モル、アルカリ土類金属試薬１モル当たり
２．０モル）を３０分で全量添加し、次いで１７８℃ま
で昇温し、その後窒素で５．０atm まで加圧し、開放系
で４時間撹拌した。Example 2 490.0 g of the carboxylation reaction product obtained in Example 1
Was transferred to a 1-liter autoclave, and 17.7 g of sulfur (0.5
5 mol, 1.1 mol per mol of alkaline earth metal reagent) at 103 ° C., then raise the temperature to 150 ° C.
Pressurize to 3 atm with nitrogen, ethylene glycol 62.1
g (1.0 mol, 2.0 mol per mol of alkaline earth metal reagent) in 30 minutes, then raise the temperature to 178 ° C., then pressurize to 5.0 atm with nitrogen, and add 4 g to the open system. Stirred for hours.
【００４８】次に、該反応生成物に１５０ニュートラル
油１６５．５ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに６４９．９ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
５４．６ｇを留去して、蒸留残留物２９２．５ｇを得
た。その際の最終留出物温度は１９８℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２８８．４ｇを得た。この最終製品の一般的性
状を表１に示す。Next, 165.5 g of 150 neutral oil was added to the reaction product, and after stirring, 649.9 g of the mixture was transferred to a 1 l three-necked pear-shaped flask, and most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 3
54.6 g were distilled off to obtain 292.5 g of a distillation residue. The final distillate temperature at that time was 198 ° C (2 mmHg). Thereafter, a very small amount of insolubles contained in the distillation residue was removed by filtration to obtain 288.4 g of a very dark yellow-red transparent viscous liquid final product. Table 1 shows general properties of the final product.
【００４９】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は１７ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of the reaction product obtained in the same manner as in Example 1 was 17 mgKOH / g.
【００５０】この実施例２は、硫化反応を加圧開放系で
行い反応温度を１７８℃とした例である。表１よりわか
るように、反応温度が高いため酸価が低下しているが、
色相は明るく、回収フェノールは濁っていない。Example 2 is an example in which the sulfurization reaction was carried out in a pressure-opening system and the reaction temperature was set at 178 ° C. As can be seen from Table 1, the acid value has decreased due to the high reaction temperature.
The hue is bright and the recovered phenol is not cloudy.
【００５１】比較例３ 実施例１で得たカルボキシル化反応生成物４９０．２ｇ
を１lオートクレーブに移し、硫黄１７．７ｇ（０．５
５モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１００℃で添加し、次いで１５０℃まで昇温し、
窒素で１．０atmまで加圧し、エチレングリコール６
２．１ｇ（１．０モル、アルカリ土類金属試薬１モル当
たり２．０モル）を３０分で全量添加し、次いで窒素で
５．０atm まで加圧し、開放系で４時間撹拌した。Comparative Example 3 490.2 g of the carboxylation reaction product obtained in Example 1
Was transferred to a 1-liter autoclave, and 17.7 g of sulfur (0.5
5 mol, 1.1 mol per mol of alkaline earth metal reagent) at 100 ° C., then raise the temperature to 150 ° C.
Pressurize to 1.0 atm with nitrogen, ethylene glycol 6
2.1 g (1.0 mol, 2.0 mol per mol of alkaline earth metal reagent) was added in 30 minutes, and the mixture was pressurized to 5.0 atm with nitrogen and stirred for 4 hours in an open system.
【００５２】次に、該反応生成物に１５０ニュートラル
油１６５．６ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに６２８．８ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
４１．２ｇを留去して、蒸留残留物２８０．７ｇを得
た。その際の最終留出物温度は１９５℃（３mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２７７．２ｇを得た。この最終製品の一般的性
状を表１に示す。Next, 165.6 g of 150 neutral oil was added to the reaction product, and after stirring, 628.8 g of the mixture was transferred to a 1-liter three-necked pear-shaped flask, and most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 3
41.2 g was distilled off to obtain 280.7 g of a distillation residue. The final distillate temperature at that time was 195 ° C (3 mmHg). Thereafter, a very small amount of insolubles contained in the distillation residue was removed by filtration to obtain 277.2 g of a very dark yellow-red transparent viscous liquid final product. Table 1 shows general properties of the final product.
