JPH0513137B2 - - Google Patents
Info
- Publication number
- JPH0513137B2 JPH0513137B2 JP59110883A JP11088384A JPH0513137B2 JP H0513137 B2 JPH0513137 B2 JP H0513137B2 JP 59110883 A JP59110883 A JP 59110883A JP 11088384 A JP11088384 A JP 11088384A JP H0513137 B2 JPH0513137 B2 JP H0513137B2
- Authority
- JP
- Japan
- Prior art keywords
- tert
- butylphenol
- dtbp
- reaction
- catalyst
- 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
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims description 85
- 239000003054 catalyst Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 25
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical class CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 238000004821 distillation Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 19
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 12
- 239000004927 clay Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 6
- 238000010555 transalkylation reaction Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 claims description 4
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 3
- KHWQFISNNNRGLV-UHFFFAOYSA-N 2,4,6-tributylphenol Chemical compound CCCCC1=CC(CCCC)=C(O)C(CCCC)=C1 KHWQFISNNNRGLV-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 12
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 11
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical compound [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- -1 and as a result Chemical compound 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006210 debutylation Effects 0.000 description 2
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical class CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 1
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 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
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は２，４−ジ−tert−ブチルフエノール
の製造方法に関し、更に詳しくは、tert−ブチル
フエノール類のトランスアルキル化反応により
２，４−ジ−tert−ブチルフエノールを製造する
方法において、
（） 原料のtert−ブチルフエノール類中のフ
エノール核の総数に対するtert−ブチル基の総
数の比が約1.5〜2.5になるように原料を調製
し、
（） 触媒として、活性白土若しくは酸性白土
を、原料のtert−ブチルフエノール類に対し１
〜10重量％用い、
かつ
（） 反応を90〜150℃の温度で行うことを特
徴とする収率の高い２，４−ジ−tert−ブチル
フエノールの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing 2,4-di-tert-butylphenol, and more specifically, to a method for producing 2,4-di-tert-butylphenol by a transalkylation reaction of tert-butylphenols. - In the method for producing di-tert-butylphenol, () the raw material is prepared so that the ratio of the total number of tert-butyl groups to the total number of phenol nuclei in the raw material tert-butylphenol is about 1.5 to 2.5. , () As a catalyst, activated clay or acid clay is used at a rate of 1% per tert-butylphenol as a raw material.
The present invention relates to a method for producing 2,4-di-tert-butylphenol with a high yield, characterized in that 10% by weight of 2,4-di-tert-butylphenol is used, and (2) the reaction is carried out at a temperature of 90 to 150°C.
（従来技術）
２，４−ジ−tert−ブチルフエノール（以下
２，４−DTBP）は、ガソリン等の燃料油の酸
化防止剤として、極めて有用な化合物であるに止
まらず、樹脂添加剤（例えば、IRGAFOS 168
、IRGAFOS Ｐ−EPQ
等）の原料としても、
有用な化合物であり、今後とも需要の伸長が期待
される。(Prior Art) 2,4-di-tert-butylphenol (hereinafter referred to as 2,4-DTBP) is not only an extremely useful compound as an antioxidant for fuel oils such as gasoline, but also as a resin additive (e.g. , IRGAFOS 168
, IRGAFOS P-EPQ, etc.)
It is a useful compound, and demand is expected to continue growing in the future.
従来、２，４−DTBPの有利な工業的製造法
は確立されていなかつた。公知の製造法としては
(1)フエノールとイソブチレン又はtert−ブチルエ
ーテル類の如き、イソブチレン基を有する化合物
とのアルキル化反応(2)tert−ブチルフエノール類
のトランスアルキル化反応による方法が知られて
いる。(1)の方法は、リン酸、硫酸、沸化水素酸な
どのブロンステツド酸、塩化アルミニウム、沸化
硼素などのルイス酸に代表される強酸を触媒とす
るアルキル化反応であるために、反応速度が速
く、反応過程で第３ブチル基の分子内転位反応、
分子間不均化反応が極めて速く生起するため、
２，４−DTBP以外にも多くの異性体混合物を
副生するという欠点を有している。しかも、２，
４−DTBPの収率は、概ね熱力学的平衡組成に
より決められるため、低くならざるを得ないとい
う欠点をも有している。例えば、SPAN.336838
に記載されている、フエノールとイソブチレンか
ら硫酸触媒の存在下に、２，４−DTBPを製造
する場合の例を掲げると、２，４−DTBPは52
％と低く、それ以外の副生物として、２−tert−
ブチルフエノール（以下２−TBPという）22％、
４−tert−ブチルフエノール（以下４−TBPとい
う）17％、２，６−ジ−tert−ブチルフエノール
（以下２，６−DTBPという）１％、２，４，６
−トリ−tert−ブチルフエノール（以下２，４，
６−TTBPという）１％という結果となつてい
る。 Hitherto, no advantageous industrial production method for 2,4-DTBP has been established. As a known manufacturing method
(1) Alkylation reaction of phenol with a compound having an isobutylene group such as isobutylene or tert-butyl ethers (2) Transalkylation reaction of tert-butyl phenols is known. Method (1) is an alkylation reaction catalyzed by strong acids such as Bronsted acids such as phosphoric acid, sulfuric acid, and hydrofluoric acid, and Lewis acids such as aluminum chloride and boron fluoride, so the reaction rate is is fast, and intramolecular rearrangement of tertiary butyl group occurs during the reaction process.
