JPH083208A - Molecular weight modifier - Google Patents

Molecular weight modifier

Info

Publication number
JPH083208A
JPH083208A JP13753794A JP13753794A JPH083208A JP H083208 A JPH083208 A JP H083208A JP 13753794 A JP13753794 A JP 13753794A JP 13753794 A JP13753794 A JP 13753794A JP H083208 A JPH083208 A JP H083208A
Authority
JP
Japan
Prior art keywords
molecular weight
diphenylethylene
weight
parts
mol
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.)
Withdrawn
Application number
JP13753794A
Other languages
Japanese (ja)
Inventor
Isao Tanaka
功 田中
Kiwamu Tokuhisa
極 徳久
Takeharu Yushima
武晴 油嶋
Yuichi Tokuda
裕一 徳田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Nippon Steel Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Steel Chemical Co Ltd filed Critical Nippon Steel Chemical Co Ltd
Priority to JP13753794A priority Critical patent/JPH083208A/en
Publication of JPH083208A publication Critical patent/JPH083208A/en
Withdrawn legal-status Critical Current

Links

Abstract

PURPOSE:To obtain a mol.wt. modifier which is excellent in mol.-wt.-modifying function, hardly remains in a resin, neither leaves behind any odor or degrades the hue of a resin, and thus gives a resin with a good hue and an excellent clarity by using 1,1-diphenylethylene as the main component. CONSTITUTION:A mol.wt. modifier for free-radical polymn. mainly comprising 1,1-diphenylethylene. The diphenylethylene is usually diluted with an org. solvent before being used and has a mol.wt. of 180.2, a b.p. of 277 deg.C, and an m.p. of 8 deg.C. Since it is liq. at normal temp. and precipitates when the ambient temp. is 8 deg.C or lower, its addition to a polymn. system becomes unstable and its dilution with an org. solvent to about 50wt.% concn. before the use is pref. It may be diluted with a polymerizable monomer. It is contaminated with impurities such as 1,1-diphenylethane in the production step. The content of the impurities is pref. 20wt.% or lower, still pref. 10wt.% or lower.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明はラジカル重合における分
子量調節剤に関する。詳しくは芳香族系ビニル単量体、
メタクリレート類、アクリレート類等の重合単量体を単
独又は共重合させる際の新規な分子量調節剤に関する。
FIELD OF THE INVENTION The present invention relates to a molecular weight regulator in radical polymerization. Specifically, aromatic vinyl monomers,
The present invention relates to a novel molecular weight modifier for homopolymerization or copolymerization of polymerized monomers such as methacrylates and acrylates.

【0002】[0002]

【従来の技術】近年、スチレン、α−メチルスチレン、
p−メチルスチレン等の芳香族系ビニル単量体、アクリ
ロニトリル、メタクリロニトリル等のシアン化ビニル系
単量体、(メタ)アクリル酸エステル類(メチルメタク
リレート、メチルアクリレート、エチルメタクリレー
ト、エチルアクリレート、ブチルメタクリレート、ブチ
ルアクリレート等)、マレイン酸エステル類、イタコン
酸およびイタコン酸エステル類、N−アルキルマレイミ
ド類、フェニルマレイミド(PMI)類、熱可塑性エラ
ストマー等の重合単量体を塊状重合、溶液重合、懸濁重
合等により連続又はバッチプロセスにて単独重合又は共
重合させ、ホモポリマー、コポリマーを製造している。
これらポリマーは、単独で又はゴム、熱可塑性エラスト
マー等とアロイ化して雑貨、家電、弱電、包装材料、自
動車用等多岐の用途に渡って利用されている。
2. Description of the Related Art Recently, styrene, α-methylstyrene,
Aromatic vinyl monomers such as p-methylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and (meth) acrylic acid esters (methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl) (Methacrylate, butyl acrylate, etc.), maleic acid esters, itaconic acid and itaconic acid esters, N-alkylmaleimides, phenylmaleimide (PMI), thermoplastic elastomers, and other polymerized monomers are subjected to bulk polymerization, solution polymerization, and suspension polymerization. Homopolymers or copolymers are produced by homopolymerization or copolymerization by continuous or batch processes such as turbid polymerization.
These polymers are used alone or in alloys with rubber, thermoplastic elastomers, etc., for various purposes such as sundries, home appliances, weak electricity, packaging materials, and automobiles.

