JPH0345743B2 - - Google Patents
Info
- Publication number
- JPH0345743B2 JPH0345743B2 JP58116440A JP11644083A JPH0345743B2 JP H0345743 B2 JPH0345743 B2 JP H0345743B2 JP 58116440 A JP58116440 A JP 58116440A JP 11644083 A JP11644083 A JP 11644083A JP H0345743 B2 JPH0345743 B2 JP H0345743B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- rubber
- tert
- resin
- distillation residue
- 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
- 229920001971 elastomer Polymers 0.000 claims description 20
- 239000005060 rubber Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000004821 distillation Methods 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 claims description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000034 method Methods 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
- 238000000746 purification Methods 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000010058 rubber compounding Methods 0.000 description 13
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 8
- 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 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- JKFZLMPBXBMSPD-UHFFFAOYSA-N 2-butan-2-yl-4-tert-butylphenol Chemical compound CCC(C)C1=CC(C(C)(C)C)=CC=C1O JKFZLMPBXBMSPD-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- IXKVYSRDIVLASR-UHFFFAOYSA-N 2,3-dioctylphenol Chemical compound CCCCCCCCC1=CC=CC(O)=C1CCCCCCCC IXKVYSRDIVLASR-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は新規ゴム配合剤の製造法に関する。
少なくとも１種のイソブチレンオリゴマーとフ
エノールとをシリカ−アルミナ触媒、活性白土、
ゼオライト等の触媒の存在下に反応させることに
より、パラ−tert−ブチルフエノール（以下BP
と略記する）及びパラ−tert−オクチルフエノー
ル（以下OPと略記する）を製造することは、公
知である。この方法で製造されたBP及びOPは蒸
溜によつて精製されるが、その際かなりの量の蒸
溜残渣が残留し、蒸留残渣の有効利用の開発が望
まれている。しかしながら、従来、燃料として利
用される以外には、有効な用途は見いだされてい
ない。
本発明は、このような問題点を解決し、BP及
びOPの蒸溜残渣の有効な用途を開発することを
目的としてなされたものである。
この目的は、本発明によれば、蒸溜残渣をアル
デヒドと反応させてゴム組成物への配合剤として
優れた樹脂にすることによつて達成される。
即ち、本発明はイソブチレンオリゴマーとフエ
ノールとを触媒の存在下に反応させてパラ−tert
−ブチルフエノール及びパラ−tert−オクチルフ
エノールを製造し、精製する際に得られる蒸溜残
渣をアルデヒド類と反応させることを特徴とする
ゴム配合剤の製造法に関する。
蒸溜残渣は、イソブチレンオリゴマー、例えば
ジイソブチレン等のイソブチレンの２〜５量体の
うち少なくとも１種とフエノールとを触媒の存在
下に反応させ、BP及びOPを製造し、BPを得た
い場合には、BPより低沸点の物質を溜去し、BP
を蒸溜により取り出した後に残留するものであ
り、２，４−ジ−tert−ブチルフエノール、２−
sec−４−tert−ブチルフエノール、OP、２，４
−ジオクチルフエノール、その他の高沸点物、更
に残留BP、tert−アミルフエノール、フエノー
ルを含む。
この蒸溜残渣は一般に下記のような組成及び組
成比を有する：
フエノール ０〜２重量％
BP ５〜10重量％
ｐ−tert−アミルフエノール ５〜７重量％
２，４−ジ−tert−ブチルフエノール
20〜10重量％
２−sec−４−tert−ブチルフエノール
10〜15重量％
ｏ−オクチルフエノール ５〜15重量％
OP 30〜40重量％
その他 残 部
前記のBPの製造に使用される触媒は、シリカ
−アルミナ、活性白土、ゼオライト等の触媒であ
り、反応温度は通常、約80〜250℃である。
一方、OPの製造は、触媒としてシリカ−アル
ミナ、活性白土、ゼオライト等を使用する場合に
は、通常、約70〜150℃の反応温度で行われ、触
媒としてフリーデルクラフツ触媒、硫酸、陽イオ
ン交換触媒等を使用する場合には、通常、約70〜
130℃の反応温度で実施される。
本発明においては、こうして得た蒸溜残渣にア
ルデヒドを加え、塩基性触媒又は酸性触媒の存在
下、好ましくは、約80〜200℃で加熱、反応させ
られる。反応温度が低すぎると反応が遅くなり、
