JPH0113493B2 - - Google Patents
Info
- Publication number
- JPH0113493B2 JPH0113493B2 JP16966581A JP16966581A JPH0113493B2 JP H0113493 B2 JPH0113493 B2 JP H0113493B2 JP 16966581 A JP16966581 A JP 16966581A JP 16966581 A JP16966581 A JP 16966581A JP H0113493 B2 JPH0113493 B2 JP H0113493B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- synthetic rubber
- general formula
- solution
- thermal
- 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
Links
- 229920003051 synthetic elastomer Polymers 0.000 claims description 15
- 239000005061 synthetic rubber Substances 0.000 claims description 15
- 150000002989 phenols Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 229920001971 elastomer Polymers 0.000 description 18
- 239000005060 rubber Substances 0.000 description 18
- 239000003963 antioxidant agent Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 2
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 2
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- AFTXVIIXNFSATO-UHFFFAOYSA-N 3-(3-chloro-3-oxopropyl)sulfanylpropanoyl chloride Chemical compound ClC(=O)CCSCCC(Cl)=O AFTXVIIXNFSATO-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 phenol compound Chemical class 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は熱および酸化に対してきわめて優れた
安定性を持つ合成ゴム組成物に関する。
合成ゴムは製造、貯蔵、加工または使用時など
において熱および酸素の作用により劣化し、変
色、軟化、ゲル化、ムーニー粘度の変化あるいは
発臭などの現象を伴つてその物性が著しく低下す
ることはよく知られている。
このような現象を防止する目的で、従来より各
種のフエノール系、リン系、イオウ系などの酸化
防止剤が単独であるいは併用して合成ゴムの製
造、加工工程中に添加され使用されている。
例えばスチレン化フエノール、２，６ジ−ｔ−
ブチル−４−メチルフエノール、ｎ−オクタデシ
ル−β−（３，５−ジ−ｔ−ブチル−４−ヒドロ
キシフエニル）プロピオネート、ペンタエリスリ
トール−テトラキス〔β−（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシフエニル）プロピオネー
ト〕などのフエノール系酸化防止剤を単独で用い
たり、これらのフエノール系酸化防止剤とトリス
（ノニルフエニル）ホスフアイト、ジステアリル
ペンタエリスリトールジホスフアイトなどのリン
系酸化防止剤とを併用したり、あるいは前記のフ
エノール系酸化防止剤とジラウリルチオジプロピ
オネート、ジステアリルチオジプロピオネートな
どのイオウ系酸化防止剤とを併用する方法などが
知られている。しかし、これらの方法は熱および
酸化安定性、耐熱変色性および蒸散性などの点で
まだ充分満足すべきものではない。
本発明者らはこれらの点に解決を与えるべく
種々検討の結果、特定のフエノール系化合物を合
成ゴムに配合することにより、従来技術よりきわ
めて優れた熱および酸化安定性を有し、かつ耐熱
変色性に著しく優れることを見い出し、本発明に
至つた。
すなわち本発明は、一般式（）
Ａ〔−Ｓ（−CH2）−o〕−nＳ−Ａ （）
（式中、ｎは２〜９の整数を表わし、ｍは０また
は１である。Ａは
を表わす。ここでＲは炭素数１〜４のアルキル基
を表わす。）
で示されるフエノール系化合物を合成ゴムに配合
してなる安定化された合成ゴム組成物を提供する
ものである。
本発明に用いられる上記一般式（）化合物に
おいて、Ｒは炭素数１〜４のアルキル基を表わす
が、酸化防止剤としての性能上メチル基とエチル
基が好ましく、特にメチル基が好ましい。また、
ｎは２〜９の整数を表わすが、酸化防止剤として
の性能上３〜６が好ましい。
本発明で用いる一般式（）で示されるフエノ
ール系化合物の代表例を表−１に示す。
The present invention relates to synthetic rubber compositions having excellent thermal and oxidative stability. Synthetic rubber deteriorates due to the action of heat and oxygen during manufacturing, storage, processing, or use, and its physical properties may deteriorate significantly with phenomena such as discoloration, softening, gelation, changes in Mooney viscosity, or odor. well known. In order to prevent such a phenomenon, various phenol-based, phosphorus-based, sulfur-based, and other antioxidants have been added singly or in combination during the manufacturing and processing steps of synthetic rubber. For example, styrenated phenol, 2,6 di-t-
