JPS6155107A - Production of olefin/diene copolymer - Google Patents
Production of olefin/diene copolymerInfo
- Publication number
- JPS6155107A JPS6155107A JP17671784A JP17671784A JPS6155107A JP S6155107 A JPS6155107 A JP S6155107A JP 17671784 A JP17671784 A JP 17671784A JP 17671784 A JP17671784 A JP 17671784A JP S6155107 A JPS6155107 A JP S6155107A
- Authority
- JP
- Japan
- Prior art keywords
- olefin
- butadiene
- diene compound
- fraction obtained
- diene
- 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.)
- Granted
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920001577 copolymer Polymers 0.000 title abstract description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 diene compound Chemical class 0.000 claims abstract description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000003208 petroleum Substances 0.000 claims abstract description 3
- KOYGZROXUOTUEE-UHFFFAOYSA-N butane;but-1-ene Chemical compound CCCC.CCC=C KOYGZROXUOTUEE-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001273 butane Substances 0.000 abstract 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 238000004227 thermal cracking Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、オレフィン−ジエン共重合体の製造方法に関
し、詳しくは特定の温度範囲で収率良く、不飽和度の低
いオレフィン−ジエン共重合体の効率良い製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an olefin-diene copolymer, and more particularly, to an efficient method for producing an olefin-diene copolymer with a high yield and a low degree of unsaturation within a specific temperature range. .
従来、イソブチレンなどのオレフィンとブタジェンなど
のジエン化合物とをフリーデルクラフト型触媒の存在下
に共重合してオレフィン−ジエン共重合体を製造するこ
とが知られている。ところが、従来の方法においてはゲ
ル状重合体の生成を抑制するため、重合温度は一り５℃
〜室温程度という低温度に抑え、かつ多量のジエンを使
用していた。したがって、オレフィンの転化率が低く、
しかも不飽和度も比較的高いものであった。Conventionally, it has been known to copolymerize an olefin such as isobutylene and a diene compound such as butadiene in the presence of a Friedel-Crafts type catalyst to produce an olefin-diene copolymer. However, in conventional methods, the polymerization temperature is lowered to 5°C to suppress the formation of gel-like polymers.
The temperature was kept low, around room temperature, and a large amount of diene was used. Therefore, the olefin conversion rate is low,
Moreover, the degree of unsaturation was also relatively high.
そこで、本発明者は、これらの問題点を解消した製造方
法を開発すべく鋭意研究した結果、特定の配合量、かつ
特定の温度範囲で共重合を行なうと目的が達成されるこ
とを見い出し、この知見に基づいて本発明を完成した。Therefore, as a result of intensive research to develop a production method that eliminates these problems, the present inventor discovered that the purpose could be achieved by carrying out copolymerization in a specific amount and within a specific temperature range. The present invention was completed based on this knowledge.
すなわち本発明は、オレフィン１００重量部あたりジエ
ン系化合物を５〜４０重量部の割合で加え、フリーデル
タラット型触媒の存在下、３０〜１５０℃の温度で共重
合させることを特徴とするオレフィン−ジエン共重合体
の製造方法を提供するものである。That is, the present invention provides an olefin, which is characterized in that a diene compound is added at a ratio of 5 to 40 parts by weight per 100 parts by weight of olefin, and copolymerized at a temperature of 30 to 150°C in the presence of a Friedelta-Rat type catalyst. A method for producing a diene copolymer is provided.
本発明の原料であるオレフィンとしては、種々のものが
使用される。具体的には、エチレン、プロピレン、ブテ
ンなどが挙げられる。特に石油の熱分解によって得られ
る炭素数４の留分からブタジェンを除いたイソブチレン
を主成分とするブタン−ブテン留分が好適である。なお
、原料のオレフィンは、ブタジェンを含むブタン−ブテ
ン留分て希釈し、濃度を調節して用いても良い。Various kinds of olefins can be used as the raw material of the present invention. Specific examples include ethylene, propylene, and butene. Particularly suitable is a butane-butene fraction whose main component is isobutylene obtained by removing butadiene from a C4 fraction obtained by thermal decomposition of petroleum. Note that the raw material olefin may be diluted with a butane-butene fraction containing butadiene, and the concentration may be adjusted before use.
