JPH02194005A - Production of alpha-methylstyrene copolymer - Google Patents
Production of alpha-methylstyrene copolymerInfo
- Publication number
- JPH02194005A JPH02194005A JP1013296A JP1329689A JPH02194005A JP H02194005 A JPH02194005 A JP H02194005A JP 1013296 A JP1013296 A JP 1013296A JP 1329689 A JP1329689 A JP 1329689A JP H02194005 A JPH02194005 A JP H02194005A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- peroxide
- methylstyrene
- polymerization initiator
- polymeric
- 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.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 15
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 25
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 16
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- -1 butylperoxyhexahydrobenzoate Chemical compound 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
- 241000252233 Cyprinus carpio Species 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- CIKJANOSDPPCAU-UHFFFAOYSA-N ditert-butyl cyclohexane-1,4-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1CCC(C(=O)OOC(C)(C)C)CC1 CIKJANOSDPPCAU-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- ZAKVZVDDGSFVRG-UHFFFAOYSA-N prop-1-en-2-ylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CC(=C)C1=CC=CC=C1 ZAKVZVDDGSFVRG-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、α−メチルスチレン系共重合体を製造するに
あたり、生産性良く且つ機械強度の優れた共重合体を得
るため、重合開始剤として特定のポリメリックペルオキ
シエステルを用いる工業的に有利なα−メチルスチレン
系共重合体の製造方法に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention is directed to the production of α-methylstyrene copolymers using a polymerization initiator to obtain a copolymer with good productivity and excellent mechanical strength. The present invention relates to an industrially advantageous method for producing an α-methylstyrene copolymer using a specific polymeric peroxyester.
（従来の技術）
α−メチルスチレンは重合体の耐熱性改良のためによく
用いられている。従来、−射的にこれら共重合体の製造
方法に於ては、重合開始剤としてジ−ｔ−ブチルペルオ
キシへキサヒドロテレフタレート、ジ−ｔ−ブチルペル
オキシ−３，３，５−）リメチルシクロヘキサン等の１
分子中にペルオキシ結合を２個有する２官能ペルオキシ
ドが、生成共重合体の機械強度向上を目的として用いら
れている。例えば特開昭６０−２０６８０９号公報、特
開昭６０−２０６８１０号公報、特開昭６１−１８５５
１２号公報にそれらの例が開示されている。またそれら
共重合体の製造方法に於て同目的で、次に示した
１分子中に３個以上のペルオキシ結合を有する特定のジ
アシル型ポリメリックペルオキシドを用いる方法が特開
昭６０−１５２５１７号公報に開示されている。(Prior Art) α-methylstyrene is often used to improve the heat resistance of polymers. Conventionally, in methods for producing these copolymers, di-t-butylperoxyhexahydroterephthalate and di-t-butylperoxy-3,3,5-)limethylcyclohexane are used as polymerization initiators. etc. 1
A bifunctional peroxide having two peroxy bonds in its molecule is used for the purpose of improving the mechanical strength of the resulting copolymer. For example, JP-A No. 60-206809, JP-A No. 60-206810, JP-A No. 61-1855.
Examples thereof are disclosed in Publication No. 12. Furthermore, for the same purpose in producing these copolymers, JP-A-60-152517 discloses a method using a specific diacyl-type polymeric peroxide having three or more peroxy bonds in one molecule as shown below. Disclosed.