高すぎると得られる樹脂に濁りを生じる。
アルデヒドとしては、ホルムアルデヒド、パラ
ホルムアルデヒド、アセトアルデヒド等が挙げら
れ、これらのアルデヒドのうち１種以上をそのま
ま、又は水または有機溶剤に溶解させて使用する
ことができる。アルデヒドの添加量は、蒸溜残渣
100重量部に対して15〜70重量部が好ましく、特
に、20〜50重量部が好ましい。アルデヒドの量が
少ないと分子量が小さすぎ、多すぎると樹脂に濁
りが生じる。
塩基性触媒としては、アンモニア又はアルカリ
金属若しくはアルカリ土類金属の水酸化部、例え
ば水酸化ナトリウム、水酸化カリウム、水酸化リ
チウム、水酸化カルシウム或は水酸化バリウム等
を、蒸溜残渣100重量部に対して0.1〜0.5重量部
使用するのが好ましい。塩基性触媒が少なすぎる
と反応が遅くなり、多すぎるとあとで触媒の除去
が困難になる。
酸性触媒としては、塩酸、蓚酸、硫酸、硝酸、
パラトルエンスルホン酸、スルフアミン酸、マレ
イン酸等を、蒸溜残渣100重量部に対して0.1〜
0.5重量部使用するのが好ましい。酸性触媒が少
なすぎると反応が遅くなり、多すぎるとあとで触
媒の除去が困難になる。
得られる樹脂は固形状でしかもゴムと溶融可能
にするためにその軟化点が60〜160℃になるよう
に、前記原料、配合、反応温度等により反応を適
宜調整するのが好ましく、特に軟化点が80〜120
℃になるように調整するのが好ましい。この調整
のために、反応開始時又は反応の途中に更にアル
キルフエノール、アラキルフエノール、アリール
フエノール、ビスフエノールＡ、クマロン樹脂、
クマロン−インデン樹脂、石油樹脂、エポキシ樹
脂等を適宜、選択して添加することができる。ク
マロン樹脂、クマロン−インデン樹脂、石油樹
脂、ロジン及びロジン変性樹脂、テルペン樹脂、
キシレン樹脂、エポキシ樹脂等は、蒸溜残渣とア
ルデヒドとの反応後に添加することもできる。
こうして得た本発明による樹脂は、ゴム組成物
に配合すると、タツキネス、引張強さ及び伸びを
著しく向上させる。即ち、こうして得た樹脂はゴ
ム配合剤として優れ、特に従来、脂肪族系石油樹
脂が使用されているタイヤ製造用ゴム組成物に配
合する場合に優れた効果を示す。
本発明によるゴム配合剤を配合するゴム成分は
任意の合成ゴム及び天然ゴムであつてよい。特
に、天然ゴム、スチレン−ブタジエンゴム、ブタ
ジエンゴム、ニトリルゴム、クロロプレンゴム等
に配合することができる。本発明による得られる
ゴム配合剤はゴム100重量部に対し、１〜10重量
部配合するのが好ましい。ゴム配合剤が少なすぎ
ると配合することによる効果が小さく、多すぎて
も改質効果の向上があまりなく、加硫を遅らせる
ことがある。ゴム組成物は、必要に応じて常用の
添加剤、例えば可塑剤、充填剤、顔料、加硫剤、
加硫促進剤、老化防止剤等を含んでいてよい。
次に、実施例に基づいて本発明を詳述するが、
本発明はこれに限定されるものではない。なお、
実施例に使用するBP及びOPの蒸溜残渣の組成及
び組成比は下記のとおりである。
フエノール ０重量％
BP ９重量％
ｐ−tert−アミルフエノール ５重量％
２，４−ジ−tert−ブチルフエノール 20重量％
２−sec−４−tert−ブチルフエノール 12重量％
ｏ−オクチルフエノール ９重量％
OP 34重量％
その他 11重量％
実施例 １
蒸溜残渣1000ｇにパラホルムアルデヒド250ｇ
及び塩酸５ｇを加え、100℃で３時間反応させた。
更に、昇温して150〜170℃で２時間反応させて軟
化点（球環法）が94℃、色相（USロジン色相標
準計）Ｆの樹脂を得た。この樹脂を以下ゴム配合
剤Ａと記す。
実施例 ２
蒸溜残渣1000ｇにパラホルムアルデヒド180ｇ
及び水酸化カルシウム５ｇを加え、100℃で５時
間反応させた。その後、塩酸で中和してPH６〜７
にし、水洗により塩化カルシウムを除去し、150
〜170℃で３時間反応させて軟化点が81℃、色相
Ｆの樹脂を得た。この樹脂を以下ゴム配合剤Ｂと
記す。
応用例 １
次に、ゴム配合剤Ａ及びＢ、ヒタノール1501日
立化成工業株式会社製商品名：以下ゴム配合剤Ｃ
と記す）及びエスコレツツ1202U（エツソスタン
ダード社製脂肪族系石油樹脂の商品名：以下ゴム
配合剤Ｄと記す）をゴム配合剤として使用し、下
記のゴム組成物を作り、バンバリーミキサーで
100℃で混合した後、150℃で30分間加硫した。得
られたゴムの物性を表１に示す。
ゴム組成物の組成
スチレン−ブタジエンゴム（JSR＃1502日本合成
ゴム(株)製、商品名） 100重量％
カーボンブラツク 50重量％
プロセスオイル 10重量％
ステアリン酸 ３重量％
亜鉛華 ５重量％
ノクラツチ224（大内新興化学(株)製、商品名）
１重量％
硫 黄 ２重量％
ノクセラーCZ（大内新興化学(株)製、商品名）
１重量％
ゴム配合剤 ４重量％
The present invention relates to a method for producing a novel rubber compound. At least one isobutylene oligomer and phenol are combined with a silica-alumina catalyst, activated clay,
By reacting in the presence of a catalyst such as zeolite, para-tert-butylphenol (BP