Butyl-4-methylphenol, n-octadecyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol-tetrakis [β-(3,5-di-t-butyl- [4-Hydroxyphenyl)propionate] may be used alone, or these phenolic antioxidants may be combined with phosphorus antioxidants such as tris(nonylphenyl)phosphite or distearylpentaerythritol diphosphite. Methods are known in which the above-mentioned phenolic antioxidants and sulfur antioxidants such as dilaurylthiodipropionate and distearylthiodipropionate are used in combination. However, these methods are still not fully satisfactory in terms of thermal and oxidative stability, thermal discoloration resistance, evaporation resistance, etc. As a result of various studies to solve these problems, the present inventors found that by blending a specific phenolic compound into synthetic rubber, it has extremely superior heat and oxidation stability compared to conventional technology, and is resistant to heat discoloration. The present inventors have discovered that this material has significantly superior properties, leading to the present invention. That is, the present invention is based on the general formula ()A[-S( -CH2 ) -o ] -nSA () (wherein, n represents an integer of 2 to 9, and m is 0 or 1. A is represents. Here, R represents an alkyl group having 1 to 4 carbon atoms. ) A stabilized synthetic rubber composition is provided by blending a phenolic compound represented by the following into synthetic rubber. In the compound of general formula () used in the present invention, R represents an alkyl group having 1 to 4 carbon atoms, and methyl and ethyl groups are preferred from the viewpoint of performance as an antioxidant, with methyl group being particularly preferred. Also,
n represents an integer of 2 to 9, preferably 3 to 6 in terms of performance as an antioxidant. Representative examples of the phenolic compound represented by the general formula () used in the present invention are shown in Table 1.
【表】【table】
【表】
このような一般式（）で示されるフエノール
系化合物は、たとえば一般式（）においてｍ＝
０の場合のフエノール系化合物は一般式（）
（式中、Ｒは前記と同じ意味を有する）
で示されるフエノール類と３，3′−チオジプロピ
オン酸またはその低級アルキルエステルまたはそ
の酸クロライドとを概知の方法で反応させること
により製造することができる。
また、一般式（）においてｍ＝１の場合のフ
エノール系化合物は一般式（）
（式中、Ｒは前記と同じ意味を有する）
で示されるフエノール類モノアクリレートと下記
一般式（）
HS（−CH2）−oSH （）
（式中、ｎは前記と同じ意味を有する）
で示されるジチオール類とを既知の方法で反応さ
せることにより製造することができる。
本発明の合成ゴム組成物、合成ゴムに前記一般
式（）で示されるフエノール系化合物を配合し
てなるものであるが、その配合量は合成ゴム100
量部部に対して通常0.1〜２重量部であり、好ま
しくは0.3〜1.5重量部である。