（発明が解決しようとする課題）
しかしながら、公知の２官能ペルオキシドを用いる製造
方法では、得られる重合体の機械強度の向上はまだ充分
とはいえない。また前記特定のジアシル型ポリメリック
ペルオキシドを用いた場合、ペルオキシドの分解温度（
１０時間半減期温度）が６０〜６５℃と低く、生産性を
高めるために重合温度を上げると分子量の著しい低下を
起こして重合体の機械強度を低下させる等の欠点があり
、重合速度の低下なしに、即ち生産性良く機械強度の高
い共重合体を得ることのできる方法が強く要望されてい
た。(Problems to be Solved by the Invention) However, the mechanical strength of the obtained polymer cannot be sufficiently improved by the production method using a known bifunctional peroxide. In addition, when using the above specific diacyl type polymeric peroxide, the decomposition temperature of the peroxide (
The 10-hour half-life temperature) is as low as 60 to 65°C, and when the polymerization temperature is raised to increase productivity, there is a disadvantage that the molecular weight significantly decreases and the mechanical strength of the polymer decreases, resulting in a decrease in the polymerization rate. There has been a strong demand for a method that can produce a copolymer with good productivity and high mechanical strength without the need for oxidation.
（課題を解決するための手段）
本発明者らは、上記の従来法の問題点について長期にわ
たって鋭意研究した結果、特定の重合開始剤を用いるこ
とによって、重合速度を低下させることなく、即ち生産
性良く機械強度の高い共重合体を得る方法を見いだして
本発明を完成した。(Means for Solving the Problems) As a result of long-term intensive research into the problems of the above-mentioned conventional methods, the present inventors have found that by using a specific polymerization initiator, it is possible to reduce the polymerization rate without reducing the polymerization rate. The present invention was completed by discovering a method for obtaining a copolymer with good properties and high mechanical strength.
即ち、本発明の方法は、α−メチルスチレン及びスチレ
ンを含んでなるビニル型単量体混合物を共重合させるに
あたり、重合開始剤として、一般式で表される繰り返し
単位を有するポリメリックペルオキシエステルを使用す
ることを特徴とするα−メチルスチレン系共重合体の製
造方法に関する。That is, the method of the present invention uses a polymeric peroxyester having a repeating unit represented by the general formula as a polymerization initiator in copolymerizing a vinyl monomer mixture containing α-methylstyrene and styrene. The present invention relates to a method for producing an α-methylstyrene copolymer.
本発明に使用されるビニル型単量体は主にα−メチルス
チレン及びスチレンである。また必要に応じて上記単量
体と共重合可能な他のビニル型単量体例えば、アクリロ
ニトリル、メタクリロニトリル、アルジル酸エステル類
、メタクリル酸エステル類、酢酸ビニル、塩化ビニル、
塩化ビニリデン、マレイン酸エステル類、フマル酸エス
テル類、マレイミド類、ブタジェンまたはポリブタジェ
ン等の壬ラストマーを加えても差し支えない。またこれ
らビニル型単量体の割合は、得られる共重合体の要求性
能に応じて決めることができるが、例えばα−メチルス
チレン１０〜５０重量％、スチレン２０〜９０重量％、
及びこれらの単量体と共重合可能な他のビニル型単量体
０〜３０重量％である。α−メチルスチレンの使用量は
１０重量部より少ないと充分な耐熱性が得られず、また
５０重量部より多いと耐熱性向上においては好ましいが
重合速度の低下が著しく生産性が低下する傾向にある。The vinyl type monomers used in the present invention are mainly α-methylstyrene and styrene. If necessary, other vinyl monomers copolymerizable with the above monomers, such as acrylonitrile, methacrylonitrile, algylic acid esters, methacrylic acid esters, vinyl acetate, vinyl chloride,
It is also possible to add elastomers such as vinylidene chloride, maleates, fumarates, maleimides, butadiene or polybutadiene. The proportion of these vinyl monomers can be determined depending on the required performance of the resulting copolymer, but for example, α-methylstyrene 10 to 50% by weight, styrene 20 to 90% by weight,
and 0 to 30% by weight of other vinyl monomers copolymerizable with these monomers. If the amount of α-methylstyrene used is less than 10 parts by weight, sufficient heat resistance cannot be obtained, and if it is more than 50 parts by weight, it is preferable for improving heat resistance, but the polymerization rate tends to drop significantly and productivity decreases. be.