【００５３】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３２ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of the reaction product obtained in the same manner as in Example 1 was 32 mgKOH / g.
【００５４】この比較例３は、硫化反応を加圧開放系で
行い反応温度を１５０℃とした例である。表１よりわか
るように、硫化反応温度を低くすると、回収フェノール
は濁ってしまうばかりか、製品の色相は暗くなり、また
粘度の高い製品ができてしまう。Comparative Example 3 is an example in which the sulfidation reaction was carried out in an open-pressurized system and the reaction temperature was 150 ° C. As can be seen from Table 1, when the sulfidation reaction temperature is lowered, not only does the recovered phenol become turbid, but also the color of the product becomes dark and a product having a high viscosity is produced.
【００５５】[0055]
【表１】 [Table 1]
【００５６】実施例３ 撹拌器、冷却管、窒素ガス導入管および温度計を装着し
た５lオートクレーブに純度９４．４％のドデシルフェ
ノール２９１７．８ｇ（１０．５モル）、純度９３．２
％の酸化カルシウム１８０．６ｇ（３．０モル）を送入
し、撹拌した。この懸濁液にエチレングリコール２５
１．５ｇ（４．０５モル）にイオン交換水５．４ｇ
（０．３モル）を混合した溶液を、窒素気流中１．５at
m の加圧下、１３０℃、３０分で全量添加し、終了後こ
れを３．０atm まで窒素で加圧し、１３０℃で３時間反
応させた。その後、該反応系を徐々に減圧しながら、添
加した水、生成水、添加した大部分のエチレングリコー
ルおよび少量のドデシルフェノール（３８５．０ｇ）を
留去して、カラシ色の液状の蒸留残留物２９６５．２ｇ
が得られた。その際の塔底物の温度は１７３℃、留出物
温度は１０９℃（３mmHg）であった。EXAMPLE 3 2917.8 g (10.5 mol) of 94.4% pure dodecylphenol was placed in a 5 l autoclave equipped with a stirrer, a condenser, a nitrogen gas inlet and a thermometer, and 93.2 in purity.
180.6 g (3.0 moles) of calcium oxide were fed in and stirred. Add ethylene glycol 25 to this suspension.
1.5 g (4.05 mol) of 5.4 g of ion-exchanged water
(0.3 mol) in a nitrogen stream at 1.5 at.
The whole amount was added at 130 ° C. for 30 minutes under a pressure of m 2, and after completion, the mixture was pressurized with nitrogen to 3.0 atm and reacted at 130 ° C. for 3 hours. Thereafter, while gradually reducing the pressure of the reaction system, the added water, formed water, most of the added ethylene glycol and a small amount of dodecylphenol (385.0 g) were distilled off, and a mustard liquid distillation residue was obtained. 2965.2 g
was gotten. At that time, the temperature of the bottom product was 173 ° C., and the distillate temperature was 109 ° C. (3 mmHg).
【００５７】次に該蒸留残留物２９６５．２ｇに１７８
℃、３mmHgの状態から二酸化炭素を吹き込み５．０atm
まで昇圧し、昇圧後その状態のまま４時間保持して、暗
い灰黄赤色の液状反応生成物３０８５ｇを得た。Next, 1785.2 g of the distillation residue was added to 1785.2 g.
Injection of carbon dioxide from 3mmHg at 5.0 ℃
The pressure was maintained until the pressure was increased, and the state was maintained for 4 hours to obtain 3085 g of a dark gray-yellow red liquid reaction product.
【００５８】次に、このカルボキシル化反応生成物を１
l オートクレーブに４３８．８ｇ移し、硫黄１５．１ｇ
（０．４７モル、アルカリ土類金属試薬１モル当たり
１．１モル）を１０３℃で添加し、次いで窒素を１５ml
／minの流速で流しながら１５０℃まで昇温し、エチレ
ングリコール２６．５ｇ（０．４３モル、アルカリ土類
金属試薬１モル当たり１．０モル）を３０分で全量添加
し、次いで１６５℃まで昇温し、窒素を１５ml／minの
流速で流しながら常圧開放系で４時間撹拌した。Next, this carboxylation reaction product was
l Transfer 438.8 g to the autoclave, 15.1 g sulfur
(0.47 mol, 1.1 mol per mol of alkaline earth metal reagent) at 103 ° C. and then add 15 ml of nitrogen
The temperature was raised to 150 ° C. while flowing at a flow rate of / min, and 26.5 g (0.43 mol, 1.0 mol per mol of alkaline earth metal reagent) of ethylene glycol was added in 30 minutes. The mixture was heated and stirred for 4 hours in a normal pressure open system while flowing nitrogen at a flow rate of 15 ml / min.