一般式（）で示されるフエノール系化合物の
合成ゴムへの添加は、通常の方法たとえば乳化液
をあらかじめ調整しこれを合成ゴムラテツクスに
添加する方法、適当な有機溶剤にあらかじめ溶解
させた上で溶液重合法合成ゴムのゴムセメントに
添加する方法などが用いられ、特に制限はない。
本発明により安定化される合成ゴムとしては、
溶液重合法ポリブタジエンゴム、溶液重合法ポリ
イソプレンゴム、溶液重合法スチレン−ブタジエ
ン共重合ゴム、エチレン−プロピレン三元共重合
ゴム、イソプレン−イソブチレン共重合ゴム、乳
化重合法スチレン−ブタジエン共重合ゴム、乳化
重合法アクリロニトリル−ブタジエン共重合ゴム
などがあり、特に溶液重合法ポリブタジエンゴ
ム、溶液重合法ポリイソプレンゴム、溶液重合法
スチレン−ブタジエン共重合ゴムなどに有効であ
る。
次に参考例および実施例を挙げて本発明を詳細
に説明するが、本発明はこれらによつて限定され
るものではない。
参考例 １
（化合物−１の合成）
300ml四口フラスコに３，3′−チオジプロピオ
ン酸4.28ｇ、トルエン50ｇおよび塩化チオニル
11.0ｇを仕込み、窒素気流中で90℃まで昇温し、
３時間保温する。反応終了後、過剰の塩化チオニ
ルおよびトルエンを減圧留去する。
生成した３，3′−チオジプロピオン酸ジクロラ
イドおよび２，2′−メチレンビス（６−ｔ−ブチ
ル−４−メチルフエノール）13.62ｇをトルエン
50ｇに溶かし、10℃に保温し、これにトリエチル
アミン4.9ｇのトルエン溶液を２時間かけて滴下
する。滴下終了後、トルエチルアミン塩酸塩をろ
過し、溶媒を減圧留去して粗生成物16.3ｇを得
る。これをシリカゲルクロマトグラフイーで精製
し、ｎ−ヘキサンから再結晶することによつて、
融点101.5〜103.0℃の白色結晶の化合物−１を
得る。
元素分析 C52H70O6S （ ）内計算値
Ｃ：75.8％（75.9）、Ｈ：8.7％（8.6）
Ｓ： 3.8％（3.9）
参考例 ２
（化合物−５の合成）
200ml四口フホスコに２，2′−メチレンビス
（６−ｔ−ブチル−４−メチルフエノール）モノ
アクリレート7.93ｇ、１，６−ヘキサンジチオー
ル1.50ｇおよびエタノール50ｇを仕込み、容器内
の空気を窒素置換する。これに28％ナトリウムメ
トキシドメタノール溶液を0.17ｇ加え、昇温して
約８時間還流下に反応させる。反応終了後、30℃
に冷却し、クロロホルム50ｇを加えたのち希塩酸
で中和し、水洗、脱水後、クロロホルムを留去す
る。残渣にｎ−ヘキサン20ｇを加え、再結晶して
融点121〜122℃の白色結晶の化合物−５を74.7
ｇ（収率80％）得る。
元素分析 C58H82O6S2 （ ）内計算値
Ｃ：74.08％（74.16）、Ｈ：8.90％（8.80）
Ｓ： 6.87％（6.83）
実施例 １
酸化防止剤を含まない溶液重合法ポリブタジエ
ンゴム（JSR BR−01から酸化防止剤をアセトン
で抽出したゴムを使用した）に供試化合物をロー
ル混練したものを供試ゴムとし、熱および酸化安
定性と耐熱変色性の試験を行なつた。
その結果を表−２に示す。
なお、熱および酸化安定性は、供試ゴムを100
℃ギヤーオーブン中で熱老化させ、15時間毎にゲ
ル分（トルエン下溶分）を測定し、ゲル分が
10wt％になるまでの時間（GelI.P.とする）で評
価した。
また、耐熱変色性は、100℃ギヤーオーブン中
で15時間、60時間および120時間熱老化後にゴム
色相で評価した。
なお、表においてAO−１〜AO−７は以下の
化合物を示すものである。
AO−１ スチレン化フエノール
AO−２ ２，６−ジ−ｔ−ブチル−４−メチル
フエノール
AO−３ ｎ−オクタデシル−β−（３，５−ジ
−ｔ−ブチル−４−ヒドロキシフエニル）プロ
ピオネート
AO−４ ピンタエリスリトール−テトラキス
〔β−（３，５−ジ−ｔ−ブチル−４−ヒドロキ
シフエニル）プロピオネート〕
AO−５ トリス（ノニルフエニル）ホスフアイ
ト
AO−６ ジステアリルペンタエリスリトールジ
ホスフアイト
AO−７ ジラウリルチオジプロピオネート[Table] The phenolic compound represented by the general formula () is, for example, m=
In the case of 0, the phenolic compound has the general formula () (wherein R has the same meaning as above) and 3,3'-thiodipropionic acid or its lower alkyl ester or its acid chloride are reacted by a known method. be able to. In addition, when m = 1 in the general formula (), the phenolic compound has the general formula () (In the formula, R has the same meaning as above) Phenol monoacrylate represented by the following general formula () HS (-CH 2 ) - o SH () (In the formula, n has the same meaning as above) It can be produced by reacting dithiols represented by the following with a known method. The synthetic rubber composition of the present invention is made by blending a phenol compound represented by the general formula () with synthetic rubber, and the amount of the compound is 100% of the synthetic rubber.