【0003】これらポリマーの分子量を調節する目的
で、t−ドデシルメルカプタン(TDM)、n−ドデシ
ルメルカプタン(NDM)、n−オクチルメルカプタン
(NOM)等のメルカプタン系、α−メチルスチレンダ
イマー(MSD)、ターピノーレン等のモノテルペノイ
ド系等の分子量調節剤を重合系に適量、通常重合単量体
総量の0.05〜1.0重量部添加することが行なれて
いることは周知である。
In order to control the molecular weight of these polymers, mercaptans such as t-dodecyl mercaptan (TDM), n-dodecyl mercaptan (NDM) and n-octyl mercaptan (NOM), α-methylstyrene dimer (MSD), It is well known that a proper amount of a molecular weight regulator such as a monoterpenoid system such as terpinolene can be added to a polymerization system, usually 0.05 to 1.0 part by weight based on the total amount of polymerized monomers.

【0004】しかし、これらの分子量調節剤は数々の欠
点を有している。例えば、t−ドデシルメルカプタン
(TDM)、n−ドデシルメルカプタン(NDM)、n
−オクチルメルカプタン(NOM)等のメルカプタン系
分子量調節剤は製品ポリマー中に微量ながら残存し、製
品にメルカプト基(−SH)特有の腐敗臭をもたらす。
特に製品ポリマーとゴム、熱可塑性エラストマー等とを
アロイ化した場合は顕著である。
However, these molecular weight regulators have a number of drawbacks. For example, t-dodecyl mercaptan (TDM), n-dodecyl mercaptan (NDM), n
-A mercaptan-based molecular weight regulator such as octyl mercaptan (NOM) remains in the product polymer in a small amount, but brings a rotten odor specific to the mercapto group (-SH) to the product.
This is particularly noticeable when the product polymer is alloyed with rubber, thermoplastic elastomer or the like.

【0005】α−メチルスチレンダイマー(MSD)
は、プロセスによって分子量分布が拡がり、強度的に不
足したポリマーとなることがある。また、蒸気圧が低い
ために製品中に残存しやすいという欠点をもっている。
Α-Methylstyrene dimer (MSD)
May have a molecular weight distribution broadened by the process, resulting in a polymer lacking in strength. Further, it has a drawback that it is likely to remain in the product because of its low vapor pressure.

【0006】ターピノーレン等のモノテルペノイド系分
子量調節剤は、松やに等の天然原料から分離精製して得
られるものであるために、不純物が多く、製品の色相悪
化(黄色劣化)の原因になるために、あまり量産化のプ
ロセスには、使用されていないのが現状である。
Since the monoterpenoid type molecular weight regulator such as terpinolene is obtained by separating and purifying from natural raw materials such as pine and sea urchin, it contains many impurities and causes deterioration of hue (yellow deterioration) of the product. However, it is currently not used in mass production processes.

【0007】[0007]

【発明が解決しようとする課題】本発明の目的は、芳香
族系ビニル単量体、シアン化ビニル系単量体、(メタ)
アクリル酸エステル単量体等の重合において、分子量調
節能に優れると共に、製品中に残存し難く、後に臭気を
残したり、色相悪化の原因とならない新規な分子量調節
剤を提供することである。
The object of the present invention is to produce aromatic vinyl monomers, vinyl cyanide monomers, (meth).
It is an object of the present invention to provide a novel molecular weight regulator which is excellent in the ability to control the molecular weight in the polymerization of acrylic acid ester monomers and the like, is hard to remain in the product, and does not leave an odor or cause deterioration of hue.

【0008】[0008]

【課題を解決するための手段】本発明者らは、前記の課
題を解決するため鋭意研究を行った結果、長期にわたる
試験の上で、1,1−ジフェニルエチレンを主成分とし
て含ませた分子量調節剤がラジカル重合用として優れた
調節剤であることを確認して、本発明を完成した。すな
わち、本発明は1,1−ジフェニルエチレンを主成分と
するラジカル重合用分子量調節剤である。
Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the molecular weight of 1,1-diphenylethylene as a main component is included in a long-term test. The present invention has been completed by confirming that the regulator is an excellent regulator for radical polymerization. That is, the present invention is a molecular weight regulator for radical polymerization having 1,1-diphenylethylene as a main component.