【００５９】次に、該反応生成物に１５０ニュートラル
油１４１．３ｇを添加し、撹拌した後、１l三口梨型フ
ラスコに５２３．９ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分２
７５．８ｇを留去して、蒸留残留物２４３．６ｇを得
た。その際の最終留出物温度は１９３℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２３９．５ｇを得た。この最終製品の一般的性
状を表２に示す。Next, 141.3 g of 150 neutral oil was added to the reaction product, and after stirring, 523.9 g was transferred to a 1-liter three-necked pear-shaped flask, and most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 2
75.8 g were distilled off to obtain 243.6 g of a distillation residue. The final distillate temperature at that time was 193 ° C. (2 mmHg). Thereafter, a very small amount of insolubles contained in the distillation residue was removed by filtration to obtain 239.5 g of a very dark yellow-red transparent viscous liquid final product. Table 2 shows the general properties of the final product.
【００６０】また、この反応生成物２．００ｇを採り、
実施例１と同様にして得た酸価は３０ｍｇＫＯＨ／ｇで
あった。Further, 2.00 g of this reaction product was taken,
The acid value obtained in the same manner as in Example 1 was 30 mgKOH / g.
【００６１】実施例４ 実施例３で得たカルボキシル化反応生成物５０３．７ｇ
を１lオートクレーブに移し、硫黄１７．３ｇ（０．５
４モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１０６℃で添加し、次いで窒素を１５ml／minの
流速で通気しながら１５０℃まで昇温し、エチレングリ
コール１５．２ｇ（０．２５モル、アルカリ土類金属試
薬１モル当たり０．５モル）を３０分で全量添加し、次
いで１６５℃まで昇温し、窒素を１５ml／minの流速で
流しながら、常圧開放系で４時間撹拌した。Example 4 503.7 g of the carboxylation reaction product obtained in Example 3
Was transferred to a 1-liter autoclave, and 17.3 g of sulfur (0.5
4 mol, 1.1 mol per mol of alkaline earth metal reagent) were added at 106 ° C., and the temperature was raised to 150 ° C. while passing nitrogen at a flow rate of 15 ml / min. 25 mol, 0.5 mol per mol of alkaline earth metal reagent) in 30 minutes, and then raise the temperature to 165 ° C., while flowing nitrogen at a flow rate of 15 ml / min. Stirred.
【００６２】次に、該反応生成物に１５０ニュートラル
油１６２．１ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに５８１．９ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
０１．１ｇを留去して、蒸留残留物２７４．２ｇを得
た。その際の最終留出物温度は１９１℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２６８．６ｇを得た。この最終製品の一般的性
状を表２に示す。Next, 162.1 g of 150 neutral oil was added to the reaction product, and after stirring, 581.9 g was transferred to a 1-liter three-necked pear-shaped flask, and most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 3
01.1 g was distilled off to obtain 274.2 g of a distillation residue. At that time, the final distillate temperature was 191 ° C. (2 mmHg). Thereafter, a very small amount of insolubles contained in the distillation residue was removed by filtration to obtain 268.6 g of a very dark yellow-red transparent viscous liquid final product. Table 2 shows the general properties of the final product.
【００６３】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３３ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of the reaction product obtained in the same manner as in Example 1 was 33 mgKOH / g.
【００６４】この実施例４は、硫化反応を常圧開放系で
行いエチレングリコール添加量をアルカリ土類金属試薬
１モル当たり０．５モル添加して行った例である。Example 4 is an example in which the sulfurization reaction was carried out in an open system under normal pressure, and the amount of ethylene glycol added was 0.5 mol per mol of the alkaline earth metal reagent.