The amount is usually 0.1 to 2 parts by weight, preferably 0.3 to 1.5 parts by weight. The phenolic compound represented by the general formula () can be added to synthetic rubber using the usual methods, such as preparing an emulsion in advance and adding it to synthetic rubber latex, or dissolving it in an appropriate organic solvent in advance and adding it to the synthetic rubber. Methods such as adding legal synthetic rubber to rubber cement are used, and there are no particular restrictions. The synthetic rubber stabilized by the present invention includes:
Solution polymerized polybutadiene rubber, solution polymerized polyisoprene rubber, solution polymerized styrene-butadiene copolymer rubber, ethylene-propylene ternary copolymer rubber, isoprene-isobutylene copolymer rubber, emulsion polymerized styrene-butadiene copolymer rubber, emulsified Examples include polymerized acrylonitrile-butadiene copolymer rubber, and are particularly effective for solution-polymerized polybutadiene rubber, solution-polymerized polyisoprene rubber, and solution-polymerized styrene-butadiene copolymer rubber. Next, the present invention will be explained in detail with reference to Reference Examples and Examples, but the present invention is not limited thereto. Reference Example 1 (Synthesis of Compound-1) 4.28 g of 3,3'-thiodipropionic acid, 50 g of toluene, and thionyl chloride in a 300 ml four-necked flask.
Pour 11.0g and raise the temperature to 90℃ in a nitrogen stream.
Keep warm for 3 hours. After the reaction is completed, excess thionyl chloride and toluene are distilled off under reduced pressure. 13.62 g of the produced 3,3'-thiodipropionic acid dichloride and 2,2'-methylenebis(6-t-butyl-4-methylphenol) were added to toluene.
Dissolve the solution in 50 g, keep warm at 10°C, and add a toluene solution of 4.9 g of triethylamine dropwise over 2 hours. After the addition is complete, toluethylamine hydrochloride is filtered and the solvent is distilled off under reduced pressure to obtain 16.3 g of a crude product. By purifying this by silica gel chromatography and recrystallizing from n-hexane,
Compound-1 is obtained as white crystals with a melting point of 101.5-103.0°C. Elemental analysis C 52 H 70 O 6 S Calculated values in parentheses C: 75.8% (75.9), H: 8.7% (8.6) S: 3.8% (3.9) Reference example 2 (Synthesis of compound-5) 200ml four-necked Fufosco 7.93 g of 2,2'-methylenebis(6-t-butyl-4-methylphenol) monoacrylate, 1.50 g of 1,6-hexanedithiol and 50 g of ethanol were charged into the container, and the air in the container was replaced with nitrogen. Add 0.17 g of 28% sodium methoxide methanol solution to this, raise the temperature, and react under reflux for about 8 hours. After the reaction is completed, 30℃
After adding 50 g of chloroform, the mixture was neutralized with dilute hydrochloric acid, washed with water, dehydrated, and the chloroform was distilled off. Add 20g of n-hexane to the residue and recrystallize to obtain Compound-5 as white crystals with a melting point of 121-122°C at 74.7°C.
g (yield: 80%). Elemental analysis C 58 H 82 O 6 S 2 Calculated values in parentheses C: 74.08% (74.16), H: 8.90% (8.80) S: 6.87% (6.83) Example 1 Solution polymerized polybutadiene without antioxidant The test compound was roll-kneaded into rubber (rubber from JSR BR-01 with the antioxidant extracted with acetone) and tested for thermal and oxidative stability and thermal discoloration resistance. . The results are shown in Table-2. The thermal and oxidation stability of the sample rubber is 100%.
Heat aged in a gear oven at °C, and measured the gel content (solubilized in toluene) every 15 hours.
Evaluation was made based on the time taken to reach 10 wt% (referred to as GelI.P.). Further, heat discoloration resistance was evaluated by rubber hue after heat aging in a gear oven at 100°C for 15 hours, 60 hours, and 120 hours. In addition, in the table, AO-1 to AO-7 indicate the following compounds. AO-1 Styrenated phenol AO-2 2,6-di-t-butyl-4-methylphenol AO-3 n-octadecyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate AO-4 Pintaerythritol-tetrakis [β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] AO-5 Tris(nonylphenyl)phosphite AO-6 Distearylpentaerythritol diphosphite AO-7 Dilaurylthiodipropionate
【表】【table】
【表】【table】
【表】
実施例 ２
酸化防止剤を含まない溶液重合法ポリイソプレ
ンゴム（JSR IR−2200から酸化防止剤をアセト
ンで抽出したゴムを使用した）の５％トルエン溶
液に供試化合物を添加し、撹拌して均一溶液とし
た後トルエンを除去したものを供試ゴムとし、熱
および酸化安定性と耐熱変色性の試験を行なつ
た。
その結果を表−３に示す。
なお熱および酸化安定性は、供試ゴムを70℃ギ
ヤーオーブン中で７日間熱老化させた後ウオーレ
ス・ラピツド・プラスチメーターより可塑度を測
定し、下記式により可塑度保持率（PRI）を求め
て評価した。
PRI（％）＝熱老化後の可塑度／熱老化前の可塑度×1
00
また、耐熱変色性は、70℃ギヤーオーブン中で
７日間熱老化後のゴム色相で評価した。[Table] Example 2 A test compound was added to a 5% toluene solution of solution polymerized polyisoprene rubber containing no antioxidant (rubber from JSR IR-2200 with the antioxidant extracted with acetone). After stirring to make a homogeneous solution, toluene was removed, and test rubber was used to test thermal and oxidative stability and thermal discoloration resistance. The results are shown in Table-3. The thermal and oxidative stability was determined by heat aging the sample rubber in a gear oven at 70°C for 7 days, measuring the plasticity using a Wallace Rapid Plastimeter, and calculating the plasticity retention rate (PRI) using the following formula. It was evaluated. PRI (%) = Plasticity after heat aging / Plasticity before heat aging x 1