【0009】本発明において、1,1−ジフェニルエチ
レンは、通常有機溶媒に希釈して使用される。1,1−
ジフェニルエチレンは分子量180.2、沸点277
℃、融点8℃で、常温では液体であるが、外気温が8℃
以下となると析出してしまうために重合系への添加が不
安定となる。従って、有機溶媒に50重量%程度、希釈
して使用することが望ましい。また、重合単量体で混合
希釈してもよい。
In the present invention, 1,1-diphenylethylene is usually diluted with an organic solvent before use. 1,1-
Diphenylethylene has a molecular weight of 180.2 and a boiling point of 277.
℃, melting point 8 ℃, liquid at room temperature, outside temperature is 8 ℃
If the amount is less than the above, precipitation will occur and the addition to the polymerization system will become unstable. Therefore, it is desirable to dilute the organic solvent by about 50% by weight before use. Moreover, you may mix and dilute with a polymerization monomer.

【0010】ここで、有機溶媒とは、ベンゼン、トルエ
ン、キシレン等の芳香族炭化水素、アセトン、メチルエ
チルケトン、メチルイソブチルケトン等のケトン類、メ
タノール、プロパノール等のアルコール類等であるが、
これらは重合単量体の種類やプロセスによって変わるも
のであって特に限定はしない。
Here, the organic solvent includes aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol and propanol.
These vary depending on the type and process of the polymerized monomer and are not particularly limited.

【0011】1,1−ジフェニルエチレンは製造の際、
若干の1,1−ジフェニルエタン等の不純物を含むが、
これらは全体の20重量%以下であることが好ましく、
更に10重量%以下であることが特に好ましい。
When 1,1-diphenylethylene is produced,
Contains some impurities such as 1,1-diphenylethane,
These are preferably 20% by weight or less of the whole,
It is particularly preferable that the amount is 10% by weight or less.

【0012】[0012]

【実施例】以下に実施例によって、本発明を更に具体的
に説明するが、本発明はこの実施例によって何等限定さ
れるものではない。実施例と比較例に使用した設備を説
明する。
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The equipment used in the examples and comparative examples will be described.

【0013】重合単量体、溶媒、分子量調節剤、開始剤
その他添加剤からなる仕込み液を原料槽、及び添加剤槽
から定量ポンプを介して、撹拌機と温度調節機能を備え
た容量50リッターの完全混合槽型反応器に連続的に供
給する。所定の温度で平均滞留時間を4時間に合わせる
ようにギアポンプを介して反応器内の容量が変化しない
ように連続的に反応器から抜き出す。反応器から抜き出
された反応物は未反応単量体、溶媒を除去するために減
圧吸引口を有する二軸押出機に送られ、ペレット化され
製品ポリマーとなる。
50 liters of capacity, equipped with a stirrer and a temperature control function, from a raw material tank and an additive tank via a metering pump for a charge liquid consisting of a polymerized monomer, a solvent, a molecular weight modifier, an initiator and other additives. Is continuously fed to the complete mixing tank type reactor. It is continuously withdrawn from the reactor through a gear pump so that the average residence time is adjusted to 4 hours at a predetermined temperature so that the capacity in the reactor does not change. The reaction product extracted from the reactor is sent to a twin-screw extruder having a vacuum suction port to remove unreacted monomer and solvent, and pelletized into a product polymer.

【0014】(実施例1)アクリロニトリル(AN)、
スチレン(ST)の共重合を行った。溶媒にエチルベン
ゼン(EB)とメチルエチルケトン(MEK)を用い
た。原料組成比率は、AN/ST/EB/MEKの重量
比率をそれぞれ40/40/10/10とした。重合開
始剤は使用せず重合温度は145℃で行った。
(Example 1) Acrylonitrile (AN),
Copolymerization of styrene (ST) was performed. Ethylbenzene (EB) and methyl ethyl ketone (MEK) were used as the solvent. As the raw material composition ratio, the weight ratio of AN / ST / EB / MEK was set to 40/40/10/10, respectively. Polymerization was carried out at 145 ° C. without using a polymerization initiator.