本発明に使用される重合開始剤は、−分子中にペルオキ
シ結合を３個以上有するポリメリックペルオキシエステ
ルであり、繰返し単位は３から５０好ましくはｌＯから
５０が適当である。またその添加量は単量体の種類及び
組合せにより異なるが、般には通常の重合におけるペル
オキシドの添加量でよく、例えば単量体の仕込量１００
重量部に対して純品換算で０．０１〜５重量部である。The polymerization initiator used in the present invention is a polymeric peroxyester having three or more peroxy bonds in the molecule, and the number of repeating units is suitably 3 to 50, preferably 10 to 50. The amount added varies depending on the type and combination of monomers, but in general, the amount added of peroxide in normal polymerization may be sufficient, for example, the amount of monomer charged 100
It is 0.01 to 5 parts by weight in terms of pure product.
その量が０．０１重量部より少なくなると重量速度が遅
くなる傾向にあり、また５重量部より多くなると重合速
度が大きくなり重合を制御しにくくなる傾向にあるので
好ましくない。またその添加方法は初期添加でも逐次添
加でもかまわない。If the amount is less than 0.01 parts by weight, the weight rate tends to be slow, and if it is more than 5 parts by weight, the polymerization rate tends to increase and it becomes difficult to control the polymerization, which is not preferable. Moreover, the addition method may be initial addition or sequential addition.
前記ポリメリックペルオキシエステルは、例えば次のよ
うにして合成される。即ち、一般式（式中Ｒ２は −Ｃ
Ｈ２ＣＨ，−−ＣミＣ−ラム水溶液の存在下で、次の一
般式
を表す。）
で表される二塩基酸クロライドを反応させることにより
得られる。またこれはポリメリックペルオキシエステル
の分解温度（１０時間半減期温度）は、７５〜８５℃の
間にある。The polymeric peroxyester is synthesized, for example, as follows. That is, the general formula (wherein R2 is -C
In the presence of an aqueous solution of H2CH,--CmiC-ram, the following general formula is represented. ) It can be obtained by reacting dibasic acid chloride represented by: Also, the decomposition temperature (10 hour half-life temperature) of the polymeric peroxyester is between 75 and 85°C.
本発明に使用されるポリメリックペルオキシエステルは
単独あるいは２種類以上を併用することもできる。また
一般に使用される単官能ペルオキシド、２官能ペルオキ
シド、或はジアシル型ポリメリックペルオキシドと併用
するさともできる。The polymeric peroxyesters used in the present invention can be used alone or in combination of two or more. It can also be used in combination with commonly used monofunctional peroxides, difunctional peroxides, or diacyl type polymeric peroxides.
併用することにより重合温度、重合速度、重合生成物の
分子量、分子量分布等を変えることが可能である。By using them together, it is possible to change the polymerization temperature, polymerization rate, molecular weight, molecular weight distribution, etc. of the polymerized product.
本発明において用いられる重合方法は、通常の懸濁重合
法、塊状重合法、或は溶液重合でもよい。The polymerization method used in the present invention may be a conventional suspension polymerization method, bulk polymerization method, or solution polymerization method.
また重合温度は一般に６０−１５０℃であり、好ましく
は７０〜１３０℃の温度範囲である。重合温度が６０℃
未満では重合時間が長くなる傾向にあり、１５０℃を越
えると重合物の分子量が低下し、また重合開始剤の寿命
が短くなって不利である。The polymerization temperature is generally 60-150°C, preferably 70-130°C. Polymerization temperature is 60℃
If it is less than 150°C, the polymerization time tends to be long, and if it exceeds 150°C, the molecular weight of the polymer will decrease and the life of the polymerization initiator will be shortened, which is disadvantageous.
（発明の効果）
特定の重合開始剤を用いる本発明は、以下に述べる特徴
を有している。(Effects of the Invention) The present invention, which uses a specific polymerization initiator, has the following characteristics.