It is known to produce para-tert-octylphenol (hereinafter abbreviated as OP) and para-tert-octylphenol (hereinafter abbreviated as OP). BP and OP produced by this method are purified by distillation, but a considerable amount of distillation residue remains during this process, and it is desired to develop an effective use of the distillation residue. However, until now, no effective use has been found for it other than as a fuel. The present invention was made with the aim of solving these problems and developing effective uses for the distillation residues of BP and OP. This object is achieved according to the invention by reacting the distillation residue with aldehydes to form a resin which is excellent as a compounding agent in rubber compositions. That is, the present invention involves reacting isobutylene oligomer and phenol in the presence of a catalyst to produce para-tert.
The present invention relates to a method for producing a rubber compounding agent, which comprises reacting a distillation residue obtained during the production and purification of -butylphenol and para-tert-octylphenol with aldehydes. The distillation residue is used to produce BP and OP by reacting at least one isobutylene oligomer, for example, isobutylene dimer to pentamer such as diisobutylene, with phenol in the presence of a catalyst. , distill off substances with a lower boiling point than BP, and BP
It is what remains after distillation of 2,4-di-tert-butylphenol, 2-
sec-4-tert-butylphenol, OP, 2,4
-Contains dioctylphenol and other high-boiling substances, as well as residual BP, tert-amylphenol, and phenol. This distillation residue generally has the following composition and composition ratio: Phenol 0-2% by weight BP 5-10% by weight p-tert-amylphenol 5-7% by weight 2,4-di-tert-butylphenol
20-10% by weight 2-sec-4-tert-butylphenol
10-15% by weight o-Octylphenol 5-15% by weight OP 30-40% by weight Others Balance The catalysts used in the production of BP are silica-alumina, activated clay, zeolite, etc. The temperature is typically about 80-250°C. On the other hand, the production of OP is usually carried out at a reaction temperature of about 70 to 150°C when silica-alumina, activated clay, zeolite, etc. are used as catalysts, and Friedel-Crafts catalysts, sulfuric acid, cations, etc. are used as catalysts. When using an exchange catalyst etc., it is usually about 70~
It is carried out at a reaction temperature of 130°C. In the present invention, an aldehyde is added to the distillation residue thus obtained, and the mixture is heated and reacted preferably at about 80 to 200°C in the presence of a basic catalyst or an acidic catalyst. If the reaction temperature is too low, the reaction will be slow;
If the temperature is too high, the resulting resin becomes cloudy. Examples of the aldehyde include formaldehyde, paraformaldehyde, and acetaldehyde, and one or more of these aldehydes can be used as is or dissolved in water or an organic solvent. The amount of aldehyde added is based on the distillation residue.