【0015】分子量調節剤として1,1−ジフェニルエ
チレンを原料(AN+ST)100重量部に対して0.
10重量部、0.25重量部、0.50重量部、添加し
た。同時に1,1−ジフェニルエチレンを無添加の場合
も行った。得られたペレットを東ソー製ゲルパーミエー
ションクロマトグラフィー分析によりポリスチレン換算
値として重量平均分子量MWと数平均分子量MN及び分子
量分布(MW/MN)を求めた。結果を表1に示した。こ
こでMW、MN及びMW/MNは次式(1)〜(3)によ
る。 MW=Σ(Nii 2)/Σ(Nii) (1) MN=Σ(Nii)/ΣNi (2) MW/MN (3) 但し MW:重量平均分子量 MN:数平均分子量 MW/MN:分子量分布 Ni:iという分子の総数 Mi:iという分子の分子量
As the molecular weight regulator, 1,1-diphenylethylene is added to 100 parts by weight of the raw material (AN + ST).
10 parts by weight, 0.25 parts by weight, 0.50 parts by weight were added. At the same time, it was carried out also when 1,1-diphenylethylene was not added. The obtained pellets were subjected to gel permeation chromatography analysis manufactured by Tosoh Corporation, and the weight average molecular weight M W , the number average molecular weight M N and the molecular weight distribution (M W / M N ) were obtained as polystyrene equivalent values. The results are shown in Table 1. Here, MW , MN, and MW / MN are based on the following equations (1) to (3). M W = Σ (N i M i 2 ) / Σ (N i M i ) (1) M N = Σ (N i M i ) / ΣN i (2) M W / M N (3) where M W : Weight average molecular weight M N : Number average molecular weight M W / M N : Molecular weight distribution N i : Total number of molecules i i : Molecular weight of molecule i i

【0016】[0016]

【表1】 [Table 1]

【0017】得られたペレットを東芝機械 IS−13
0F射出成形機を用いて230℃において、スクリュー
での滞留時間を1分と7分とで夫々カラープレートを成
形し、YI値を測定した。YI(イエローインデック
ス)値はスガ試験機デジタル測色色差計AUD−SCH
−A型を用い、試験法:JIS K−7103−77に
従って測定した。YI値の差を経過時間(6分)で除し
て劣化速度とし表2に示した。
The pellets thus obtained were manufactured by Toshiba Machine IS-13.
A color plate was molded using a 0F injection molding machine at 230 ° C. with a residence time on the screw of 1 minute and 7 minutes, respectively, and the YI value was measured. YI (yellow index) value is Suga Test Instruments digital colorimetric color difference meter AUD-SCH
-A type was used and it measured according to the test method: JIS K-7103-77. The difference in YI value is divided by the elapsed time (6 minutes) to obtain the deterioration rate, which is shown in Table 2.

【0018】[0018]

【表2】 [Table 2]

【0019】また、得られたペレットを65重量部、A
BS樹脂(日本合成ゴム:DP−606)35重量部を
ドライブレンドして二軸押出し機で混練再ペレット化し
た。1000ccの集気瓶(すりあわせ密閉式蓋付き)を
5本用意して、各集気瓶にABSブレンドペレットを4
00g秤量し蓋をして、24℃の部屋で24時間放置す
る。5人のモニターを選出し、各自鼻を集気瓶の口に近
付け、蓋を開けて臭気を感じるかどうかを判断する。少
しでも感じる場合は0ポイント、5ポイント満点で全員
臭気を感じない時は5ポイントとし、臭気を測定した。
結果を表3に示した。
Further, 65 parts by weight of the obtained pellets, A
35 parts by weight of BS resin (Japan Synthetic Rubber: DP-606) was dry blended and kneaded and re-pelletized by a twin-screw extruder. Prepare five 1000cc air collection bottles (with a lid that can be ground together) and place 4 ABS blend pellets in each air collection bottle.
Weigh 00 g, cover with a lid, and leave in a room at 24 ° C. for 24 hours. Five monitors are selected, each nose is brought close to the mouth of the air collection bottle, and the lid is opened to determine whether or not an odor is felt. The odor was measured by giving 0 points if any, and 5 points when no odor was felt by all.
The results are shown in Table 3.