【００６５】実施例５ 実施例３で得たカルボキシル化反応生成物５１０．３ｇ
を１lオートクレーブに移し、硫黄１７．５ｇ（０．５
５モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１００℃で添加し、次いで窒素を１５ml／minの
流速で通気しながら１５０℃まで昇温し、エチレングリ
コール６１．６ｇ（１．０モル、アルカリ土類金属試薬
１モル当たり２．０モル）を３０分で全量添加し、次い
で１７８℃まで昇温し、窒素を１５ml／minの流速で流
しながら、常圧開放系で４時間撹拌した。Example 5 510.3 g of the carboxylation reaction product obtained in Example 3
Was transferred to a 1-liter autoclave, and 17.5 g (0.5
5 mol, 1.1 mol per mol of alkaline earth metal reagent) were added at 100 ° C., and the temperature was raised to 150 ° C. while passing nitrogen at a flow rate of 15 ml / min, and 61.6 g of ethylene glycol (1. 0 mol, 2.0 mol per 1 mol of alkaline earth metal reagent) in 30 minutes, then raise the temperature to 178 ° C. and flow nitrogen at a flow rate of 15 ml / min. Stirred.
【００６６】次に、該反応生成物に１５０ニュートラル
油１６４．２ｇを添加し、撹拌した後、１l三口梨型フ
ラスコに６３５．２ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
５４．９ｇを留去して、蒸留残留物２７８．０ｇを得
た。その際の最終留出物温度は１９７℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２６９．８ｇを得た。この最終製品の一般的性
状を表２に示す。Next, 164.2 g of 150 neutral oil was added to the reaction product, and after stirring, 635.2 g was transferred to a 1-liter three-necked pear-shaped flask, and most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 3
54.9 g were distilled off to obtain 278.0 g of a distillation residue. At that time, the final distillate temperature was 197 ° C. (2 mmHg). Thereafter, a very small amount of insolubles contained in the distillation residue was removed by filtration to obtain 269.8 g of a very dark yellow-red transparent viscous liquid final product. Table 2 shows the general properties of the final product.
【００６７】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は１８ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of the reaction product obtained in the same manner as in Example 1 was 18 mgKOH / g.
【００６８】この実施例５は、硫化反応を常圧開放系で
行いエチレングリコール添加量をアルカリ土類金属試薬
１モル当たり２．０モル添加し、反応温度を１７８℃で
行った例である。回収フェノールに濁りは生じないが、
反応温度が若干高めのため、酸化が低下している。Example 5 is an example in which the sulfurization reaction was carried out in an open system under normal pressure, ethylene glycol was added in an amount of 2.0 mol per mol of the alkaline earth metal reagent, and the reaction temperature was 178 ° C. There is no turbidity in the recovered phenol,
Oxidation is reduced due to slightly elevated reaction temperature.
【００６９】実施例６ 実施例１で得たカルボキシル化反応生成物５３７．８ｇ
を１lオートクレーブに移し、硫黄１９．４ｇ（０．６
０モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１００℃で添加し、次いで窒素を１５ml／minの
流速で通気しながら１６５℃まで昇温し、エチレングリ
コール６８．２ｇ（１．１モル、アルカリ土類金属試薬
１モル当たり２．０モル）を３０分で全量添加し、窒素
を１５ml／minの流速で流したまま、常圧開放系、１６
５℃で４時間撹拌した。Example 6 537.8 g of the carboxylation reaction product obtained in Example 1
Was transferred to a 1-liter autoclave, and 19.4 g of sulfur (0.6
0 mol, 1.1 mol per 1 mol of alkaline earth metal reagent) was added at 100 ° C., and the temperature was raised to 165 ° C. while passing nitrogen at a flow rate of 15 ml / min, and 68.2 g of ethylene glycol (1. 1 mol, 2.0 mol per mol of alkaline earth metal reagent) in 30 minutes, and while the nitrogen was flowing at a flow rate of 15 ml / min, the system was opened under normal pressure.
Stirred at 5 ° C for 4 hours.
