JPS6046122B2 - Method for producing thermoplastic polymer - Google Patents
Method for producing thermoplastic polymerInfo
- Publication number
- JPS6046122B2 JPS6046122B2 JP55176202A JP17620280A JPS6046122B2 JP S6046122 B2 JPS6046122 B2 JP S6046122B2 JP 55176202 A JP55176202 A JP 55176202A JP 17620280 A JP17620280 A JP 17620280A JP S6046122 B2 JPS6046122 B2 JP S6046122B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl monomer
- weight
- maleic anhydride
- polymer
- copolymer
- 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Description
【発明の詳細な説明】
本発明は、イミド基を有する熱可塑性重合体の製法、
更に詳しくは、ゴム状重合体に芳香族ビニル単量体、無
水マレイン酸およびこれらと共重合可能なビニル単量体
からなる単量体混合物をグラフト重合させた共重合体を
、アンモニアおよび/または第1級アミンと反応させ耐
熱安定性、耐衝撃性および加工性にすぐれた熱可塑性重
合体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing a thermoplastic polymer having an imide group,
More specifically, a copolymer obtained by graft-polymerizing a rubber-like polymer with a monomer mixture consisting of an aromatic vinyl monomer, maleic anhydride, and a vinyl monomer copolymerizable with these is prepared by graft-polymerizing a rubber-like polymer with ammonia and/or The present invention relates to a method for producing a thermoplastic polymer having excellent heat stability, impact resistance, and processability by reacting with a primary amine.
従来から芳香族ビニル単量体、無水マレイン酸および
、これらと共重合可能なビニル単量体よりなる共重合体
の製造法が知られている(特公昭40−15829号、
特公昭45−31953号、特公昭49一1015時)
。A method for producing a copolymer consisting of an aromatic vinyl monomer, maleic anhydride, and a vinyl monomer copolymerizable with these has been known (Japanese Patent Publication No. 40-15829,
Special Publication No. 45-31953, Special Publication No. 49-1015)
.
また、ゴム状重合体に、無水マレイン酸、芳香族ビニ
ル単量体および/またはこれらと共重合可能なビニル単
量体をグラフト重合させた耐衝撃性を改良した熱可塑性
重合体の製造方法が提案されている。In addition, there is a method for producing a thermoplastic polymer with improved impact resistance, in which a rubbery polymer is graft-polymerized with maleic anhydride, an aromatic vinyl monomer, and/or a vinyl monomer copolymerizable with these. Proposed.
(特開昭42090号、特開昭49−28693号、特
開昭53−7825冴、特開昭53−8049時) し
かし、これら無水マレイン酸を共重合した重合体は、高
い熱変形温度を有しているが、いずれの場合も共重合体
連鎖中に無水マレイン酸に起因する酸無水物基が存在す
るために、高温時の水に対してはもちろんのこと、熱に
対しても化学変化を起し、分解し易く、射出または押出
加工する際に著しい制約があり、又加工品を水または水
蒸気に接触させたり、高温下にさらしたりすると、機械
的特性、特に衝撃強度が低下するという欠点があつた。
本発明はこれらの欠点を解決したものであつて、ゴム状
重合体5〜6唾量部に芳香族ビニル単量体50〜80重
量%、無水マレイン酸5〜4唾量%、およびこれらと共
重合可能なビニル単量体0〜(至)重量%からなる単量
体混合物60〜95重量部をグラフト重合させた共重合
体を(イ)溶液、(口)炭化水素溶媒中、懸濁、(ハ)
塊状溶融のいずれかの状態で、触媒の存在下アンモニア
および/または第1級アミンと、温度80〜350℃で
反応させ、前記重合体の酸無水物をイミド基とすること
により、すぐれた耐熱性(高い熱変形温度)、耐衝撃性
および加工法、さらに水および熱に対しても化学的に安
定である熱可塑性重合体の製造方法を提供しようとする
ものてある。(JP-A-42090, JP-A-49-28693, JP-A-53-7825, JP-A-53-8049) However, these copolymerized maleic anhydride polymers have a high heat distortion temperature. However, in both cases, because there is an acid anhydride group derived from maleic anhydride in the copolymer chain, it is chemically resistant not only to water at high temperatures but also to heat. It is susceptible to decomposition and decomposition, has significant limitations during injection or extrusion processing, and mechanical properties, especially impact strength, decrease when the processed product is exposed to water or steam or to high temperatures. There was a drawback.