即ち、特定のポリメリックペルオキシエステルを重合開
始剤としてα−メチルスチレン系共重合体を製造した場
合、単官能ペルオキシド、２官能ペルオキシド或はジア
シル型ポリメ゛リックペルオキシドを用いた従来法に比
べて、重合速度を低下させることなしに即ち生産性良く
機械強度の優れた共重合体を得ることができるようにな
った。That is, when an α-methylstyrene copolymer is produced using a specific polymeric peroxyester as a polymerization initiator, the polymerization rate is lower than that of the conventional method using a monofunctional peroxide, a difunctional peroxide, or a diacyl type polymeric peroxide. It has now become possible to obtain a copolymer with good productivity and excellent mechanical strength without reducing the speed.
（実施例） 以下、本発明を実施例により具体的に説明する。(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例１
「スチレン−α−メチルスチレン共重合（塊状重合）及
び共重合体の物性測定」
スチレン８０重量％とα−メチルスチレン２０重量％と
の混合物１１に重合開始剤として次のポリメリックペル
オキシエステル
２１５０にした以外実施例１と同様にして行った。そき
結果を第１表に示した。Example 1 "Styrene-α-methylstyrene copolymerization (bulk polymerization) and measurement of physical properties of copolymer" The following polymeric peroxyester was added as a polymerization initiator to a mixture 11 of 80% by weight of styrene and 20% by weight of α-methylstyrene. It was carried out in the same manner as in Example 1 except that the temperature was changed to 2150. The results are shown in Table 1.
実施例３
重合開始剤を次に示す
０．０１モルを溶解して調製した試料５ｍｊ！を内径１
２鮒のガラスアンプルに封入し、９０℃で８時間重合を
行った。しかる後、反応液を取り出しベンゼンに溶解さ
せ、内部Ｓ準法によるガスクロマトグラフィーより未反
応の単量体を定量して重合転化率を算出した。また生成
した重合体の機械強度（引張り強度（ＪＩＳ Ｋ−６８
７１） 、曲げ強度ＪＩＳ Ｋ−６８７１））を測定し
た。それらの結果を第１表に示した。Example 3 Sample 5mj! prepared by dissolving 0.01 mol of polymerization initiator shown below! Inner diameter 1
Two pieces of carp were sealed in a glass ampoule, and polymerization was performed at 90°C for 8 hours. Thereafter, the reaction solution was taken out and dissolved in benzene, and the unreacted monomer was quantified by gas chromatography using an internal S semi-method to calculate the polymerization conversion rate. In addition, the mechanical strength (tensile strength (JIS K-68
71) and bending strength JIS K-6871)) were measured. The results are shown in Table 1.
実施例２ 重合開始剤を次に示す。Example 2 The polymerization initiator is shown below.
７２５０にした以外実施例１と同様にして行った。その
結果を第１表に示した。The same procedure as in Example 1 was carried out except that 7250 was used. The results are shown in Table 1.
実施例４ 重合開始剤を次に示す １３３００にした以外実施例１と同様にして行った。Example 4 The polymerization initiators are shown below. The test was carried out in the same manner as in Example 1 except that the temperature was changed to 13,300.
その結果を第１表に示した。The results are shown in Table 1.
比較例１
重合開始剤を既存のジアシル型ポリメリックペルオキシ
ドである
ドロフタレートを用いた以外、実施例１と同様にして行
った。その結果を第１表に示した。Comparative Example 1 A polymerization was carried out in the same manner as in Example 1 except that dolphthalate, which is an existing diacyl type polymeric peroxide, was used as a polymerization initiator. The results are shown in Table 1.
にした以外、実施例１と同様にして行った。その結果を
第１表に示した。The procedure was carried out in the same manner as in Example 1, except that . The results are shown in Table 1.
比較例２
重合開始剤を本発明で使用されているペルオキシドとよ
く似た分解速度を有する単官能ペルオキシドであるｔ−
ブチルペルオキシへキサヒドロベンゾエートを用いた以
外、実施例１と同様にして行った。その結果を第１表に
示した。Comparative Example 2 The polymerization initiator was t- which is a monofunctional peroxide with a similar decomposition rate to the peroxide used in the present invention.