【００７０】次に、該反応生成物に１５０ニュートラル
油１８１．７ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに７０２．３ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
８５．４ｇを留去して、蒸留残留物３１２．０ｇを得
た。その際の最終留出物温度は２００℃（２．５mmHg）
であった。この後、蒸留残留物中に含まれる極少量の不
溶解物をろ過により除去し、極暗い黄赤色透明粘稠な液
状の最終製品３０８．１ｇを得た。この最終製品の一般
的性状を表２に示す。Next, 181.7 g of 150 neutral oil was added to the reaction product, and after stirring, 702.3 g of the mixture was transferred to a 1-liter three-necked pear-shaped flask, and most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 3
85.4 g was distilled off to obtain 312.0 g of a distillation residue. The final distillate temperature at that time is 200 ° C (2.5mmHg)
Met. Thereafter, a very small amount of insolubles contained in the distillation residue was removed by filtration to obtain 308.1 g of a very dark yellow-red transparent viscous liquid final product. Table 2 shows the general properties of the final product.
【００７１】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は２７ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of the reaction product obtained in the same manner as in Example 1 was 27 mgKOH / g.
【００７２】この実施例６は、硫化反応を常圧開放系で
行いエチレングリコール添加量をアルカリ土類金属試薬
１モル当たり２．０モル添加し、反応温度を１６５℃で
行った例である。Example 6 is an example in which the sulfurization reaction was carried out in an open system at normal pressure, the amount of ethylene glycol added was 2.0 mol per mol of the alkaline earth metal reagent, and the reaction temperature was 165 ° C.
【００７３】比較例４ 実施例３で得たカルボキシル化反応生成物５１０．２ｇ
を１lオートクレーブに移し、硫黄１７．５ｇ（０．５
５モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１００℃で添加し、次いで窒素を１５ml／minの
流速で通気しながら１５０℃まで昇温し、エチレングリ
コール６１．６ｇ（１．０モル、アルカリ土類金属試薬
１モル当たり２．０モル）を３０分で全量添加し、窒素
を１５ml／minの流速で流しながら、常圧開放系、１５
０℃で４時間撹拌した。Comparative Example 4 510.2 g of the carboxylation reaction product obtained in Example 3
Was transferred to a 1-liter autoclave, and 17.5 g (0.5
5 mol, 1.1 mol per mol of alkaline earth metal reagent) were added at 100 ° C., and the temperature was raised to 150 ° C. while passing nitrogen at a flow rate of 15 ml / min, and 61.6 g of ethylene glycol (1. 0 mol, 2.0 mol per 1 mol of alkaline earth metal reagent) in 30 minutes, and nitrogen was allowed to flow at a flow rate of 15 ml / min.
Stirred at 0 ° C. for 4 hours.
【００７４】次に、該反応生成物に１５０ニュートラル
油１６４．２ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに６５９．８ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
６１．７ｇを留去して、蒸留残留物２８９．１ｇを得
た。その際の最終留出物温度は１９７℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２８５．９ｇを得た。この最終製品の一般的性
状を表２に示す。Next, 164.2 g of 150 neutral oil was added to the reaction product, and after stirring, 659.8 g of the mixture was transferred to a 1 l three-necked pear-shaped flask, and most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 3
61.7 g were distilled off to obtain 289.1 g of a distillation residue. At that time, the final distillate temperature was 197 ° C. (2 mmHg). Thereafter, a very small amount of insolubles contained in the distillation residue was removed by filtration to obtain 285.9 g of an extremely dark yellow-red transparent viscous liquid final product. Table 2 shows the general properties of the final product.
【００７５】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３９ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of the reaction product obtained in the same manner as in Example 1 was 39 mgKOH / g.
【００７６】この比較例４は硫化反応を常圧開放系で行
いエチレングリコール添加量をアルカリ土類金属試薬１
モル当たり２．０モル添加し、反応温度を１５０℃で行
った例である。反応温度が若干低いため、酸化は高い値
だが、回収フェノールに濁りを生じている。また、色相
も若干高めである。In Comparative Example 4, the sulfidation reaction was carried out in an open system at normal pressure, and the amount of ethylene glycol added was changed to the alkaline earth metal reagent 1
This is an example in which 2.0 mol was added per mol and the reaction temperature was 150 ° C. Oxidation is high because the reaction temperature is slightly lower, but the recovered phenol is turbid. The hue is also slightly higher.