It is preferably 15 to 70 parts by weight, particularly preferably 20 to 50 parts by weight, per 100 parts by weight. If the amount of aldehyde is too small, the molecular weight will be too small, and if it is too large, the resin will become cloudy. As a basic catalyst, ammonia or an alkali metal or alkaline earth metal hydroxide, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, or barium hydroxide, is added to 100 parts by weight of the distillation residue. It is preferable to use 0.1 to 0.5 parts by weight. Too little basic catalyst will slow down the reaction, while too much will make it difficult to remove the catalyst later. Examples of acidic catalysts include hydrochloric acid, oxalic acid, sulfuric acid, nitric acid,
Add para-toluenesulfonic acid, sulfamic acid, maleic acid, etc. from 0.1 to 100 parts by weight of the distillation residue.
Preferably, 0.5 part by weight is used. Too little acidic catalyst slows down the reaction; too much acidic catalyst makes it difficult to remove the catalyst later. In order to make the resulting resin solid and meltable with rubber, it is preferable to adjust the reaction appropriately by adjusting the raw materials, formulation, reaction temperature, etc. so that the softening point is 60 to 160°C, and in particular the softening point is 80~120
It is preferable to adjust the temperature to ℃. For this adjustment, at the start of the reaction or during the reaction, alkylphenol, aracylphenol, arylphenol, bisphenol A, coumaron resin, etc.
Coumarone-indene resin, petroleum resin, epoxy resin, etc. can be selected and added as appropriate. Coumaron resin, coumaron-indene resin, petroleum resin, rosin and rosin modified resin, terpene resin,
A xylene resin, an epoxy resin, etc. can also be added after the reaction between the distillation residue and the aldehyde. When the resin according to the present invention thus obtained is blended into a rubber composition, it significantly improves tackiness, tensile strength and elongation. That is, the resin thus obtained is excellent as a rubber compounding agent, and exhibits particularly excellent effects when blended into tire manufacturing rubber compositions in which aliphatic petroleum resins have conventionally been used. The rubber component with which the rubber compound according to the invention is compounded may be any synthetic or natural rubber. In particular, it can be blended with natural rubber, styrene-butadiene rubber, butadiene rubber, nitrile rubber, chloroprene rubber, and the like. The rubber compounding agent obtained according to the present invention is preferably blended in an amount of 1 to 10 parts by weight per 100 parts by weight of rubber. If the amount of the rubber compounding agent is too small, the effect of mixing it will be small, and if it is too large, the modification effect will not be improved much and vulcanization may be delayed. The rubber composition may contain conventional additives such as plasticizers, fillers, pigments, vulcanizing agents,
It may contain a vulcanization accelerator, an anti-aging agent, etc. Next, the present invention will be explained in detail based on examples.
The present invention is not limited to this. In addition,
The composition and composition ratio of the distillation residues of BP and OP used in the examples are as follows. Phenol 0% by weight BP 9% by weight p-tert-amylphenol 5% by weight 2,4-di-tert-butylphenol 20% by weight 2-sec-4-tert-butylphenol 12% by weight o-octylphenol 9% by weight OP 34% by weight Others 11% by weight Example 1 250g of paraformaldehyde in 1000g of distillation residue
and 5 g of hydrochloric acid were added, and the mixture was reacted at 100° C. for 3 hours.
Further, the temperature was raised and the reaction was carried out at 150 to 170°C for 2 hours to obtain a resin with a softening point (ball method) of 94°C and a hue (US rosin hue standard meter) of F. This resin is hereinafter referred to as rubber compound A. Example 2 180g of paraformaldehyde to 1000g of distillation residue
and 5 g of calcium hydroxide were added, and the mixture was reacted at 100° C. for 5 hours. After that, neutralize with hydrochloric acid to make the pH 6-7.
Calcium chloride was removed by washing with water, and the
The reaction was carried out at ~170°C for 3 hours to obtain a resin with a softening point of 81°C and a hue of F. This resin is hereinafter referred to as rubber compound B. Application example 1 Next, rubber compounding agents A and B, Hytanol 1501 manufactured by Hitachi Chemical Co., Ltd. Product name: Rubber compounding agent C below
) and Escorets 1202U (trade name of aliphatic petroleum resin manufactured by Etsuso Standard Co., Ltd.; hereafter referred to as rubber compounding agent D) were used as rubber compounding agents to prepare the following rubber composition, and then mixed with a Banbury mixer.