The same procedure as in Example 1 was carried out except that butylperoxyhexahydrobenzoate was used. The results are shown in Table 1.
比較例３
重合開始剤を本発明で使用されているペルオキシドとよ
く似た分解速度を有する２官能ペルオキシドであるジー
ｔ−へキシルベルオキシヘキサ上第
表
第１表から明らかなように、本発明のペルオキシドを用
いた場合、比較例１にある従来のジアシル型ポリメリッ
クペルオキシドを用いた場合と比べて重合転化率に於て
著しい向上がみられる。また本発明のペルオキシドを用
いて得られた共重合体の機械的強度は、比較例１．２．
３を用いて得られた共重合体に比べて著しい向上がみら
れる。Comparative Example 3 The polymerization initiator was di-t-hexylberoxyhexane, a bifunctional peroxide with a decomposition rate similar to that of the peroxide used in the present invention, as shown in Table 1 above. When this peroxide is used, the polymerization conversion rate is significantly improved compared to when the conventional diacyl type polymeric peroxide in Comparative Example 1 is used. Moreover, the mechanical strength of the copolymer obtained using the peroxide of the present invention was compared with Comparative Example 1.2.
A remarkable improvement is seen compared to the copolymer obtained using No. 3.
実施例２
「スチレン−α−メチルスチレン−アクリロニトリル共
重合（懸濁重合）及び共重合体の物性測定」スチレン６
０重量％、α−メチルスチレン３０重量％、アクリロニ
）ＩＪル１０重量％の混合物１ｚに重合開始剤として、
次のポリメリックペルオキシエステル
８時間後の転化率
０．０４モルを溶解した試料１００ｇを水４００ｇ、燐
酸第三カルシウム２ｇ１ドデシルベンゼンスルホン酸ソ
ーダ０．０２ ｇからなる懸濁剤と混合し、窒素置換さ
れた１１０オートクレーブに封入し、９０℃で１５時間
重合を行った。しかる後、反応液をＤＭＦに溶解させ内
部標準法によるガスクロマトグラフィーより未反応の単
量体を定量して重合転化率を算出した。また生成した重
合体の機械的強度（曲げ強度（ＪＩＳ Ｋ−６８７１）
、Ｉｚｏｄ衝撃強度（ＪＩＳ Ｋ−６８７１）を測定
した。それらの結果を第２表に示した。Example 2 "Styrene-α-methylstyrene-acrylonitrile copolymerization (suspension polymerization) and measurement of physical properties of copolymer" Styrene 6
As a polymerization initiator, a mixture 1z of 0% by weight, 30% by weight of α-methylstyrene, and 10% by weight of acrylonitrile (IJ) was added as a polymerization initiator.
Next, 100 g of a sample in which 0.04 mol of polymeric peroxyester was dissolved was mixed with a suspending agent consisting of 400 g of water, 2 g of tertiary calcium phosphate, 0.02 g of sodium dodecylbenzenesulfonate, and the mixture was purged with nitrogen. The mixture was placed in a 110 autoclave, and polymerization was carried out at 90°C for 15 hours. Thereafter, the reaction solution was dissolved in DMF, and unreacted monomers were quantified by gas chromatography using an internal standard method to calculate the polymerization conversion rate. In addition, the mechanical strength (flexural strength (JIS K-6871) of the produced polymer
, Izod impact strength (JIS K-6871) was measured. The results are shown in Table 2.
比較例４
重合開始剤を既存のジアシル型ポリメリックペルオキシ
ドである
ンゾエートを用いた以外、実施例２と同様にして行った
。その結果を第２表に示した。Comparative Example 4 Comparative example 4 was carried out in the same manner as in Example 2 except that inzoate, which is an existing diacyl type polymeric peroxide, was used as a polymerization initiator. The results are shown in Table 2.