Because intermolecular disproportionation reactions occur extremely quickly,
It has the disadvantage that many isomer mixtures other than 2,4-DTBP are produced as by-products. Moreover, 2,
Since the yield of 4-DTBP is largely determined by the thermodynamic equilibrium composition, it also has the disadvantage of being low. For example, SPAN.336838
For example, when 2,4-DTBP is produced from phenol and isobutylene in the presence of a sulfuric acid catalyst, as described in
%, and as other by-products, 2-tert-
Butylphenol (hereinafter referred to as 2-TBP) 22%,
4-tert-butylphenol (hereinafter referred to as 4-TBP) 17%, 2,6-di-tert-butylphenol (hereinafter referred to as 2,6-DTBP) 1%, 2,4,6
-tri-tert-butylphenol (hereinafter 2, 4,
The result was 1% (referred to as 6-TTBP).
これらの改良法として、US patent 3290389，
3367981に、触媒として弱酸であるアルミナを使
用する方法、US patent 4275249に0.3〜５％の
沸素や塩素を含有するアルミナを触媒とする方
法、US patent 4260833 Li−Ａ2O5を触媒とし
て使用する方法が記載されている。しかし、いず
れの改良方法も、イソブチレン／フエノールモル
比を理論量の２以上の過剰の条件下に、しかも
150〜250℃以上の過激な反応条件を必要とするた
め、イソブチレンオリゴマーの副生及びtertブチ
ル基の脱離等の副反応を避けることができず、必
ずしも工業的製造法としては好ましい方法とは言
いいがたい。 These improved methods include US patent 3290389,
3367981 describes a method using alumina, which is a weak acid, as a catalyst; US patent 4275249 describes a method using alumina containing 0.3 to 5% fluorine or chlorine as a catalyst; US patent 4260833 uses Li-A 2 O 5 as a catalyst. It describes how to do this. However, in all of the improvement methods, the isobutylene/phenol molar ratio is in excess of 2 or more over the theoretical amount, and
Because it requires extreme reaction conditions of 150 to 250°C or higher, side reactions such as the by-product of isobutylene oligomers and the elimination of tert-butyl groups cannot be avoided, so it is not necessarily a preferable method for industrial production. It's hard to say.
(2)の方法は、これまでに硫酸を使用する方法、
塩化アルミニウムを使用する方法、イオン交換樹
脂を使用する方法などが知られている。しかし、
これらの方法は各々次に示すような欠点を有して
いるために、工業的製造法としては使用されてい
ない。即ち、硫酸などのブロンステツド酸を触媒
とする方法は、装置上、高温では腐食が激しく、
触媒の中和、水洗工程を必要とし、またフエノー
ルを含む排水による公害の心配がある、など問題
点が多い。本発明者等の実験結果に於いても、硫
酸を使用した場合には、上記問題点以外にも、ス
ルホン化の副反応が併発することが認められ、ス
ルホン化物の存在により、中和及び水洗工程に於
ける油水分離性が極めて悪化すること、更に中和
水洗工程以後であつても、微量のスルホン化物が
油層に残存するため、２，４−DTBP蒸留精製
時に酸触媒として働き、蒸留塔底部で２，４−
DTBPの脱ブチル化反応を引き起こし、４−
TBPしか回収されないという事実を見い出して
いる。 Method (2) has so far been a method using sulfuric acid,
A method using aluminum chloride, a method using an ion exchange resin, etc. are known. but,
Each of these methods has the following drawbacks and is therefore not used as an industrial manufacturing method. In other words, the method using Bronsted acid such as sulfuric acid as a catalyst causes severe corrosion at high temperatures due to the equipment.
There are many problems, such as the need for catalyst neutralization and water washing steps, and the risk of pollution caused by wastewater containing phenol. In addition to the above-mentioned problems, the experimental results of the present inventors also show that when sulfuric acid is used, side reactions of sulfonation also occur, and due to the presence of sulfonates, neutralization and washing with water occur. In addition, even after the neutralization and water washing process, a trace amount of sulfonated substances remain in the oil layer, which acts as an acid catalyst during the distillation purification of 2,4-DTBP, causing the distillation column to deteriorate. 2,4- at the bottom
It causes the debutylation reaction of DTBP, and 4-
It has been discovered that only TBP is recovered.
塩化アルミニウムを使用する方法は、反応装置
の腐食、中和、水洗工程を必要とし、廃水公害の
心配があるなどの問題点がある。 The method using aluminum chloride has problems such as corrosion of the reaction equipment, neutralization, and water washing steps, and there are concerns about wastewater pollution.