【００７７】[0077]
【表２】 [Table 2]
【００７８】実施例７ 実施例３で得たカルボキシル化反応生成物５１０．３ｇ
を１lオートクレーブに移し、硫黄１７．５ｇ（０．５
５モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１０８℃で添加し、次いで窒素を１５ml／minの
流速で通気しながら１５０℃まで昇温し、エチレングリ
コール４６．２ｇ（０．７５モル、アルカリ土類金属試
薬１モル当たり１．５モル）を３０分で全量添加し、そ
の後１６５℃まで昇温し、窒素を１５ml／minの流速で
流しながら、常圧開放系、１６５℃で４時間撹拌した。Example 7 510.3 g of the carboxylation reaction product obtained in Example 3
Was transferred to a 1-liter autoclave, and 17.5 g (0.5
5 mol, 1.1 mol per mol of alkaline earth metal reagent) were added at 108 ° C., and the temperature was raised to 150 ° C. while passing nitrogen at a flow rate of 15 ml / min, and 46.2 g of ethylene glycol (0. 75 mol, 1.5 mol per mol of alkaline earth metal reagent) in 30 minutes, and then raise the temperature to 165 ° C., while flowing nitrogen at a flow rate of 15 ml / min. For 4 hours.
【００７９】次に、該反応生成物に１５０ニュートラル
油１６４．２ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに６５９．８ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
３７．９ｇを留去して、蒸留残留物２７６．５ｇを得
た。その際の最終留出物温度は１９１℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２７２．５ｇを得た。この最終製品の一般的性
状を表３示す。Next, 164.2 g of 150 neutral oil was added to the reaction product, and after stirring, 659.8 g of the mixture was transferred to a 1-liter three-necked pear-shaped flask, and most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 3
37.9 g were distilled off to obtain 276.5 g of a distillation residue. At that time, the final distillate temperature was 191 ° C. (2 mmHg). Thereafter, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 272.5 g of an extremely dark yellow-red transparent viscous liquid final product. Table 3 shows the general properties of the final product.
【００８０】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３１ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of the reaction product obtained in the same manner as in Example 1 was 31 mgKOH / g.
【００８１】実施例８ 比較例１で得たカルボキシル化反応生成物３４９．１ｇ
を１lオートクレーブに移し、硫黄１３．６ｇ（０．４
２モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１０３℃で添加し、次いで窒素を３０ml／minの
流速で通気しながら１５０℃まで昇温し、エチレングリ
コール３５．９ｇ（０．５８モル、アルカリ土類金属試
薬１モル当たり１．５モル）を３０分で全量添加し、そ
の後、１６５℃まで昇温し、窒素を３０ml／minの流速
で流しながら、常圧開放系、１６５℃で４時間撹拌し
た。Example 8 349.1 g of carboxylation reaction product obtained in Comparative Example 1
Was transferred to a 1-liter autoclave, and 13.6 g (0.4
2 mol, 1.1 mol per mol of alkaline earth metal reagent) were added at 103 ° C., and the temperature was raised to 150 ° C. while passing nitrogen at a flow rate of 30 ml / min, and 35.9 g of ethylene glycol (0. 58 mol, 1.5 mol per mol of alkaline earth metal reagent) in 30 minutes, and then raise the temperature to 165 ° C. while flowing nitrogen at a flow rate of 30 ml / min. Stirred at C for 4 hours.
【００８２】次に、該反応生成物に１５０ニュートラル
油８４．２ｇを添加し、撹拌した後、１l 三口梨型フラ
スコに４２０．９ｇ移しとり、大部分のエチレングリコ
ールとドデシルフェノールおよび少量の潤滑油留分１９
６．７ｇを留去して、蒸留残留物２２１．２を得た。そ
の際の最終留出物温度は１９２℃（１．５mmHg）であっ
た。この後、蒸留残留物中に含まれる極少量の不溶解物
をろ過により除去し、極暗い黄赤色透明粘稠な液状の最
終製品２１７．９ｇを得た。この最終製品の一般的性状
を表３示す。Next, 84.2 g of 150 neutral oil was added to the reaction product, and after stirring, 420.9 g was transferred to a 1-liter three-necked pear-shaped flask, and most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Distillate 19
6.7 g were distilled off to obtain a distillation residue 221.2. At that time, the final distillate temperature was 192 ° C (1.5 mmHg). Thereafter, a very small amount of insolubles contained in the distillation residue was removed by filtration to obtain 217.9 g of a very dark yellow-red transparent viscous liquid final product. Table 3 shows the general properties of the final product.