比較例６
重合開始剤を本発明で使用されているペルオキシドとよ
く似た分解速度を有する２官能ペルオキシドであるジー
ｔ−へキシルペルオキシへキサヒドロフタレートを用い
た以外、実施例２と同様にして行った。その結果を第２
表に示した。Comparative Example 6 The same procedure as in Example 2 was used except that the polymerization initiator was di-t-hexylperoxyhexahydrophthalate, which is a bifunctional peroxide with a similar decomposition rate to the peroxide used in the present invention. went. The result is the second
Shown in the table.
にした以外、実施例２と同様にして行った。その結果を
第２表に示した。The procedure was carried out in the same manner as in Example 2 except that . The results are shown in Table 2.
比較例５
重合開始剤を本発明で使用されているペルオキシドとよ
く似た分解速度を有する単官能ペルオキシドであるｔ−
ブチルペルオキシへキサヒドロベ第２表から明らかなよ
うに、本発明のペルオキシドを用いた場合、比較例４に
ある従来のジアシル型ポリメリックペルオキシドを用い
た場合と比べて重合転化率に於て著しい向上がみられる
。また本発明のペルオキシドを用いて得られた共重合体
の機械的強度は、比較例４． ５． ６を用いて得られ
た共重合体に比べて著しい向上がみられる。Comparative Example 5 The polymerization initiator was t-, a monofunctional peroxide with a similar decomposition rate to the peroxide used in the present invention.
Butylperoxyhexahydrobe As is clear from Table 2, when the peroxide of the present invention was used, there was a significant improvement in the polymerization conversion rate compared to when the conventional diacyl type polymeric peroxide in Comparative Example 4 was used. It will be done. Furthermore, the mechanical strength of the copolymer obtained using the peroxide of the present invention was as compared with Comparative Example 4. 5. A remarkable improvement is seen compared to the copolymer obtained using No. 6.
実施例３
［スチレン−α−メチルスチレン−アクリロニトリル共
重合（懸濁重合）及び共重合体の物性測定」スチレン６
０重量％、α−メチルスチレン３０重量％、アクリロニ
トリル１０重量％の混合物１１をスチレン２０重量％、
α−メチルスチレン５０重量％、アクリロニトリル３０
重量％の混合物ＩＩ！にした以外実施例２と同様にして
行い、それらの結果を第３表に示した。Example 3 [Styrene-α-methylstyrene-acrylonitrile copolymerization (suspension polymerization) and measurement of physical properties of copolymer” Styrene 6
Mixture 11 of 0% by weight, 30% by weight of α-methylstyrene, and 10% by weight of acrylonitrile was mixed with 20% by weight of styrene,
α-methylstyrene 50% by weight, acrylonitrile 30%
% by weight of mixture II! The test was conducted in the same manner as in Example 2 except that the results were shown in Table 3.
比較例７
重合開始剤を既存のジアシル型ポリメリックペルオキシ
ドである
にした以外、実施例３と同様にした行った。その結果を
第３表に示した。Comparative Example 7 The same procedure as in Example 3 was carried out except that the polymerization initiator was an existing diacyl type polymeric peroxide. The results are shown in Table 3.
比較例８
重合開始剤を本発明で使用されているペルオキシドとよ
く似た分解速度を有する単官能ペルオキシドであるｔ−
ブチルペルオキシへキサヒドロベンゾエートを用いた以
外、実施例３と同様にして行った。その結果を第３表に
示した。Comparative Example 8 The polymerization initiator was t-, a monofunctional peroxide with a similar decomposition rate to the peroxide used in the present invention
The same procedure as in Example 3 was carried out except that butylperoxyhexahydrobenzoate was used. The results are shown in Table 3.
比較例９
重合開始剤を本発明で使用されているペルオキシドとよ
く似た分解速度を有する２官能ペルオキシトチするジー
ｔ−へキシルペルオキシへキサヒドロフタレートを用い
た以外、実施例３と同様にして行った。その結果を第３
表に示した。Comparative Example 9 The same procedure as in Example 3 was used except that the polymerization initiator was di-t-hexyl peroxyhexahydrophthalate, which has a decomposition rate similar to that of the peroxide used in the present invention. went. The result is the third
Shown in the table.