The present invention solves these drawbacks by adding 50 to 80% by weight of an aromatic vinyl monomer, 5 to 4% by weight of maleic anhydride, and 5 to 6 parts by weight of a rubbery polymer. A copolymer obtained by graft polymerization of 60 to 95 parts by weight of a monomer mixture consisting of 0 to 95% by weight of a copolymerizable vinyl monomer is suspended in (a) a solution or (a) a hydrocarbon solvent. ,(c)
Excellent heat resistance can be obtained by reacting the polymer with ammonia and/or primary amine in the presence of a catalyst at a temperature of 80 to 350°C in any state of bulk melting, and converting the acid anhydride of the polymer into an imide group. The present invention seeks to provide a method for producing thermoplastic polymers that are chemically stable with respect to water and heat, as well as having good properties (high heat distortion temperature), impact resistance and processing methods.
本発明において、ゴム状重合体含有量は最終的に得られ
る熱可塑性重合体に要求される衝撃強度により、イミド
化前の共重合体を基準に5〜4唾量%の範囲で選択する
ことが出来る。In the present invention, the rubbery polymer content is selected in the range of 5 to 4% based on the copolymer before imidization, depending on the impact strength required of the final thermoplastic polymer. I can do it.
ゴム状重合体の含有量が増加すると、衝撃強度が向上す
るが、ゴム状重合体含有量が4呼量%をこえると最終的
に得られる熱可塑性重合体の加工性が悪く、また、5重
量%未満では衝撃改良効果が不充分である。一般的に、
芳香族ビニル単量体と無水マレイン酸とは交互共重合性
が強く、通常のラジカル重合.条件下の重合では芳香族
ビニルと無水マレイン酸のモル比が1:1の組成をもつ
交互共重合体が生成するが、これは機械的強度、成形加
工性の点では劣るが、耐熱性は著しく優れている。As the content of the rubbery polymer increases, the impact strength improves; however, when the content of the rubbery polymer exceeds 4% by weight, the processability of the final thermoplastic polymer is poor, and If it is less than % by weight, the impact improving effect is insufficient. Typically,
Aromatic vinyl monomers and maleic anhydride have strong alternating copolymerizability, and can be easily copolymerized using normal radical polymerization. Polymerization under these conditions produces an alternating copolymer with a molar ratio of aromatic vinyl and maleic anhydride of 1:1, which is inferior in mechanical strength and moldability, but has poor heat resistance. Remarkably superior.
本発明においては機械的強度および成形加工性を保持し
な.がら、しかも優れた耐熱性を得るためには、無水マ
レイン酸5〜4鍾量%、芳香族ビニル単量体50〜8鍾
量%、およびこれらと共重合可能なビニル単量体0〜3
呼量%の範囲とすることが必要であり、さらに生成する
共重合体の組成は使用した単・量体組成に近い均質なも
のであることが望ましい。このような均質な組成分布の
共重合体を得る方法として、芳香族ビニル単量体と、無
水マレイン酸およびこれらと共重合可能な単量体との単
量体混合物の重合速度より実質的に遅い速度で無水マレ
イン酸を添加しながらラジカル重合させればよく、これ
に用いるラジカル重合開始剤は混合モノマー中に初めか
ら一括して添加してもよく、また無水マレイン酸と共に
分割添加してもなんら差支えはない。また、ゴム質重合
体は予め、芳香族ビニル単量体等のモノマーに溶解し、
あるいは必要に応じて有機溶剤を添加し、稀釈して、使
用される。In the present invention, mechanical strength and moldability must be maintained. However, in order to obtain excellent heat resistance, 5 to 4 weight percent of maleic anhydride, 50 to 8 weight percent of aromatic vinyl monomer, and 0 to 3 weight percent of vinyl monomer copolymerizable with these are required.