【００８３】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３２ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of the reaction product obtained in the same manner as in Example 1 was 32 mgKOH / g.
【００８４】[0084]
【表３】 [Table 3]
【００８５】[0085]
【発明の効果】本製造法によると、アルカリ土類金属サ
リシレートおよびフェネートの硫化混合物の製造法にお
いて、硫化反応を反応温度１６０℃以上、常圧または加
圧の開放系にて二価アルコールをそれぞれの系によって
定められる特定量以上存在させる条件下で行うことによ
り、従来品と比較してアルカリ土類金属サリシレート及
びフェネートの硫化混合物の色相を著しく明るくするこ
とができるばかりでなく、回収される未反応フェノール
類が白濁せずに再利用可能となる。フェノール類は高価
であり、溶媒として多量に使用するため回収されたフェ
ノール類が再利用できることにより大幅なコスト削減と
なる。According to the present production method, in a method for producing a sulfurized mixture of an alkaline earth metal salicylate and a phenate, a dihydric alcohol is reacted in an open system at a reaction temperature of 160 ° C. or higher at normal pressure or pressure, respectively. By performing the reaction under the condition of being present in an amount equal to or more than the specific amount determined by the system, not only can the color of the sulfurized mixture of the alkaline earth metal salicylate and phenate be significantly brightened as compared with the conventional product, but Reacted phenols can be reused without becoming cloudy. Phenols are expensive and can be used in large amounts as a solvent, so that the recovered phenols can be reused, resulting in significant cost reduction.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ１０Ｍ 125/10 Ｃ１０Ｍ 125/10 129/08 129/08 129/10 129/10 // Ｃ１０Ｎ 10:04 30:04 30:20 60:10 70:00 (72)発明者 上田 早苗 埼玉県幸手市権現堂1134−２ 株式会社 コスモ総合研究所 研究開発センター内 (56)参考文献 特開 平６−211779（ＪＰ，Ａ) 特開 平３−26793（ＪＰ，Ａ) 特開 平５−1295（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C10M 159/22 C07C 319/14 C10N 70:00──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C10M 125/10 C10M 125/10 129/08 129/08 129/10 129/10 // C10N 10:04 30:04 30:20 60:10 70:00 (72) Inventor Sanae Ueda 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Research Institute, Inc. Research and Development Center (56) References JP-A-6-211779 (JP, A) JP JP-A-3-26793 (JP, A) JP-A-5-1295 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C10M 159/22 C07C 319/14 C10N 70:00
Claims (2)
カリ土類金属酸化物あるいは水酸化物またはそれらの混
合物（以下、「アルカリ土類金属試薬」と言う。）より
なる反応原料混合物またはこれらに水を加えたものを反
応させ、次いで水および二価アルコールを留去して得ら
れた蒸留塔底物に二酸化炭素を反応させ、得られた生成
物に二価アルコール類および元素硫黄を添加して硫化反
応を行うことからなるサリチル酸類およびフェノール類
のアルカリ土類金属塩硫化混合物の製法において、硫化
反応の際、反応温度を１６０℃以上、加圧開放系で反応
を行い、添加する二価アルコール類をアルカリ土類金属
試薬１モル当たり２．０モル以上とすることを特徴とす
るサリチル酸類およびフェノール類のアルカリ土類金属
塩硫化混合物の製法。1. A reaction raw material mixture comprising phenols, dihydric alcohols, alkaline earth metal oxides or hydroxides or a mixture thereof (hereinafter referred to as "alkaline earth metal reagent"), or a mixture thereof with water. Then, water and the dihydric alcohol are distilled off, and the bottom of the distillation column obtained is reacted with carbon dioxide.The resulting product is added with dihydric alcohols and elemental sulfur, In a method for producing a sulfurized mixture of an alkaline earth metal salt of salicylic acids and phenols, the reaction temperature is 160 ° C. or higher and the reaction is carried out in a pressurized and open system. For producing a mixture of salicylic acids and phenols in an alkaline earth metal salt sulfide mixture, wherein the amount of the alkaline earth metal reagent is at least 2.0 mol per mol of the alkaline earth metal reagent. .