第３表から明らかなように、本発明のペルオキシドを用
いた場合、比較例７にある従来のジアシル型ポリメリッ
クペルオキシドを用いた場合と比べて重合転化率に於て
著しい向上がみられる。また本発明のペルオキシドを用
いて得られた共重合体の機械的強度は、比較例？、８．
９を用いて得られた共重合体に比べて著しい向上がみら
れる。As is clear from Table 3, when the peroxide of the present invention is used, the polymerization conversion rate is significantly improved compared to when the conventional diacyl type polymeric peroxide shown in Comparative Example 7 is used. Also, is the mechanical strength of the copolymer obtained using the peroxide of the present invention as a comparative example? , 8.
A remarkable improvement is seen compared to the copolymer obtained using No. 9.
Claims (1)
ル型単量体混合物を共重合させるにあたり、重合開始剤
として、一般式（１） ▲数式、化学式、表等があります▼（１） （式中Ｒ＿１は▲数式、化学式、表等があります▼或は
▲数式、化学式、表等があります▼ を表し、Ｒ＿２は−ＣＨ＿２ＣＨ＿２−、−Ｃ≡Ｃ−、
▲数式、化学式、表等があります▼を表す。） で表される繰り返し単位を有するポリメリックペルオキ
シエステルを使用することを特徴とするα−メチルスチ
レン系共重合体の製造方法。[Claims] 1. In copolymerizing a vinyl monomer mixture containing α-methylstyrene and styrene, the polymerization initiator includes general formula (1) ▲Mathematical formula, chemical formula, table, etc.▼ (1) (In the formula, R_1 represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_2 represents -CH_2CH_2-, -C≡C-,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ Represents. ) A method for producing an α-methylstyrene copolymer, the method comprising using a polymeric peroxyester having a repeating unit represented by:
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1013296A JPH02194005A (en) | 1989-01-24 | 1989-01-24 | Production of alpha-methylstyrene copolymer |
| US07/416,835 US5041624A (en) | 1988-10-13 | 1989-10-03 | Polymeric peroxy ester and its use |
| DE68916501T DE68916501T2 (en) | 1988-10-13 | 1989-10-06 | Polymeric peroxyesters and their application. |
| EP89310238A EP0364169B1 (en) | 1988-10-13 | 1989-10-06 | Polymeric peroxy ester and its use |
| KR1019890014658A KR960004478B1 (en) | 1988-10-13 | 1989-10-13 | Polymeric peroxy ester and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1013296A JPH02194005A (en) | 1989-01-24 | 1989-01-24 | Production of alpha-methylstyrene copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02194005A true JPH02194005A (en) | 1990-07-31 |
Family
ID=11829225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1013296A Pending JPH02194005A (en) | 1988-10-13 | 1989-01-24 | Production of alpha-methylstyrene copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02194005A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005248002A (en) * | 2004-03-04 | 2005-09-15 | Ps Japan Corp | Heat-resistant styrene resin stretched sheet |
| JP2005248003A (en) * | 2004-03-04 | 2005-09-15 | Ps Japan Corp | Manufacturing method of heat-resistant styrene resin and its composition |
-
1989
- 1989-01-24 JP JP1013296A patent/JPH02194005A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005248002A (en) * | 2004-03-04 | 2005-09-15 | Ps Japan Corp | Heat-resistant styrene resin stretched sheet |
| JP2005248003A (en) * | 2004-03-04 | 2005-09-15 | Ps Japan Corp | Manufacturing method of heat-resistant styrene resin and its composition |
| JP4721645B2 (en) * | 2004-03-04 | 2011-07-13 | Ｐｓジャパン株式会社 | Method for producing heat-resistant styrenic resin and composition thereof |
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