It is necessary to set the copolymer composition within the range of nominal weight %, and furthermore, it is desirable that the composition of the copolymer produced be homogeneous close to the composition of the monomers used. As a method for obtaining such a copolymer with a homogeneous composition distribution, the polymerization rate of a monomer mixture of an aromatic vinyl monomer, maleic anhydride, and a monomer copolymerizable with these monomers can be substantially increased. Radical polymerization may be carried out while adding maleic anhydride at a slow rate, and the radical polymerization initiator used for this may be added all at once to the mixed monomer from the beginning, or may be added in portions together with maleic anhydride. There is no problem. In addition, the rubbery polymer is dissolved in advance in a monomer such as an aromatic vinyl monomer,
Alternatively, if necessary, an organic solvent may be added to dilute it before use.
本発明において用いられるゴム質重合体は、ゲル含有量
が5重量%以下であることが望ましく、また、そのガラ
ス転位点は−20℃以下のものである。これらの具体例
を挙げると、ブタジエン、イソプレン、クロiプレン等
の重合体、およびこれらジエンモノマーとその他のビニ
ル単量体、例えばスチレン、アクリロニトリル、アクリ
ル酸エステル、メタクリル酸エステル等との共重合体ゴ
ムおよびブロック共重合体ゴム、エチレンープロピレン
ージエンの共重合体ゴム、アクリル酸エステル重合体ゴ
ム、例えば、アクリル酸エチル、アクリル酸ブチル、ア
クリル酸2−エチルヘキシル、アクリル酸2−クロルエ
チル等の単独または共重合体および、これらと共重合可
能な単量体例えば、アクリロニトリル、スチレン、ブタ
ジエン、メチルメタクリレート等との共重合体などがあ
げられる。また、本発明において用いる芳香族ビニル単
量体は、スチレン、α−メチルスチレン、ビニルトルエ
ン、t−ブチルスチレン、クロロスチレン等のスチレン
単量体およびその置換単量体であつて、これらの中スチ
レンおよび、α−メチルスチレンが特に好ましい。The rubbery polymer used in the present invention preferably has a gel content of 5% by weight or less, and a glass transition point of -20°C or less. Specific examples of these include polymers such as butadiene, isoprene, and chloroprene, and copolymers of these diene monomers with other vinyl monomers such as styrene, acrylonitrile, acrylic esters, methacrylic esters, etc. Rubbers and block copolymer rubbers, ethylene-propylene-diene copolymer rubbers, acrylic acid ester polymer rubbers, such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-chloroethyl acrylate, etc. Alternatively, copolymers and monomers copolymerizable with these, such as copolymers with acrylonitrile, styrene, butadiene, methyl methacrylate, etc. may be mentioned. Further, the aromatic vinyl monomer used in the present invention is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, etc., and substituted monomers thereof. Styrene and α-methylstyrene are particularly preferred.