【0020】[0020]

【表3】 [Table 3]

【0021】(実施例2)メチルメタクリレート(MM
A)、スチレン(ST)の共重合を行った。溶媒にメチ
ルエチメケトン(MEK)を用いた。原料組成比率は、
MMA/ST/MEKの重量比率をそれぞれ40/40
/20とし重合温度は95℃で開始剤にアゾビスイソブ
チルニトリルを原料に対して250ppm添加した。分子
量調節剤に1,1−ジフェニルエチレンを原料(MMA
+ST)100重量部に対して0.10重量部、0.2
5重量部、0.50重量部、添加した。同時に1,1−
ジフェニルエチレンを無添加の場合も行った。得られた
ペレットを東ソー製ゲルパーミエーションクロマトグラ
フィー分析によりポリスチレン換算値として平均分子量
及び分子量分布を求めた。結果を表1に示した。
(Example 2) Methyl methacrylate (MM
A) and styrene (ST) were copolymerized. Methyl ethyl ketone (MEK) was used as the solvent. The raw material composition ratio is
Weight ratio of MMA / ST / MEK is 40/40 respectively
The polymerization temperature was set to / 20, the polymerization temperature was 95 ° C., and 250 ppm of azobisisobutylnitrile was added to the initiator as a starting material. Raw material of 1,1-diphenylethylene as molecular weight regulator (MMA
+ ST) 0.10 parts by weight per 100 parts by weight, 0.2
5 parts by weight, 0.50 parts by weight were added. 1,1-at the same time
The procedure was also performed without adding diphenylethylene. The obtained pellets were subjected to gel permeation chromatography analysis manufactured by Tosoh Corporation to determine the average molecular weight and the molecular weight distribution as polystyrene-converted values. The results are shown in Table 1.

【0022】(実施例3)N−フェニルマレイミド(P
MI)、アクリロニトリル(AN)、スチレン(ST)
の3元共重合を行った。溶媒にメチルエチルケトン(M
EK)を用いた。原料組成比率は、PMI/AN/ST
/MEKの重量比率をそれぞれ20/20/40/20
とし重合温度は95℃で開始剤にアゾビスイソブチルニ
トリルを原料に対して250ppm添加した。分子量調節
剤に1,1−ジフェニルエチレンを原料(PMI+AN
+ST)100重量部に対して0.10重量部、0.2
5重量部、0.50重量部、添加した。同時に1,1−
ジフェニルエチレンを無添加の場合も行った。得られた
ペレットを東ソー製ゲルパーミエーションクロマトグラ
フィー分析によりポリスチレン換算値として平均分子量
及び分子量分布を求めた。結果を表1に示した。
Example 3 N-phenylmaleimide (P
MI), acrylonitrile (AN), styrene (ST)
Was terpolymerized. Methyl ethyl ketone (M
EK) was used. Raw material composition ratio is PMI / AN / ST
The weight ratio of / MEK is 20/20/40/20 respectively
The polymerization temperature was 95 ° C., and 250 ppm of azobisisobutylnitrile was added to the initiator as the initiator. Raw material of 1,1-diphenylethylene for molecular weight regulator (PMI + AN
+ ST) 0.10 parts by weight per 100 parts by weight, 0.2
5 parts by weight, 0.50 parts by weight were added. 1,1-at the same time
The procedure was also performed without adding diphenylethylene. The obtained pellets were subjected to gel permeation chromatography analysis manufactured by Tosoh Corporation to determine the average molecular weight and the molecular weight distribution as polystyrene-converted values. The results are shown in Table 1.

【0023】(実施例4)スチレン(ST)の重合を行
った。溶媒にメチルエチメケトン(MEK)を用いた。
原料組成比率は、ST/MEKの重量比率をそれぞれ8
0/20とし重合温度は95℃で開始剤にアゾビスイソ
ブチルニトリルを原料100重量部に対して250ppm
添加した。分子量調節剤に1,1−ジフェニルエチレン
を原料に対して0.10重量部、0.25重量部、0.
50重量部、添加した。同時に1,1−ジフェニルエチ
レンを無添加の場合も行った。得られたペレットを東ソ
ー製ゲルパーミエーションクロマトグラフィー分析によ
りポリスチレン換算値として平均分子量及び分子量分布
を求めた。結果を表1に示した。
Example 4 Styrene (ST) was polymerized. Methyl ethyl ketone (MEK) was used as the solvent.
The raw material composition ratio is 8 for the ST / MEK weight ratio.
The polymerization temperature is 0/20, the polymerization temperature is 95 ° C., and azobisisobutylnitrile is used as an initiator in an amount of 250 ppm with respect to 100 parts by weight of the raw material.
Was added. 1,1-diphenylethylene was used as a molecular weight modifier in 0.10 parts by weight, 0.25 parts by weight, and 0.1% by weight of the raw material.
50 parts by weight were added. At the same time, it was carried out also when 1,1-diphenylethylene was not added. The obtained pellets were subjected to gel permeation chromatography analysis manufactured by Tosoh Corporation to determine the average molecular weight and the molecular weight distribution as polystyrene-converted values. The results are shown in Table 1.