第３のイオン交換樹脂を触媒とする方法は、反
応装置の腐食、中和水洗工程とそれに伴なう廃水
公害の心配はないが、イオン交換樹脂の物理的強
度の低下を防ぐために、反応温度を100℃以下と
低くせざるを得ないために、２，４−DTBP収
率が低いという欠点を有している。 The method using the third ion-exchange resin as a catalyst does not have to worry about corrosion of the reaction equipment, neutralization water washing process, and associated wastewater pollution, but the reaction temperature must be Since the temperature must be kept as low as 100°C or less, the yield of 2,4-DTBP is low.
（発明が解決しようとする問題点）
本発明は、２，４−DTBP以外の副生物の生
成が少なく、その結果、２，４−DTBPを収率
良く製造できると共に、反応装置の材質上の問題
がなく、中和、水洗工程を必要としない経済的に
有利な２，４−DTBPの製造方法を提供するも
のである。(Problems to be Solved by the Invention) The present invention produces less by-products other than 2,4-DTBP, and as a result, 2,4-DTBP can be produced with high yield, and The object of the present invention is to provide an economically advantageous method for producing 2,4-DTBP that is free from problems and does not require neutralization or washing steps.
（発明の概要）
すなわち本発明は、tert−ブチルフエノール類
のトランスアルキル化反応により２，４−ジ−
tert−ブチルフエノールを製造する方法におい
て、
（） 原料のtert−ブチルフエノール類中のフ
エノール核の総数に対するtert−ブチル基の総
数の比が約1.5〜2.5になるように原料を調製
し、
（） 触媒として、活性白土若しくは酸性白土
を、原料のtert−ブチルフエノール類に対し１
〜10重量％用い、
かつ
（） 反応を90〜150℃の温度で行うことを特
徴とする２，４−ジ−tert−ブチルフエノール
の製造方法に関するものである。(Summary of the invention) That is, the present invention provides 2,4-di-
In the method for producing tert-butylphenol, () the raw material is prepared so that the ratio of the total number of tert-butyl groups to the total number of phenol nuclei in the raw material tert-butylphenol is about 1.5 to 2.5; As a catalyst, activated clay or acid clay is used at a rate of 1% per tert-butylphenol as a raw material.
The present invention relates to a method for producing 2,4-di-tert-butylphenol, characterized in that the reaction is carried out at a temperature of 90 to 150°C.
（問題点を解決するための手段）
本発明において原料として用いるtert−ブチル
フエノール類としては、例えば２，４，６−
TTBPと２−TBPとの混合物、２，４，６−
TTBPと４−TBPとの混合物、あるいは２，４，
６−TTBPと２−TBPと４−TBPとの混合物な
どが挙げられるが、その混合割合が、原料tert−
ブチルフエノール類混合物中のフエノール核の総
数に対するtert−ブチル基の総数の比が、1.5〜
2.5の範囲、好ましくは1.8〜2.2の範囲にあるよう
に原料を混合調製することが必要である。(Means for Solving the Problems) Tert-butylphenols used as raw materials in the present invention include, for example, 2,4,6-
Mixture of TTBP and 2-TBP, 2,4,6-
A mixture of TTBP and 4-TBP, or 2,4,
Examples include mixtures of 6-TTBP, 2-TBP, and 4-TBP, but the mixing ratio depends on the raw material tert-TBP.
The ratio of the total number of tert-butyl groups to the total number of phenol nuclei in the butylphenol mixture is 1.5 to 1.
It is necessary to mix and prepare the raw materials so that they are in the range of 2.5, preferably in the range of 1.8 to 2.2.
原料tert−ブチルフエノール混合物中のフエノ
ール核の総数に対するtert−ブチル基の総数の比
が1.5未満では、反応生成分の主成分は２−TBP
や４−TBPとなり、２，４−DTBPの収率は低
下し、また2.5を超えると２，４−DTBP以外の
副生物の生成量が増加し、その結果として２，４
−DTBPの収率が低下するので、いずれも好ま
しくない。 When the ratio of the total number of tert-butyl groups to the total number of phenol nuclei in the raw material tert-butylphenol mixture is less than 1.5, the main component of the reaction product is 2-TBP.
and 4-TBP, the yield of 2,4-DTBP decreases, and when it exceeds 2.5, the amount of by-products other than 2,4-DTBP increases, and as a result, the yield of 2,4-DTBP decreases.
- None of these are preferred because the yield of DTBP decreases.