また共重合可能なビニル単量体としては、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単量体、
メチルアクリル酸エステル、エチルアクリル酸エステル
、ブチルアクリル酸エステル、等のアクリル酸エステル
単量体、メチルメタクリル酸エステル、エチルメタクリ
ル酸エステル等のメタクリル酸エステル単量体、アクリ
ル酸、メタクリル酸等のビニルカルボン酸単量体、アク
リル酸アミド、メタクリル酸アミド、アセナフチレンお
よびN−ビニルカルバゾール等であつて、これらの中、
アクリロニトリルアクリル酸エステル、メタクリル酸エ
ステルなどの単量体が特に好ましい。本発明のイミド化
反応に用いるアンモニアや第1級アミンは、無水または
水溶液いずれの状態であつても良く、また、第1級アミ
ノの具体例としてはメチルアミン、エチルアミン、n−
プロピルアミン、イソ−プロピルアミン、ブチルアミン
、ペンチルアミン、シクロヘキシルアミン等のアルキル
アミン、アニリン、トリルアミン、ナフチルアミン等の
芳香族アミン、およびクロルまたはブロム置換アニリン
等のハロゲン置換芳香族アミン、N−(2−アセトアミ
ド)−2−アミノエタンスルホン酸、p−アミノ安息香
酸、p−アミノ安息香酸ナトリウム、スルファミン酸ナ
トリウム、アミノ酢酸、β−アラニン、アクリルアミド
、0−ホスホエタノールアミン、アミノプロピルトリエ
トキシ−シラン、2●5ージクロルアニリンー4−スル
ホン酸ソーダ、p−クロルー0−アニシジン、α−クロ
ルアセトアミド、メタアクリルアミド、3−アミノプロ
パノール、4−メトキシー2−メチルアニリン、ジエチ
ルアミノエチルアミン、フルフリルアミン、アリルアミ
ン、3−アミノーベンゾトリフルオリド、等があげられ
る。In addition, examples of vinyl monomers that can be copolymerized include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile;
Acrylic ester monomers such as methyl acrylic ester, ethyl acrylic ester, butyl acrylic ester, methacrylic ester monomers such as methyl methacrylic ester and ethyl methacrylic ester, vinyl such as acrylic acid and methacrylic acid. Carboxylic acid monomers, acrylamide, methacrylic acid amide, acenaphthylene and N-vinylcarbazole, among which,
Monomers such as acrylonitrile acrylic ester and methacrylic ester are particularly preferred. The ammonia and primary amine used in the imidization reaction of the present invention may be in either an anhydrous or aqueous solution state, and specific examples of primary amino include methylamine, ethylamine, n-
Alkylamines such as propylamine, iso-propylamine, butylamine, pentylamine, cyclohexylamine, aromatic amines such as aniline, tolylamine, naphthylamine, and halogen-substituted aromatic amines such as chloro- or bromo-substituted aniline, N-(2- Acetamide)-2-aminoethanesulfonic acid, p-aminobenzoic acid, sodium p-aminobenzoate, sodium sulfamate, aminoacetic acid, β-alanine, acrylamide, 0-phosphoethanolamine, aminopropyltriethoxy-silane, 2 ●Sodium 5-dichloroaniline-4-sulfonate, p-chloro-0-anisidine, α-chloroacetamide, methacrylamide, 3-aminopropanol, 4-methoxy 2-methylaniline, diethylaminoethylamine, furfurylamine, allylamine, 3 -aminobenzotrifluoride, and the like.
これらは単独または2種以上の混合物で使用することが
できる。これらの使用量は芳香族ビニル−マレイン酸系
共重合体中のマレイン酸モル当量以上であり、好ましく
はマレイン酸モル当量の1〜1.3倍モル当量である。These can be used alone or in a mixture of two or more. The amount used is at least the molar equivalent of maleic acid in the aromatic vinyl-maleic acid copolymer, preferably 1 to 1.3 times the molar equivalent of maleic acid.
また、芳香族ビニル−マレイン酸系共重合体とアンモニ
アおよび/または第1級アミンとの反応は触媒の存在下
または不存在下で行うことが出来るが、触媒を使用する
場合、触媒として、トリメチルアミン、トリエチルアミ
ン、トリプロピルアミン、トリブチルアミン、N−N−
ジメチルアニリン等の第3級アミンが好適であり、その
使用量は共重合体中の無水マレイ7酸基に対して0.0
01〜0.5モル当量の範囲が好ましい。又、イミド化
率が90モル%以下のイミド化重合体は水および熱に対
する安定性が十分でなく好ましくない。無水マレイン酸
系共重合体のイミド化反応を溶液状態または非水性媒体
中の懸濁状態て行う場合は通常の反応容器、例えばオー
トクレーブなどを用いるのが好ましいが、塊状溶融状態
で行なう場合は脱揮装置の付いた押出機を用いても良い
。Furthermore, the reaction between the aromatic vinyl-maleic acid copolymer and ammonia and/or primary amine can be carried out in the presence or absence of a catalyst. , triethylamine, tripropylamine, tributylamine, N-N-
A tertiary amine such as dimethylaniline is preferred, and the amount used is 0.0% based on the maleic anhydride heptacid group in the copolymer.