また、ジエン系化合物としては特に制限はなく、ブタジ
ェン、イソプレン、クロロブレン等が使用できる。Further, the diene compound is not particularly limited, and butadiene, isoprene, chlorobrene, etc. can be used.
オレフィンとジエン系化合物との使用量については、特
に制限はないが、一般的にはオレフィン１００重量部に
対してジエン系化合物を５〜４０重量部、好ましくは１
０〜３０重量部である。ジエン系化合物の使用量が５重
量部以下であると、共重合体としての特ｊ生が不充分で
あり、４０重量部を超えると、共重合反応においてゲル
状物質が多量に生成するため好ましくない。There is no particular restriction on the amount of the olefin and diene compound used, but generally the diene compound is used in an amount of 5 to 40 parts by weight, preferably 1 part by weight, per 100 parts by weight of the olefin.
The amount is 0 to 30 parts by weight. If the amount of the diene compound used is less than 5 parts by weight, the properties of the copolymer will be insufficient, and if it exceeds 40 parts by weight, a large amount of gel-like material will be produced in the copolymerization reaction, so it is not preferable. do not have.
本発明に用いられるフリーデルクラフト型触媒としては
通常使用されるものであれば良く、特に制限はない。具
体的には塩化アルミニウム１塩化鉄、塩化スズ、塩化チ
タン、塩化亜鉛等があげられ、特に塩化アルミニウムが
好ましい。使用量は通常オレフィンに対して０．２〜１
．０モル％、好ま°シ＜は０．５〜０．６モル％である
。The Friedel-Crafts type catalyst used in the present invention is not particularly limited as long as it is commonly used. Specific examples include aluminum chloride, iron chloride, tin chloride, titanium chloride, and zinc chloride, with aluminum chloride being particularly preferred. The amount used is usually 0.2 to 1 per olefin.
．． 0 mol%, preferably 0.5 to 0.6 mol%.
本発明の共重合体の製造方法においては、無溶媒であっ
ても反応は進行するが、溶媒を用いることが好ましい。In the method for producing a copolymer of the present invention, the reaction proceeds even without a solvent, but it is preferable to use a solvent.
溶媒としては飽和脂肪族炭化水素、例えばペンタン、ヘ
キサン、ヘプタンなどが使用できる。As the solvent, saturated aliphatic hydrocarbons such as pentane, hexane, heptane, etc. can be used.
本発明は上記の如き原料を触媒存在下で溶媒を用いであ
るいは無溶媒下で共重合させる。In the present invention, the above raw materials are copolymerized in the presence of a catalyst using a solvent or without a solvent.
共重合反応は反応温度３０〜１５０℃、好ましくは５０
〜１１０℃で行なう。この温度範囲において共重合反応
を行なうことにより高い転化率で低不飽和度のオレフィ
ン−ジエン共重合体が得られるのである。The copolymerization reaction is carried out at a reaction temperature of 30 to 150°C, preferably 50°C.
Perform at ~110°C. By carrying out the copolymerization reaction in this temperature range, an olefin-diene copolymer with a high conversion rate and a low degree of unsaturation can be obtained.
他の反応条件は特に制限はなく、オレフィン。There are no particular restrictions on other reaction conditions, including olefin.
ジエン系化合物等の種類により適宜定めれば良い。It may be determined as appropriate depending on the type of diene compound, etc.
通常、反応圧力は１．０〜３０．０ｋｇ／ａｍ” 、好
ましくは５〜２５ ｋｇ ／ ａｍ ” 、反応時間５
〜１２０分間、好ましくは２０〜６０分間である。Usually, the reaction pressure is 1.0 to 30.0 kg/am", preferably 5 to 25 kg/am", and the reaction time is 5.
-120 minutes, preferably 20-60 minutes.