tert−ブチルフエノール類化合物とは、フエノ
ール骨格（フエノール核）にtert−ブチル基が１
個又はそれ以上結合している化合物であるが、本
発明でフエノール核の総数に対するtert−ブチル
基の総数の比とは、tert−ブチルフエノール類混
合物中に含まれるフエノール核の総数、すなわち
フエノール核を一つの化合物単位とみなしたとき
のフエノール核の全モル数に対するフエノール核
に結合しているtert−ブチル基単位の総数（全モ
ル数）の比のことであつて、例えば２，４，６−
TTBPと２−TBPのみの混合物において、フエ
ノール核の総数に対するtert−ブチル基の総数の
比を1.5〜2.5に調製するには、２，４，６−
TTBPに対する２−TBPの混合比率（モル比）
を１／３〜３の範囲にすればよい。本発明におい
ては、このtert−ブチルフエノール類として、
（） フエノールとイソブチレンをアルミニウ
ムトリフエノキシド触媒の存在下に反応させて
なる生成物から触媒除去後、蒸留工程において
２−TBPを主成分とする軽沸点留分及び高純
度２，６−DTBPを回収した後の２，４，６
−TTBPを主成分とする蒸留塔底部成分(a)と
（） フエノールとイソブチレンをアルミニウ
ムトリフエノキシド触媒の存在下に反応させて
なる生成物から触媒除去後、２，６−DTBP
を蒸留精製する工程で回収される２−TBPを
主成分とする軽沸点留分(b) 及び
本発明方法において、生成物より２，４−
DTBPを蒸留精製する工程で回収される４−
TBPを主成分とする軽沸点留分(c)から選ばれる
少なくとも一種の留分との混合物であつて、混合
物中のフエノール核の総数に対するtert−ブチル
フエノールの総数の比が1.5〜2.5の範囲にある混
合物を用いることが最も好ましい。 A tert-butylphenol compound has one tert-butyl group in the phenol skeleton (phenol nucleus).
However, in the present invention, the ratio of the total number of tert-butyl groups to the total number of phenol nuclei refers to the total number of phenol nuclei contained in the tert-butyl phenol mixture, that is, the ratio of the total number of tert-butyl groups to the total number of phenol nuclei. It is the ratio of the total number of tert-butyl group units bonded to the phenol nucleus (total number of moles) to the total number of moles of the phenol nucleus when considered as one compound unit, for example, 2, 4, 6. −
In a mixture of only TTBP and 2-TBP, 2,4,6-
Mixing ratio (molar ratio) of 2-TBP to TTBP
may be set in the range of 1/3 to 3. In the present invention, as the tert-butylphenols, () After removing the catalyst from a product obtained by reacting phenol and isobutylene in the presence of an aluminum triphenoxide catalyst, 2-TBP is used as the main component in a distillation process. 2,4,6 after recovering the light boiling fraction and high purity 2,6-DTBP
- 2,6-DTBP after removing the catalyst from the product obtained by reacting phenol and isobutylene in the presence of an aluminum triphenoxide catalyst with the distillation column bottom component (a) containing TTBP as the main component.
In the method of the present invention, 2,4-
4- recovered in the process of distilling and purifying DTBP
A mixture with at least one fraction selected from light boiling point fractions (c) containing TBP as a main component, wherein the ratio of the total number of tert-butylphenols to the total number of phenol nuclei in the mixture is in the range of 1.5 to 2.5. Most preferably, a mixture of:
本発明において、上記２，４，６−TTBPを
主成分とする蒸留塔底成分(a)は、一般的には２，
４，６−TTBP60〜97重量％と２，４−DTBP
約３〜40重量％からなる組成を有する混合物であ
り、２−TBPを主成分とする軽沸点留分(b)とは、
２−TBP70〜96重量％、フエノール約１〜10重
量％、２，６−DTBP約３〜30重量％からなる
組成の混合物であり、また４−TBPを主成分と
する軽沸点留分(c)は４−TBP約70〜97重量％、
２，４−DTBP約３〜30重量％からなる組成の
混合物である。 In the present invention, the distillation column bottom component (a) mainly containing 2,4,6-TTBP is generally 2,4,6-TTBP.
4,6-TTBP60-97% by weight and 2,4-DTBP
The light boiling point fraction (b) is a mixture having a composition of about 3 to 40% by weight and whose main component is 2-TBP.
It is a mixture with a composition consisting of 70 to 96% by weight of 2-TBP, about 1 to 10% by weight of phenol, and about 3 to 30% by weight of 2,6-DTBP, and a light boiling point fraction (c ) is 4-TBP approximately 70-97% by weight,
It is a mixture having a composition of about 3 to 30% by weight of 2,4-DTBP.
これら(a)成分と(b)及び／または(c)留分を混合し
て原料とする場合、その混合割合は、原料中のフ
エノール核の総数に対するtert−ブチルフエノー
ルの総数の比が1.5〜2.5の範囲にあれば特に限定
されるものではない。 When these (a) components and (b) and/or (c) fractions are mixed to form a raw material, the mixing ratio is such that the ratio of the total number of tert-butylphenol to the total number of phenol nuclei in the raw material is 1.5 to 1. There is no particular limitation as long as it is within the range of 2.5.
本発明において触媒として使用する、活性白土
若しくは酸性白土は通常市販されているものをそ
のまま使用することができる。あるいは、300〜
600℃の範囲で、焼成したものを使用してもよく、
特に限定されない。粒形についても特に限定しな
いが、粒径10〜2000μ程度の粒状または粉状のも
のが望ましい。 As the activated clay or acid clay used as a catalyst in the present invention, commercially available clays can be used as they are. Or 300～
You may use one that has been fired within the range of 600℃.
Not particularly limited. The particle shape is not particularly limited either, but granular or powder particles with a particle size of about 10 to 2000 μm are desirable.