A range of 0.01 to 0.5 molar equivalents is preferred. Further, imidized polymers having an imidization rate of 90 mol % or less are not preferred because they have insufficient stability against water and heat. If the imidization reaction of the maleic anhydride copolymer is carried out in a solution state or in a suspended state in a non-aqueous medium, it is preferable to use an ordinary reaction vessel such as an autoclave, but if it is carried out in a bulk molten state, it is preferable to use a reaction vessel such as an autoclave. An extruder equipped with a vaporizer may also be used.
又、本発明において、そのイミド化は下記反応式で示さ
れるが、反応式(1)の開環反応と(■)の閉環反応を
別々の装置で行なつても、同一の装置で行なつても良い
。In addition, in the present invention, the imidization is shown by the following reaction formula, but even if the ring-opening reaction of reaction formula (1) and the ring-closing reaction of (■) are performed in separate apparatuses, they can be performed in the same apparatus. It's okay.
イミド化反応は温度約80〜350℃で行われるが、好
ましくは100〜300℃である。The imidization reaction is carried out at a temperature of about 80 to 350°C, preferably 100 to 300°C.
温度が80℃未満では反応速度が遅く、反応に長時間を
要し実用的でなく、350℃をこえると重合体の熱分解
により物性の低下を生ずるので好ましくない。無水マレ
イン酸共重合体を溶液状態でイミド化する場合の溶剤と
しては、アセトン、メチルエチルケトン、メチルイソブ
チルケトン、アセトフェノン、テトラヒドロフラン、ジ
メチルフォルムアミド等があげられ、これらの中メチル
エチルケトンが特に好ましい。If the temperature is less than 80°C, the reaction rate is slow and the reaction takes a long time, making it impractical. If the temperature exceeds 350°C, the physical properties may deteriorate due to thermal decomposition of the polymer, which is not preferable. Examples of the solvent for imidizing the maleic anhydride copolymer in a solution state include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, and dimethyl formamide, among which methyl ethyl ketone is particularly preferred.
非水性媒体中で懸濁状態でイミド化する場合非水性媒体
としては、ペンタン、ヘキサン、ヘプタン、オクタン、
2−メチルペンタン、シクロペンタン、シクロヘキサン
等の脂肪族炭化水素が好適である。以上に説明した方法
によつて製造される無水マレイン酸系共重合体のイミド
化共重合体は高い熱変形温度を保持しつつ、水または熱
に対しても高度の安定性を有し、かつ、耐衝撃性等の機
械的特性成形加工性においても優れたものである。When imidizing in suspension in a non-aqueous medium, examples of the non-aqueous medium include pentane, hexane, heptane, octane,
Aliphatic hydrocarbons such as 2-methylpentane, cyclopentane, cyclohexane and the like are preferred. The imidized copolymer of maleic anhydride copolymer produced by the method described above maintains a high heat distortion temperature and has a high degree of stability against water and heat. It also has excellent mechanical properties such as impact resistance and moldability.
このイミド化共重合体はスチレン−アクリロニトリル共
重合体(SAN樹脂)、ABS樹脂、MBS樹脂等と良
好な相溶性を有しており、こられと混合することも出来
る。また、更に、安定剤、可塑剤、充填剤、着色剤等を
添加することも出来る。以下本発明を実施例について説
明する。なお実施例中の部および%は特記のない限りい
ずれも重量基準で表わした。実施例1
攪拌器を備えた2eステンレス製オーノクレーブにスチ
レン150ダ、小片に切断したポリブタジエン(旭化成
(株)製、商品名「ジエンNF55R」)38yを仕込
み、系内を窒素ガスで置換した後、室温で一昼夜攪拌し
、ゴムをスチレンに溶解させた。This imidized copolymer has good compatibility with styrene-acrylonitrile copolymer (SAN resin), ABS resin, MBS resin, etc., and can also be mixed with these. Further, stabilizers, plasticizers, fillers, colorants, etc. can also be added. The present invention will be described below with reference to Examples. In addition, all parts and percentages in the examples are expressed on a weight basis unless otherwise specified. Example 1 A 2E stainless steel ornoclave equipped with a stirrer was charged with 150 da of styrene and 38 y of polybutadiene cut into small pieces (manufactured by Asahi Kasei Corporation, trade name: "Diene NF55R"), and after replacing the inside of the system with nitrogen gas, The mixture was stirred at room temperature overnight to dissolve the rubber in the styrene.