反応終了後、触媒や未反応原料等の除去などの必要少後
処理を行ない、目的とするオレフィン−ジエン共重合体
を得る。After the reaction is completed, necessary post-treatments such as removal of the catalyst and unreacted raw materials are carried out to obtain the desired olefin-diene copolymer.
本発明の方法では高い転化率でオレフィン−ジエン共重
合体が得られ、従来法で得られたものよりも不飽和度が
低く、樹脂あるいはゴム等の粘着付与剤、軟化剤などの
添加剤として好適に使用することができる。The method of the present invention yields an olefin-diene copolymer with a high conversion rate, has a lower degree of unsaturation than those obtained by conventional methods, and can be used as an additive for tackifiers, softeners, etc. for resins or rubbers. It can be suitably used.
したがって、本発明はオレフィン−ジエン共重合体の製
造方法として極めて実用性の高いものである。Therefore, the present invention is extremely practical as a method for producing an olefin-diene copolymer.
次に、本発明を実施例により詳しく説明する。Next, the present invention will be explained in detail with reference to examples.
実施例１
温度計、攪拌機、原料入口および触媒注入口を有するオ
ートクレーブを乾燥窒素で置換後、真空ポンプで減圧と
した。次いで、この中にブタン−ブテン留分１００ｇお
よびブタジェン１２ｇを仕込んだ。攪拌を行ないながら
分子量５００のポリブテン３０ＩＩＩｌに分散させた塩
化アルミニウム１．ＯＯｇを１０分間かけて滴下し、７
０℃で６０分間反応を行なった。Example 1 An autoclave having a thermometer, a stirrer, a raw material inlet, and a catalyst inlet was purged with dry nitrogen, and then the pressure was reduced using a vacuum pump. Next, 100 g of a butane-butene fraction and 12 g of butadiene were charged into this. 1. Aluminum chloride dispersed in 30IIIl of polybutene having a molecular weight of 500 while stirring. Drop OOg over 10 minutes,
The reaction was carried out at 0°C for 60 minutes.
反応終了後、内容物を水で洗浄し、続いて、５％水酸化
ナトリウム水溶液で洗浄して塩化アルミニウムを完全に
分解除去後、得られた油層に無水硫酸ナトリウム１０ｇ
を加えて２４時間乾燥を行なった。その後、軽質分を２
０ｍｍＨｇ、１００℃で蒸留除去して液状共重合体６２
．０ｇを得た。このものの収量。After the reaction is complete, the contents are washed with water and then with a 5% aqueous sodium hydroxide solution to completely decompose and remove aluminum chloride, and 10 g of anhydrous sodium sulfate is added to the resulting oil layer.
was added and dried for 24 hours. After that, add 2 portions of light ingredients.
Distilled at 0 mmHg and 100°C to obtain liquid copolymer 62.
．． Obtained 0g. Yield of this stuff.
転化率、平均分子量および臭素価を第１表に示す。The conversion rate, average molecular weight and bromine number are shown in Table 1.
なお、使用したブタン−ブテン留分の組成は次の通りで
ある。The composition of the butane-butene fraction used is as follows.
イソブタン ５．２ 重量％ノルマルブタン
１８．８ 重量％１−ブテン １７．３
重量％イソブチン ４２．９ 重量％ｔｒａ
ｓ−２−ブテン ９．８ 重量％ｃｉｓ −２−ブ
テン ５．６ 重量％比較例１
実施例１において、反応温度を０℃としたことおよびブ
タジェンの使用量を４５ｇとしたこと以外は実施例１と
同様にして共重合体７５．８ ｇを得た。Isobutane 5.2 wt% normal butane 18.8 wt% 1-butene 17.3
Weight% Isobutyne 42.9 Weight%tra
s-2-Butene 9.8 wt% Cis-2-butene 5.6 wt% Comparative Example 1 Example 1 except that the reaction temperature was 0°C and the amount of butadiene used was 45 g. 75.8 g of copolymer was obtained in the same manner as in Example 1.