本発明では、２，４−DTBPの収率の面から
特に活性白土が好ましい触媒である。 In the present invention, activated clay is a particularly preferred catalyst from the viewpoint of the yield of 2,4-DTBP.
本発明に言うトランスアルキル化反応は、前記
触媒の存在下に、液相で、加熱することによつて
実施するが、触媒の活性低下を極力押えるために
は、触媒を固定床として用いることは避けなけれ
ばならない。従つて、反応形式としては、触媒を
攪拌下に反応液中に効率良く分散せしめることが
必要であり、触媒を流動床として用いることが好
ましい。 The transalkylation reaction referred to in the present invention is carried out in the presence of the catalyst in a liquid phase by heating, but in order to suppress the decrease in catalyst activity as much as possible, it is not recommended to use the catalyst as a fixed bed. Must be avoided. Therefore, as for the reaction format, it is necessary to efficiently disperse the catalyst in the reaction liquid under stirring, and it is preferable to use the catalyst as a fluidized bed.
また原料に対する触媒量は１〜10重量％が好ま
しく、特に１〜３重量％が好ましい。 The amount of catalyst relative to the raw material is preferably 1 to 10% by weight, particularly preferably 1 to 3% by weight.
触媒量が１重量％未満では、反応温度を高くし
なければならないが、そのために副生物の生成量
が増加し、また触媒の活性低下が促進され、その
結果２，４−DTBPの収率が低下し、また10重
量％を越えると反応速度が早いため、反応温度は
下げられるものの、４−TBPの副生量が増加し、
その結果２，４−DTBPの収率が低下するので、
いずれも好ましくない。また、反応温度は90〜
150℃が好適である。それ以下の温度では、反応
速度が遅いため２，４−DTBP収率が悪く、ま
たそれ以上の温度では脱ブチル化が著しく促進さ
れ、４−TBPの副生が増加し、それにつれて２，
４−DTBP収率が低下する。反応時間は、反応
温度及び触媒量に左右されるが、前記温度範囲及
び触媒等の範囲ならば、１時間〜10時間が好適で
ある。それ以上反応を継続すると、４−TBPの
収率が増加し、それに伴ない２，４−DTBP収
率は低下する。本反応は全て常圧下に実施する。 If the amount of catalyst is less than 1% by weight, the reaction temperature must be raised, which increases the amount of by-products produced and accelerates the decrease in catalyst activity, resulting in a decrease in the yield of 2,4-DTBP. If it exceeds 10% by weight, the reaction rate is fast, so although the reaction temperature can be lowered, the amount of 4-TBP by-product increases.
As a result, the yield of 2,4-DTBP decreases, so
Neither is preferable. Also, the reaction temperature is 90~
150°C is preferred. At lower temperatures, the reaction rate is slow and the yield of 2,4-DTBP is poor; at higher temperatures, debutylation is significantly accelerated, the by-product of 4-TBP increases, and 2,4-DTBP yield increases.
4-DTBP yield decreases. The reaction time depends on the reaction temperature and the amount of catalyst, but is preferably 1 hour to 10 hours within the above temperature range and catalyst amount. If the reaction is continued beyond that point, the yield of 4-TBP increases, and the yield of 2,4-DTBP decreases accordingly. This reaction is all carried out under normal pressure.
反応生成物の処理としては、触媒を適当な過
装置により別した後、液をそのまま蒸留精製
工程に供給する。まず、蒸留精製工程の初留分と
して、４−TBPを主成分とする留分を回収し、
次に純度99wt％以上の高純度２，４−DTBPを
製品として得る。前述した如く、４−TBPを主
成分とする留分は、再度本発明に言う２，４−
DTBP製造原料として使用することができる。 As for treatment of the reaction product, after separating the catalyst using a suitable filtration device, the liquid is directly supplied to a distillation purification process. First, as the first fraction of the distillation purification process, a fraction containing 4-TBP as the main component is collected,
Next, high-purity 2,4-DTBP with a purity of 99 wt% or more is obtained as a product. As mentioned above, the fraction mainly composed of 4-TBP is again referred to in the present invention as 2,4-TBP.
It can be used as raw material for DTBP production.
（発明の効果）
本発明によれば、２，４−DTBP以外の副生
物の生成が少なく、従つて２，４−DTBPの収
率が高く、しかも純度99重量％以上の高純度２，
４−DTBPが得られる。(Effects of the Invention) According to the present invention, the production of by-products other than 2,4-DTBP is small, and therefore the yield of 2,4-DTBP is high.
4-DTBP is obtained.
また本発明に従えば、反応装置の材質上の問題
がなく、しかも中和、水洗工程を必要としないた
め経済的に極めて有利である。 Further, according to the present invention, there is no problem with the material of the reactor, and furthermore, there is no need for neutralization and water washing steps, which is extremely advantageous economically.