これにメチルエチルケトン180yを添加し、温度80
℃に加熱した後、無水マレイン酸64yとベンゾイルパ
ーオキサイド0.3gをメチルエチルケトンに溶解した
溶液を6時間で分割添加した。更に2時間温度80゜C
に保つた。貼稠な反応液の一部をサンプリングしてガス
クロマトグラフィーにより未反応単量体の定量を行ない
、重合率および重合体中の無水マレイン酸の含有量を算
出した。この反応液にアニリン63.8y(無水マレイ
ン酸基に対し一L?モル倍)、トリエチルアミン2y1
メチルエチルケトン300ダへ添加し、温度140゜C
に昇温し、7時間反応を行なつた。この反応を冷却した
後メタノールで析出し、固型分を戸別乾燥した。これを
C−13NMR分析により分析したところ酸無水i物基
のイミド基への転化率は99%であつた。このイイミド
化共重合体は老化防止剤BBM(住友化*8学製)を0
2部添加し、30m.ノmφ脱揮装置は、スクリュー押
出機によりペレット化し、プランジャー式射出形成機で
成形し、物性を測定した。その重合結果および、共重合
体の物性をそれぞれ第1表及第2表に示した。比較例1
仕込量を2倍にした以外は、実施例1と同一条件で行つ
た。Add 180y of methyl ethyl ketone to this, and
After heating to .degree. C., a solution of 64y maleic anhydride and 0.3 g of benzoyl peroxide dissolved in methyl ethyl ketone was added in portions over 6 hours. Temperature: 80°C for another 2 hours
I kept it. A portion of the viscous reaction solution was sampled and the amount of unreacted monomer was determined by gas chromatography to calculate the polymerization rate and the content of maleic anhydride in the polymer. This reaction solution contains 63.8y of aniline (1 L? times the mole of maleic anhydride group) and 2y1 of triethylamine.
Added to 300 Da of methyl ethyl ketone and heated to 140°C.
The temperature was raised to 100.degree. C., and the reaction was carried out for 7 hours. After cooling the reaction, precipitation was performed with methanol, and the solid content was dried separately. When this was analyzed by C-13 NMR analysis, the conversion rate of acid anhydride groups to imide groups was 99%. This imidized copolymer contains 0 anti-aging agent BBM (manufactured by Sumitomo Chemical *8 Gaku).
Add 2 parts and add 30 m. In the mφ devolatilizing device, the pellets were pelletized using a screw extruder, molded using a plunger injection molding machine, and the physical properties were measured. The polymerization results and the physical properties of the copolymer are shown in Tables 1 and 2, respectively. Comparative Example 1 The same conditions as in Example 1 were carried out except that the amount of preparation was doubled.
即ち、2fのオートクレーブにスチレン300yとジエ
ンNF5R76y仕込み、窒素置換・後一昼夜攪拌し、
これに、メチルエチルケトン360y添加し、80℃に
加熱した後、無水マレイン酸128yへ、ベンゾイルパ
ーオキサイド0.6yとメチルエチルケトン140yの
溶液を6時間で添加し、更に80℃で2時間攪拌を行つ
た。冷却後、反応液の半分を取り出し、メタノール析出
を行い無水マレイン酸共重合体を得た。比較例2
比較例1の無水マレイン酸共重合体溶液をそのまま用い
て以下のイミド化反応を行つた。That is, 300y of styrene and 76y of diene NF5R were charged into a 2F autoclave, and after nitrogen purging, the mixture was stirred all day and night.