【0024】(比較例1)分子量調節剤として、1,1
−ジフェニルエチレンに変えてα−メチルスチレンダイ
マー(2,4−ジフェニル−4−メチル−1−ペンテ
ン)を原料に対して0.10重量部、0.25重量部、
0.50重量部、添加した以外は実施例1と同様とし
た。得られたペレットを東ソー製ゲルパーミエーション
クロマトグラフィー分析によりポリスチレン換算値とし
て平均分子量及び分子量分布を求めた。結果を表1に示
した
Comparative Example 1 As a molecular weight regulator, 1,1
-In place of diphenylethylene, α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-pentene) was added to the starting material in an amount of 0.10 parts by weight, 0.25 parts by weight,
The same procedure as in Example 1 was performed except that 0.50 parts by weight was added. The obtained pellets were subjected to gel permeation chromatography analysis manufactured by Tosoh Corporation to determine the average molecular weight and the molecular weight distribution as polystyrene-converted values. The results are shown in Table 1.

【0025】(比較例2)分子量調節剤として、1,1
−ジフェニルエチレンに変えてターピノーレン(1−メ
チル−4−イソプロピリデン−シクロヘキセン)を原料
に対して0.10重量部、0.25重量部、0.50重
量部、添加した以外は実施例1と同様とした。得られた
ペレットを東ソー製ゲルパーミエーションクロマトグラ
フィー分析によりポリスチレン換算値として平均分子量
及び分子量分布を求めた。結果を表1に示した。得られ
たペレットを東芝機械 IS−130F射出成形機を用
いて230℃において、スクリューでの滞留時間を1分
と7分とでカラープレートを成形しYI値を測定した。
YI(イエローインデックス)値はスガ試験機デジタル
測色色差計AUD−SCH−A型を用い、試験法:JI
S K−7103−77に従って測定した。YI値の差
を経過時間(6分)で除して劣化速度とし表2に示し
た。
(Comparative Example 2) 1,1 as a molecular weight regulator
Example 1 except that terpinolene (1-methyl-4-isopropylidene-cyclohexene) was added in place of diphenylethylene in an amount of 0.10 parts by weight, 0.25 parts by weight, 0.50 parts by weight with respect to the raw material. Same as above. The obtained pellets were subjected to gel permeation chromatography analysis manufactured by Tosoh Corporation to determine the average molecular weight and the molecular weight distribution as polystyrene-converted values. The results are shown in Table 1. A color plate was molded from the obtained pellets at 230 ° C. using a Toshiba Machine IS-130F injection molding machine, and the residence time on the screw was 1 minute and 7 minutes, and the YI value was measured.
The YI (yellow index) value uses a Suga tester digital calorimetric color difference meter AUD-SCH-A type, and a test method: JI
It was measured according to SK-7103-77. The difference in YI value is divided by the elapsed time (6 minutes) to obtain the deterioration rate, which is shown in Table 2.

【0026】(比較例3)分子量調節剤として、1,1
−ジフェニルエチレンに変えてn−ドデシルメルカプタ
ン(NDM)原料に対して0.10重量部、0.25重
量部、0.50重量部、添加した以外は実施例1と同様
とした。得られたペレットを東ソー製ゲルパーミエーシ
ョンクロマトグラフィー分析によりポリスチレン換算値
として平均分子量及び分子量分布を求めた。結果を表1
に示した。また、得られたペレットを65重量部、AB
S樹脂(日本合成ゴム:DP−606)35重量部をド
ライブレンドして二軸押出し機で混練再ペレット化し
た。1000ccの集気瓶(すりあわせ密閉式蓋付き)を
5本用意して、各集気瓶にABSブレンドペレットを4
00g秤量し蓋をして、24℃の部屋で24時間放置す
る。5人のモニターを選出し、各自鼻を集気瓶の口に近
付け、蓋を開けて臭気を感じるかどうかを判断する。少
しでも感じる場合は0ポイント、5ポイント満点で全員
臭気を感じない時は5ポイントとし、臭気を測定した。
結果を表3に示した。
(Comparative Example 3) 1,1 as a molecular weight regulator
The same procedure as in Example 1 was carried out except that 0.10 parts by weight, 0.25 parts by weight, and 0.50 parts by weight were added to the n-dodecyl mercaptan (NDM) raw material instead of -diphenylethylene. The obtained pellets were subjected to gel permeation chromatography analysis manufactured by Tosoh Corporation to determine the average molecular weight and the molecular weight distribution as polystyrene-converted values. The results are shown in Table 1.
It was shown to. In addition, 65 parts by weight of the obtained pellet, AB
35 parts by weight of S resin (Japan Synthetic Rubber: DP-606) was dry blended and kneaded and re-pelletized by a twin-screw extruder. Prepare five 1000cc air collection bottles (with a lid that can be ground together) and place 4 ABS blend pellets in each air collection bottle.
Weigh 00 g, cover with a lid, and leave in a room at 24 ° C. for 24 hours. Five monitors are selected, each nose is brought close to the mouth of the air collection bottle, and the lid is opened to determine whether or not an odor is felt. The odor was measured by giving 0 points if any, and 5 points when no odor was felt by all.
The results are shown in Table 3.