更に本発明においては、２，６−DTBPの副
生物として回収される２−TBP及び２，４，６
−TTBP、とりわけ後者を２，４−DTBPに有
効に変換できるという利点を有している。すなわ
ち、すでに知られているように２，６−DTBP
は、フエノールをオルソアルキル化触媒、すなわ
ち、アルミニウムトリフエノキシドの存在下に、
イソブチレンと反応させて製造されているが、特
開昭57−95928の記載例によれば、２，６−
DTBP収率は、71mol％であり、その他に２−
TBP11mol％、２，４−DTBP2mol％、２，４，
６−TTBP9mol％が副生する。その中でも２−
TBPは２，６−DTBPの合成中間体であるため
に、２，６−DTBP蒸留精製工程の初留分とし
て回収された後、再び２，６−DTBP製造反応
器に循環し、２，６−DTBPに変換することが
できる。しかし、２，４，６−TTBPはかなり
多量に副生するものの、アルミニウムトリフエノ
キシド触媒によつては、４位（水酸基に対して
para位）のtert−ブチル基の脱アルキル化反応が
進行しないために、そのまま２，６−DTBP反
応器へ循環することができないという問題点があ
つた。従い従来は、２，６−DTBP蒸留精製時
の釜残部をそのまま焼却する以外に処理法のない
のが実情であつた。本発明により、この２，４，
６−TTBPを主成分として含む蒸留塔底部を、
２，４−DTBP原料として有効に利用すること
が可能となつた。 Furthermore, in the present invention, 2-TBP and 2,4,6 recovered as by-products of 2,6-DTBP
-TTBP, especially the latter, has the advantage of being able to be effectively converted into 2,4-DTBP. That is, as already known, 2,6-DTBP
In the presence of an orthoalkylation catalyst, i.e. aluminum triphenoxide, phenol is
It is produced by reacting with isobutylene, but according to the description in JP-A-57-95928, 2,6-
The DTBP yield was 71 mol%, in addition to 2-
TBP11mol%, 2,4-DTBP2mol%, 2,4,
9 mol% of 6-TTBP is produced as a by-product. Among them, 2-
Since TBP is a synthetic intermediate for 2,6-DTBP, it is recovered as the first fraction of the 2,6-DTBP distillation purification process and then recycled to the 2,6-DTBP production reactor. -Can be converted to DTBP. However, although 2,4,6-TTBP is produced as a by-product in a fairly large amount, depending on the aluminum triphenoxide catalyst, 2,4,6-TTBP is
Since the dealkylation reaction of the tert-butyl group at the para position does not proceed, there was a problem in that it could not be recycled as it was to the 2,6-DTBP reactor. Therefore, in the past, there was no other treatment method than to directly incinerate the residue from the distillation process of 2,6-DTBP. According to the present invention, these 2, 4,
6-The bottom of the distillation column containing TTBP as the main component,
It has now become possible to use it effectively as a raw material for 2,4-DTBP.
（実施例）
実施例 １
フエノール2.26Kgと、２倍モルのイソブチレン
をアルミニウムトリフエノキシドを触媒として用
いて反応させ、２，６−DTBP生成物を得た。
生成物は生成物のアルミニウムを除去するために
硫酸洗浄、苛性洗浄、水洗を行い、20段オルダー
シヨ蒸留塔を用いて蒸留を行い、軽沸留分(b)（沸
点は52〜68℃／１mmＨｇ）616ｇ（成分組成：フ
エノール２重量％、２−TBP86重量％、２，６
−DTBP12重量％）、２，６−DTBP主留分（沸
点は85℃／１mmＨｇ）4.24Kg（２，６−DTBP純
度：99重量％）及び蒸留塔底成分(a)964ｇ（成分
組成：２，６−DTBP3重量％、２，４−
DTBP15重量％、２，４，６−TTBP77重量％）
を得た。(Examples) Example 1 2.26 kg of phenol and 2 times the mole of isobutylene were reacted using aluminum triphenoxide as a catalyst to obtain a 2,6-DTBP product.
The product is washed with sulfuric acid, caustic, and water to remove aluminum, and then distilled using a 20-stage Oldersho distillation column to obtain a light-boiling fraction (b) (boiling point: 52-68℃/1mmHg). ) 616g (Component composition: 2% by weight of phenol, 86% by weight of 2-TBP, 2,6
-DTBP12% by weight), 2,6-DTBP main fraction (boiling point 85℃/1mmHg) 4.24Kg (2,6-DTBP purity: 99% by weight) and distillation column bottom component (a) 964g (component composition: 2 ,6-DTBP3wt%,2,4-
DTBP15% by weight, 2,4,6-TTBP77% by weight)
I got it.