After mixing at 100°C, vulcanization was performed at 150°C for 30 minutes. Table 1 shows the physical properties of the obtained rubber. Composition of the rubber composition Styrene-butadiene rubber (JSR #1502 manufactured by Japan Synthetic Rubber Co., Ltd., trade name) 100% by weight Carbon black 50% by weight Process oil 10% by weight Stearic acid 3% by weight Zinc white 5% by weight Nokuratsu 224 ( Manufactured by Ouchi Shinko Kagaku Co., Ltd. (product name)
1% by weight Sulfur 2% by weight Noxeler CZ (manufactured by Ouchi Shinko Chemical Co., Ltd., trade name)
1% by weight Rubber compounding agent 4% by weight
【表】
なお、タツキネスはピクマタツクテスター（東
洋精機(株)）を用いて測定した。引張応力、引張強
及びさ伸びはJIS−Ｋ−6301に準じて測定した。
前記の表から明らかなとおり、本発明によるゴ
ム配合剤Ａ及びＢを配合したゴムは、脂肪族系石
油樹脂（ゴム配合剤Ｄ）を配合した場合より、タ
ツキネス、引張応力、引張強さ及び伸びのいずれ
においても優れている。一方、ゴム配合剤Ｃ（OP
ホルムアルデヒド樹脂）と比較すると、ゴム配合
剤Ａ及びＢは、タツキネスは若干劣るが、その他
の特性がほとんど同等のゴム物性を有し、引張応
力において若干優れているゴムを生じる。
本発明により、パラ−tert−ブチルフエノール
又はパラ−tert−オクチルフエノールの蒸溜残渣
を有効活用できるだけでなく、ゴム配合剤として
新規でしかも優れた効果を示すものが提供でき
る。[Table] Tatsukiness was measured using a Pikma Tatsuku Tester (Toyo Seiki Co., Ltd.). Tensile stress, tensile strength and elongation were measured according to JIS-K-6301. As is clear from the above table, the rubber compounded with the rubber compounding agents A and B according to the present invention has better tackiness, tensile stress, tensile strength, and elongation than the rubber compounded with the aliphatic petroleum resin (rubber compounding agent D). It is excellent in both. On the other hand, rubber compound C (OP
In comparison with formaldehyde resins), rubber compounding agents A and B produce rubbers that are slightly inferior in tackiness, but have almost the same rubber physical properties in other properties and are slightly superior in tensile stress. The present invention not only makes it possible to effectively utilize the distillation residue of para-tert-butylphenol or para-tert-octylphenol, but also provides a new and excellent rubber compounding agent.
Claims (1)
媒の存在下に反応させてパラ−tert−ブチルフエ
ノール又はパラ−tert−オクチルフエノールを製
造し、精製する際に得られる蒸溜残渣をアルデヒ
ド類と反応させることを特徴とするゴム配合剤の
製造法。1. A process characterized by reacting isobutylene oligomer and phenol in the presence of a catalyst to produce para-tert-butylphenol or para-tert-octylphenol, and reacting the distillation residue obtained during purification with aldehydes. A method for producing a rubber compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11644083A JPS608343A (en) | 1983-06-28 | 1983-06-28 | Production of compounding ingredient for rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11644083A JPS608343A (en) | 1983-06-28 | 1983-06-28 | Production of compounding ingredient for rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS608343A JPS608343A (en) | 1985-01-17 |
| JPH0345743B2 true JPH0345743B2 (en) | 1991-07-12 |
Family
ID=14687156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11644083A Granted JPS608343A (en) | 1983-06-28 | 1983-06-28 | Production of compounding ingredient for rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS608343A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100692292B1 (en) * | 2005-09-06 | 2007-03-09 | 금호타이어 주식회사 | Rim flange rubber composition for tire with white sidewall |
| JP2016169690A (en) * | 2015-03-13 | 2016-09-23 | ヤンマー株式会社 | Fuel injection pump |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4927541A (en) * | 1972-07-11 | 1974-03-12 | ||
| JPS57151633A (en) * | 1975-01-28 | 1982-09-18 | Schenectady Chemical | Adhesion imparting agent-elastomer composition |
-
1983
- 1983-06-28 JP JP11644083A patent/JPS608343A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4927541A (en) * | 1972-07-11 | 1974-03-12 | ||
| JPS57151633A (en) * | 1975-01-28 | 1982-09-18 | Schenectady Chemical | Adhesion imparting agent-elastomer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS608343A (en) | 1985-01-17 |
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