結果を第１表に示す。The results are shown in Table 1.
実施例２
実施例１と同様のオートクレーブを乾燥窒素で置換後、
真空ポンプで減圧した。次いで、この中にブタン−ブテ
ン留分（実施例１と同じ）２４０ｇおよびイソプレン２
８．８ｇを仕込んだ。攪拌しなから、分子量５００のポ
リブテン３０ｍＡに分散させた塩化アルミニウム１．０
０ｇを１０分かけて滴下し、次いで１００℃で６０分間
反応を行なった。その後、実施例１と同様に処理して液
状共重合体６０．１ｇを得。Example 2 After replacing the same autoclave as in Example 1 with dry nitrogen,
The pressure was reduced using a vacuum pump. Next, 240 g of butane-butene fraction (same as in Example 1) and 2
8.8g was charged. Without stirring, 1.0 mA of aluminum chloride dispersed in 30 mA of polybutene having a molecular weight of 500.
0 g was added dropwise over 10 minutes, and the reaction was then carried out at 100° C. for 60 minutes. Thereafter, it was treated in the same manner as in Example 1 to obtain 60.1 g of a liquid copolymer.
た。このものの収量、転化率、平均分子量および臭素価
を第２表に示す。Ta. The yield, conversion rate, average molecular weight and bromine number of this product are shown in Table 2.
比較例２
ぐ
実施例２において、反応温度を０℃としたことおよびイ
ソプレンの使用量を４５．０ ｇとしたこと以外は実施
例２と同様にして共重合体６９．０ ｇ得た。Comparative Example 2 69.0 g of a copolymer was obtained in the same manner as in Example 2, except that the reaction temperature was 0° C. and the amount of isoprene used was 45.0 g.
結果を第１表に示す。The results are shown in Table 1.
第１表 第２表 手続補正書（自発） 昭和５９年１０月１日Table 1 Table 2 Procedural amendment (voluntary) October 1, 1980
Claims (3)
５〜４０重量部の割合で加え、フリーデルクラフト型触
媒の存在下、３０〜１５０℃の温度で共重合させること
を特徴とするオレフィン−ジエン共重合体の製造方法。(1) Olefin-diene copolymerization characterized by adding a diene compound at a ratio of 5 to 40 parts by weight per 100 parts by weight of olefin and copolymerizing at a temperature of 30 to 150°C in the presence of a Friedel-Crafts type catalyst. Method for producing polymers.
素数４の留分からブタジエンを除いたブタン−ブテン留
分である特許請求の範囲第１項記載の方法。(2) The method according to claim 1, wherein the olefin is a butane-butene fraction obtained by removing butadiene from a C4 fraction obtained by thermal decomposition of petroleum.
ロロプレンのいずれかである特許請求の範囲第１項記載
の方法。(3) The method according to claim 1, wherein the diene compound is any one of butadiene, isoprene, and chloroprene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17671784A JPS6155107A (en) | 1984-08-27 | 1984-08-27 | Production of olefin/diene copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17671784A JPS6155107A (en) | 1984-08-27 | 1984-08-27 | Production of olefin/diene copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6155107A true JPS6155107A (en) | 1986-03-19 |
| JPH0372092B2 JPH0372092B2 (en) | 1991-11-15 |
Family
ID=16018532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17671784A Granted JPS6155107A (en) | 1984-08-27 | 1984-08-27 | Production of olefin/diene copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6155107A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4926705A (en) * | 1972-07-07 | 1974-03-09 | ||
| JPS51127191A (en) * | 1976-03-24 | 1976-11-05 | Ici Ltd | Process for producing synthetic resin |
-
1984
- 1984-08-27 JP JP17671784A patent/JPS6155107A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4926705A (en) * | 1972-07-07 | 1974-03-09 | ||
| JPS51127191A (en) * | 1976-03-24 | 1976-11-05 | Ici Ltd | Process for producing synthetic resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0372092B2 (en) | 1991-11-15 |
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