00 Heat discoloration resistance was evaluated by the rubber hue after heat aging for 7 days in a gear oven at 70°C.
【表】【table】
Claims (1)
系化合物を配合してなることを特徴とする安定化
された合成ゴム組成物。 Ａ〔−Ｓ（−CH2）−o〕−nＳ−Ａ （式中、ｎは２〜９の整数を表わし、ｍは０また
は１である。Ａは を表わす。ここでＲは炭素数１〜４のアルキル基
を表わす。）[Scope of Claims] 1. A stabilized synthetic rubber composition characterized by blending a phenolic compound represented by the following general formula into synthetic rubber. A[-S( -CH2 ) -o ] -n S-A (wherein, n represents an integer from 2 to 9, and m is 0 or 1. A is represents. Here, R represents an alkyl group having 1 to 4 carbon atoms. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16966581A JPS5871934A (en) | 1981-10-22 | 1981-10-22 | Stabilized synthetic rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16966581A JPS5871934A (en) | 1981-10-22 | 1981-10-22 | Stabilized synthetic rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5871934A JPS5871934A (en) | 1983-04-28 |
| JPH0113493B2 true JPH0113493B2 (en) | 1989-03-07 |
Family
ID=15890651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16966581A Granted JPS5871934A (en) | 1981-10-22 | 1981-10-22 | Stabilized synthetic rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5871934A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60156326A (en) * | 1984-12-05 | 1985-08-16 | 株式会社 四国製作所 | Running type roll baler |
| JPS60156327A (en) * | 1984-12-05 | 1985-08-16 | 株式会社 四国製作所 | Self-running type roll baler |
-
1981
- 1981-10-22 JP JP16966581A patent/JPS5871934A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5871934A (en) | 1983-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6346774B2 (en) | ||
| JPS6218445A (en) | Butadiene polymer composition | |
| AU655543B2 (en) | Polysiloxanic stabilizers containing sterically hindered phenol groups and oxamidic groups | |
| JPS5971341A (en) | Stabilizer for synthetic resin | |
| JPS6411222B2 (en) | ||
| JPH03177442A (en) | Stabilizer mixture for elastomer | |
| US4035559A (en) | Novel aromatic polyvinyl compounds | |
| JPH0113493B2 (en) | ||
| US7553897B2 (en) | Organic thiol stabilizers and plasticizers for halogen-containing polymers | |
| US4362887A (en) | Synergistic antioxidant mixtures | |
| US4370434A (en) | Mercapto acid ester antioxidants for polymers | |
| US3357946A (en) | Polymeric olefin compositions stabilized with a thiodialkanoic acid ester and a trihydroxyaryl hydrocarbon | |
| JPS58149932A (en) | Stabilized synthetic rubber composition | |
| JPS58120651A (en) | Stabilized synthetic rubber composition | |
| JPH032184B2 (en) | ||
| JPH032897B2 (en) | ||
| JPS5889634A (en) | Stabilized synthetic rubber composition | |
| JPS58132034A (en) | Stabilized synthetic rubber composition | |
| JPH0234977B2 (en) | ||
| JPH0124418B2 (en) | ||
| JPS58120652A (en) | Stabilized synthetic rubber composition | |
| JPH0660156B2 (en) | Phenolic compound and method for producing the same | |
| SU840065A1 (en) | Rubber mixture based on butadienenitrile rubber | |
| JPH0347268B2 (en) | ||
| JPS5891741A (en) | Stabilized synthetic rubber composition |