次に、冷却管、攪拌器、温度計を付した四ツ口
フラスコに上記の軽沸留分(b)227ｇ、蒸留塔底成
分(a)964ｇ及び２，４−DTBP蒸留軽沸留分(c)
217ｇ（成分組成：４−TBP87重量％、２，４−
DTBP12重量％）を仕込み、攪拌下、反応温度
が110℃に到達後、活性白土（日本活性白土社製
SA−254）28ｇを加え、３時間攪拌した。過後
10段オルダーシヨ蒸留塔を用いて蒸留を行い、軽
沸留分（沸点は154〜166℃／50mmＨｇ）217ｇ
（成分組成：４−TBP87重量％、２，４−
DTBP12重量％）及び２，４−DTBP主留分
（沸点は170℃／50mmＨｇ）909ｇ（２，４−
DTBP純度：99％）を得た。ガスクロ分析の結
果、２，４−DTBPの総収率は69％であつた。
尚、４−TBP、２，４−DTBP共にNMR赤外線
吸収スペクトル、マススペクトルにより固定し
た。 Next, 227 g of the above light boiling fraction (b), 964 g of the distillation column bottom component (a), and the 2,4-DTBP distillation light boiling fraction ( c)
217g (composition: 4-TBP87% by weight, 2,4-
DTBP (12% by weight) was charged, and after the reaction temperature reached 110℃ under stirring, activated clay (manufactured by Nippon Shakushirado Co., Ltd.) was added.
SA-254) 28g was added and stirred for 3 hours. After the past
Distillation was carried out using a 10-stage oldersho distillation column, and 217g of light boiling fraction (boiling point: 154-166℃/50mmHg) was obtained.
(Component composition: 4-TBP87% by weight, 2,4-
DTBP12% by weight) and 2,4-DTBP main fraction (boiling point 170℃/50mmHg) 909g (2,4-DTBP)
DTBP purity: 99%) was obtained. As a result of gas chromatography analysis, the total yield of 2,4-DTBP was 69%.
In addition, both 4-TBP and 2,4-DTBP were fixed by NMR infrared absorption spectrum and mass spectrum.
比較例 １
冷却管、攪拌器、温度計を付した四ツ口フラス
コに実施例1.と同様のトランスアルキル化原料
414ｇ（組成は、フエノール0.3重量％、２−
TBP15重量％、４−TBP13重量％、２，４−
DTBP12重量％、２，６−DTBP4重量％、２，
４，６−TTBP53重量％）を仕込み、攪拌下、
反応温度が150℃に到達後、硫酸8.3ｇを加え、10
〜20分間攪拌する。反応後は反応液を室温まで冷
却し、生成物を取り出し、5.8％の炭酸ナトリウ
ムを含む20％硫酸ナトリウム水溶液900ｇを加え、
攪拌し中和した。油水分離性が悪いので、１晩放
置後油水分離を行う。有機層を10段のオルダーシ
ヨ蒸留塔を用いて蒸留を行うと、４−TBP留分
（沸点155〜163℃／100mmＨｇ）184ｇ（成分組
成：フエノール８重量％、４−TBP89重量％）
が得られたのみであり、２，４−DTBP留分は
得られなかつた。Comparative Example 1 The same transalkylation raw material as in Example 1 was placed in a four-necked flask equipped with a condenser, stirrer, and thermometer.
414g (composition: phenol 0.3% by weight, 2-
TBP15% by weight, 4-TBP13% by weight, 2,4-
DTBP12% by weight, 2,6-DTBP4% by weight, 2,
4,6-TTBP53% by weight) and stirred,
After the reaction temperature reached 150℃, add 8.3g of sulfuric acid and
Stir for ~20 minutes. After the reaction, the reaction solution was cooled to room temperature, the product was taken out, and 900 g of a 20% aqueous sodium sulfate solution containing 5.8% sodium carbonate was added.
Stir and neutralize. Since oil and water separation properties are poor, oil and water separation is performed after leaving it for one night. When the organic layer was distilled using a 10-stage oldersho distillation column, 184 g of 4-TBP fraction (boiling point 155-163°C/100 mmHg) (composition: phenol 8% by weight, 4-TBP 89% by weight)
was obtained, and no 2,4-DTBP fraction was obtained.
比較例 ２
冷却管、攪拌器、温度計を付した四ツ口フラス
コに実施例1.と同様のトランスアルキル化原料
450ｇを仕込み、攪拌下、反応温度が90℃に到達
後、陽イオン交換樹脂（アンバーリスト15）45ｇ
を加えて５時間攪拌した。反応液は過し、液
を10段のオルダーシヨ蒸留塔を用いて蒸留を行う
と、軽沸留分（沸点は145〜162℃／100mmＨｇ）
66ｇ（成分組成：４−TBP85重量％、２，４−
DTBP9重量％、２，６−DTBP4重量％）及び
２，４−DTBP主留分（沸点は165〜170℃／50
mmＨｇ）196ｇ（２，４−DTBP純度：98％）が
得られた。ガスクロ分析の結果、２，４−
DTBPの総収率は49％であつた。Comparative Example 2 The same transalkylation raw material as in Example 1 was placed in a four-necked flask equipped with a condenser, a stirrer, and a thermometer.
Pour 450g of cation exchange resin (Amberlyst 15) under stirring and after the reaction temperature reaches 90℃.
was added and stirred for 5 hours. The reaction solution is filtered, and the solution is distilled using a 10-stage Oldersho distillation column to produce a light boiling fraction (boiling point: 145-162℃/100mmHg).