カリ土類金属酸化物あるいは水酸化物またはそれらの混
合物（以下、「アルカリ土類金属試薬」と言う。）より
なる反応原料混合物またはこれらに水を加えたものを反
応させ、次いで水および二価アルコールを留去して得ら
れた蒸留塔底物に二酸化炭素を反応させ、得られた生成
物に二価アルコール類および元素硫黄を添加して硫化反
応を行うことからなるサリチル酸類およびフェノール類
のアルカリ土類金属塩硫化混合物の製法において、硫化
反応の際、反応温度を１６０℃以上、常圧開放系で反応
を行い、添加する二価アルコール類をアルカリ土類金属
試薬１モル当たり０．５モル以上とすることを特徴とす
るサリチル酸類およびフェノール類のアルカリ土類金属
塩硫化混合物の製法。2. A reaction raw material mixture comprising phenols, dihydric alcohols, alkaline earth metal oxides or hydroxides or a mixture thereof (hereinafter referred to as "alkaline earth metal reagent"), or a mixture of these with water. Then, water and the dihydric alcohol are distilled off, and the bottom of the distillation column obtained is reacted with carbon dioxide.The resulting product is added with dihydric alcohols and elemental sulfur, In the method for producing a sulfurized mixture of alkaline earth metal salts of salicylic acids and phenols by performing a sulfidation reaction, the reaction is carried out at a reaction temperature of 160 ° C. or higher at a normal pressure open system during the sulfidation reaction, and the dihydric alcohol to be added For producing an alkaline earth metal salt sulfide mixture of salicylic acids and phenols, wherein the amount of the alkaline earth metal reagent is 0.5 mol or more per mol of the alkaline earth metal reagent. .
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9539493A JP2819491B2 (en) | 1993-03-30 | 1993-03-30 | Preparation of alkaline earth metal sulfide mixtures of salicylic acids and phenols |
| TW082107528A TW278098B (en) | 1992-09-18 | 1993-09-14 | |
| KR1019930018784A KR100277413B1 (en) | 1992-09-18 | 1993-09-17 | Method for preparing a mixture of salicylic acid compound and sulfided alkaline earth metal salt of phenol |
| CN93119338A CN1035015C (en) | 1992-09-18 | 1993-09-18 | Process for producing mixture of sulfurized alkaline earth metal salts of salicylic acid compound and phenol |
| EP93115102A EP0588368B1 (en) | 1992-09-18 | 1993-09-20 | Process for producing mixture of sulfurized alkaline earth metal salts of salicylic acid compound and phenol |
| DE69318240T DE69318240T2 (en) | 1992-09-18 | 1993-09-20 | Process for the preparation of a mixture of sulfur-containing alkaline earth metal salts of salicylic acid compounds and phenol |
| SG1996005673A SG49060A1 (en) | 1992-09-18 | 1993-09-20 | Process for producing mixture of sulfurized alkaline earth metal salts of salicyclic acid compound and phenol |
| US08/424,566 US5538650A (en) | 1992-09-18 | 1995-04-17 | Process for producing mixture of sulfurized alkaline earth metal salts of salicylic acid compound and phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9539493A JP2819491B2 (en) | 1993-03-30 | 1993-03-30 | Preparation of alkaline earth metal sulfide mixtures of salicylic acids and phenols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06287580A JPH06287580A (en) | 1994-10-11 |
| JP2819491B2 true JP2819491B2 (en) | 1998-10-30 |
Family
ID=14136440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9539493A Expired - Lifetime JP2819491B2 (en) | 1992-09-18 | 1993-03-30 | Preparation of alkaline earth metal sulfide mixtures of salicylic acids and phenols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2819491B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4868183A (en) * | 1986-07-21 | 1989-09-19 | Otsuka Pharmaceutical Factory, Inc. | N-pyrazinyl substituted P-aminophenols |
| WO1999064481A1 (en) * | 1998-06-05 | 1999-12-16 | Idemitsu Kosan Co., Ltd. | Succinimide compound, process for producing the same, lubricating oil additive, and lubricating oil composition for internal combustion engine |
-
1993
- 1993-03-30 JP JP9539493A patent/JP2819491B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06287580A (en) | 1994-10-11 |
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