【0027】表1の実施例1〜4より、1,1−ジフェ
ニルエチレンの分子量調節効果は明らかであり、比較例
1〜3に使用した他の分子量調節剤の分子量分布よりも
シャープになっている。特に比較例1のα−メチルスチ
レンダイマー(2,4−ジフェニル−4−メチル−1−
ペンテン)を分子量調節剤に用いた場合は、分子量分布
が2.5−2.6と極端に鈍化した。
From Examples 1 to 4 in Table 1, the molecular weight controlling effect of 1,1-diphenylethylene is clear, and is sharper than the molecular weight distributions of the other molecular weight controlling agents used in Comparative Examples 1 to 3. There is. Particularly, α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-) of Comparative Example 1 was used.
When (pentene) was used as the molecular weight regulator, the molecular weight distribution was extremely slow at 2.5-2.6.

【0028】表2のYI(イエローインデックス)の時
間当たりの劣化度(ΔYI/分)は実施例1の1,1−
ジフェニルエチレンを使用した場合と比較例2のターピ
ノーレン(1−メチル−4−イソプロピリデン−シクロ
ヘキセン)を分子量調節剤に用いた場合では、1,1−
ジフェニルエチレンを使用した場合がΔYI/分値(劣
化速度)が小さく良好であった。
Degree of deterioration (ΔYI / min) per hour of YI (yellow index) in Table 2 is 1,1- of Example 1.
When diphenylethylene was used and terpinolene (1-methyl-4-isopropylidene-cyclohexene) of Comparative Example 2 was used as the molecular weight modifier, 1,1-
When diphenylethylene was used, the ΔYI / min value (deterioration rate) was small and good.

【0029】表3のABS樹脂と混練再ペレット化した
ものの臭気試験では1,1−ジフェニルエチレンを使用
した場合はポイントゼロで臭気なし。比較例3のn−ド
デシルメルカプタン(NDM)を分子量調節剤に用いた
場合では、ポイント5であり、モニター全員が臭気を感
じている。
In the odor test of the kneaded and re-pelletized ABS resin shown in Table 3, when 1,1-diphenylethylene was used, there was no odor at point 0. When n-dodecyl mercaptan (NDM) of Comparative Example 3 was used as the molecular weight modifier, the point was 5, and all the monitors felt an odor.

【0030】[0030]

【発明の効果】芳香族系ビニル単量体、シアン化ビニル
系単量体、(メタ)アクリル酸エステル単量体等のラジ
カル重合において、本発明の1,1−ジフェニルエチレ
ンを添加することにより、分子量分布をシャープにする
ことができると共に、製品中に残存することが少なく、
後に臭気を残さず、黄色劣化などの色相悪化もない色調
良好、透明性に優れた樹脂が得られる。
Effects of the Invention In radical polymerization of aromatic vinyl monomers, vinyl cyanide monomers, (meth) acrylic acid ester monomers, etc., by adding 1,1-diphenylethylene of the present invention, , The molecular weight distribution can be sharpened, and it rarely remains in the product,
It is possible to obtain a resin having a good color tone and excellent transparency, which does not leave an odor afterwards and does not deteriorate in hue such as yellow deterioration.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 1,1−ジフェニルエチレンを主成分と
するラジカル重合用分子量調節剤。
1. A molecular weight regulator for radical polymerization, which comprises 1,1-diphenylethylene as a main component.
JP13753794A 1994-06-20 1994-06-20 Molecular weight modifier Withdrawn JPH083208A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP13753794A JPH083208A (en) 1994-06-20 1994-06-20 Molecular weight modifier