66g (composition: 4-TBP85% by weight, 2,4-
DTBP9wt%, 2,6-DTBP4wt%) and 2,4-DTBP main fraction (boiling point 165-170℃/50
mmHg) (2,4-DTBP purity: 98%) was obtained. As a result of gas chromatography, 2,4-
The total yield of DTBP was 49%.
Claims (1)
ル化反応により２，４−ジ−tert−ブチルフエノ
ールを製造する方法において、 （） 原料のtert−ブチルフエノール類中のフ
エノール核の総数に対するtert−ブチル基の総
数の比が約1.5〜2.5になるように原料を調整
し、 （） 触媒として、活性白土若しくは酸性白土
を、原料のtert−ブチルフエノール類に対し、
１〜10重量％用い、 かつ （） 反応を90〜140℃の温度で行うことを特
徴とする２，４−ジ−tert−ブチルフエノール
の製造方法。 ２ tert−ブチルフエノール類として、２，４，
６−トリ−tert−ブチルと、４−tert−ブチルフ
エノール及び２−tert−ブチルフエノールから選
ばれた少なくとも一種のtert−ブチルフエノール
との混合物を用いることを特徴とする特許請求の
範囲第１項記載の方法。 ３ tert−ブチルフエノール類として、 （） フエーノルとイソブチレンをアルミニウ
ムトリフエノキシド触媒の存在下に反応させて
なる生成物から触媒除去後蒸留工程において２
−tert−ブチルフエノールを主成分とする軽沸
点留分及び高純度２，６−ジ−tert−ブチルフ
エノールを回収した後の２，４，６−トリ−
tert−ブチルフエノールを主成分とする蒸留塔
底部成分(a)と、 （） フエノールとイソブチレンをアルミニウ
ムトリフエノキシド触媒の存在下に反応させて
なる生成物から触媒除去後、２，６−ジ−tert
−ブチルフエノールを蒸留精製する工程で回収
される２−tert−ブチルフエノールを主成分と
する軽沸点留分(b) 及び 本発明方法において、生成物より２，４−ジ
−tert−ブチルフエノールを蒸留精製する工程
で回収される４−tert−ブチルフエノールを主
成分とする軽沸点留分(c)から選ばれる少なくと
も一種の留分 との混合物を用いることを特徴とする特許請求の
範囲第１項記載の方法。[Scope of Claims] 1. In a method for producing 2,4-di-tert-butylphenol by transalkylation reaction of tert-butylphenols, () based on the total number of phenol nuclei in the raw material tert-butylphenols. The raw materials are adjusted so that the ratio of the total number of tert-butyl groups is about 1.5 to 2.5, () activated clay or acid clay is used as a catalyst to the tert-butyl phenols of the raw material,
1. A method for producing 2,4-di-tert-butylphenol, comprising: using 1 to 10% by weight, and () carrying out the reaction at a temperature of 90 to 140°C. 2 As tert-butylphenols, 2,4,
Claim 1, characterized in that a mixture of 6-tri-tert-butyl and at least one type of tert-butylphenol selected from 4-tert-butylphenol and 2-tert-butylphenol is used. Method described. 3. As tert-butylphenols, () 2.
2,4,6-tri-butylphenol after recovering the light-boiling fraction mainly composed of -tert-butylphenol and high-purity 2,6-di-tert-butylphenol.
A distillation column bottom component (a) containing tert-butylphenol as a main component and (2) 2,6-di- tert
- A light-boiling fraction (b) mainly composed of 2-tert-butylphenol recovered in the step of distilling and purifying butylphenol; and In the method of the present invention, 2,4-di-tert-butylphenol is recovered from the product Claim 1, characterized in that a mixture with at least one kind of fraction selected from the light boiling point fraction (c) containing 4-tert-butylphenol as a main component recovered in the distillation purification step is used. The method described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59110883A JPS60255742A (en) | 1984-06-01 | 1984-06-01 | Production of 2,4-di-tert-butylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59110883A JPS60255742A (en) | 1984-06-01 | 1984-06-01 | Production of 2,4-di-tert-butylphenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60255742A JPS60255742A (en) | 1985-12-17 |
| JPH0513137B2 true JPH0513137B2 (en) | 1993-02-19 |
Family
ID=14547105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59110883A Granted JPS60255742A (en) | 1984-06-01 | 1984-06-01 | Production of 2,4-di-tert-butylphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60255742A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0725713B2 (en) * | 1986-12-23 | 1995-03-22 | 三井石油化学工業株式会社 | Method for producing 2,4-di-t-butylphenol |
| JPH0725714B2 (en) * | 1986-12-26 | 1995-03-22 | 三井石油化学工業株式会社 | Method for producing 2,4-di-t-butylphenol |
| US8828916B2 (en) * | 2006-12-28 | 2014-09-09 | Chevron Oronite Company Llc | Method to prepare nonylated diphenylamine using recycle sequential temperatures |
| EP3347336B1 (en) | 2015-09-11 | 2019-06-12 | Basf Se | Process for the alkylation of phenols |
-
1984
- 1984-06-01 JP JP59110883A patent/JPS60255742A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60255742A (en) | 1985-12-17 |
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