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP13753794A JPH083208A (en) 1994-06-20 1994-06-20 Molecular weight modifier

Publications (1)

Publication Number Publication Date
JPH083208A true JPH083208A (en) 1996-01-09

Family

ID=15201010

Family Applications (1)

Application Number Title Priority Date Filing Date
JP13753794A Withdrawn JPH083208A (en) 1994-06-20 1994-06-20 Molecular weight modifier

Country Status (1)

Country Link
JP (1) JPH083208A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2357889A (en) * 1999-10-25 2001-07-04 Fuji Electric Co Ltd Fluorescent colour conversion film
WO2001098373A1 (en) * 2000-06-16 2001-12-27 Basf Aktiengesellschaft Method for the production of a polymerisation reaction product
US6716905B1 (en) * 1998-12-23 2004-04-06 Coatings Ag Coating agent
US6737468B1 (en) 1999-07-02 2004-05-18 Basf Coatings Ag Base coat and its use for producing color and/or effect-producing base coatings and multi-layer coatings
EP0807640B2 (en) 1996-05-13 2009-02-18 Arkema France Polymerization in the presence of a stable free radical and free radical initiator

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0807640B2 (en) 1996-05-13 2009-02-18 Arkema France Polymerization in the presence of a stable free radical and free radical initiator
US6716905B1 (en) * 1998-12-23 2004-04-06 Coatings Ag Coating agent
US6737468B1 (en) 1999-07-02 2004-05-18 Basf Coatings Ag Base coat and its use for producing color and/or effect-producing base coatings and multi-layer coatings
GB2357889A (en) * 1999-10-25 2001-07-04 Fuji Electric Co Ltd Fluorescent colour conversion film
WO2001098373A1 (en) * 2000-06-16 2001-12-27 Basf Aktiengesellschaft Method for the production of a polymerisation reaction product

Similar Documents

Publication Publication Date Title
JP5022444B2 (en) Thermoplastic resin with uniform composition and narrow molecular weight distribution and method for producing the same
US5489657A (en) Bulk process for making maleimide copolymers
JPS6284109A (en) Production of thermoplastic resin composition
US8378026B2 (en) Transparent rubber modified styrene resin and method for preparing the same by continuous bulk polymerization
JPS62106915A (en) Transparency and impact property modifier for polyvinyl chloride
US9315658B2 (en) Alkyl(meth)acrylate-based thermoplastic resin composition and thermoplastic resin with high scratch resistance and low yellowness
JPH083208A (en) Molecular weight modifier
JP2896331B2 (en) Rubber modified styrenic resin composition
KR100726485B1 (en) Continuous bulk polymerization process for transparent abs resin
KR20090049470A (en) Heat-resistant copolymer, method for preparing the same and thermoplastic resin composition having excellent color characteristics and impact strength using thereof
KR100829850B1 (en) Continuous bulk polymerization process of rubber-modified transparent styrenic resin having uniform composition, good transparency and high impact strength
EP0052259B1 (en) High nitrile resin and process for preparing the same
JP2699945B2 (en) Thermoplastic resin composition
JPS63135443A (en) Abs molding composition reduced in residual butadiene content
JPH09216980A (en) Resin composition
JPH10292087A (en) Abs molding composition having very high notched bar impact strength and produced in manner not including emulsion
KR20180073061A (en) Abs graft copolymer, method for preparing the graft copolymer, abs resin composition and molding product comprising the graft copolymer
JPH02175740A (en) Vinyl chloride resin composition
JPS61235450A (en) Resin composition
JPH1160640A (en) Maleimide-based copolymer and thermoplastic resin composition
JPH0940838A (en) Low lustrous and heat-resistant resin composition having excellent flow impact balance
EP4056649A1 (en) Thermoplastic resin composition, manufacturing method therefor and molded article manufactured therefrom
JPH1046003A (en) Maleimide abs resin composition
JP2005068428A (en) Heat-resistant rubber-modified styrene resin composition
EP0007931A1 (en) Rubber-modified terpolymers with improved heat distortion resistance

Legal Events

Date Code Title Description
A300 Withdrawal of application because of no request for examination

Free format text: JAPANESE INTERMEDIATE CODE: A300

Effective date: 20010904