To this, 360 y of methyl ethyl ketone was added and heated to 80° C., and then a solution of 0.6 y of benzoyl peroxide and 140 y of methyl ethyl ketone was added to 128 y of maleic anhydride over 6 hours, followed by further stirring at 80° C. for 2 hours. After cooling, half of the reaction solution was taken out and precipitated with methanol to obtain a maleic anhydride copolymer. Comparative Example 2 The maleic anhydride copolymer solution of Comparative Example 1 was used as it was to carry out the following imidization reaction.
アニリン63.8f11トリエチルアミン2y1メチル
エチルケトン300yを重合体溶液に加えて、75℃に
温度を保ち、7時間反応を行つた。Aniline 63.8f11 triethylamine 2y1 methyl ethyl ketone 300y were added to the polymer solution, and the reaction was carried out for 7 hours while maintaining the temperature at 75°C.
得られたイミド化共重合体を実施例1と同様に処理し、
物性測定を行つた。比較例3ゴムを使用せず、スチレン
の仕込を188yとした以外は実施例1と同一で行つた
。The obtained imidized copolymer was treated in the same manner as in Example 1,
Physical properties were measured. Comparative Example 3 The same procedure as Example 1 was carried out except that no rubber was used and the styrene was charged at 188y.
(注1)熱安定性:窒素気流50cc′Minl昇温速
度 10℃Iminの条件での熱平秤
分析における重合体の重量減 少
が1%の場合の温度を示 す。(Note 1) Thermal stability: Thermal balance under the conditions of nitrogen flow 50cc'Minl and heating rate 10℃Imin.
The temperature is shown when the weight loss of the polymer in analysis is 1%.
(注2)耐熱性:ビカツト軟化点(5k9荷重)
ASTMD−1525に準じた。(Note 2) Heat resistance: Vikatsuto softening point (5k9 load)
According to ASTM D-1525.
(注3)衝撃強度:ノツチ付アイゾツト衝撃強度
ASTMD−256に準じた。実施例2ゴム状重
合体として中高ニトリルゴム(以下NBRと略記)(日
本合成ゴム社製商品名「N−2301)」)15部、ス
チレン65部、無水マレイン酸20部を使用した以外は
実施例1と同じ条件で行つた。(Note 3) Impact strength: Notched Izotsu impact strength
According to ASTM D-256. Example 2 The same procedure was carried out except that 15 parts of medium-high nitrile rubber (hereinafter abbreviated as NBR) (trade name "N-2301" manufactured by Nihon Gosei Rubber Co., Ltd.), 65 parts of styrene, and 20 parts of maleic anhydride were used as the rubbery polymer. The same conditions as in Example 1 were used.
その条件および結果を第3表に示す。実施例3、4
ゴム状重合体として、スチレン含量30%および40%
の2種のスチレン−ブタジエンブロック共重合体(以下
ブロックゴムという)ジエン社製商品名「TR−110
」および「TR−406」とスチレン、無水マレイン酸
との共重合体を製造し、これをアニリンで無水マレイン
酸基をイミド化してイミド化共重合体を製造した。The conditions and results are shown in Table 3. Examples 3, 4 Styrene content of 30% and 40% as rubbery polymer
Two types of styrene-butadiene block copolymers (hereinafter referred to as block rubber) manufactured by Diene Co., Ltd. under the trade name "TR-110"
" and "TR-406", styrene, and maleic anhydride were produced, and the maleic anhydride groups were imidized with aniline to produce an imidized copolymer.
仕込組成および結果を第,.:゜3表に示す。なお、そ
の条件は実施例1と同じ条件で行つた。実施例5
ポリブタジエン旭化成社製商品名『ジエンNF−35R
」1娼をスチレン7娼、メチルメタアクリレート(以下
MMAと略記)5部に溶解しメチルエチルケトン7娼で
稀釈した後、80℃に加熱し、無水マレイン酸15部、
ベンゾイルパーオキサイド0.丘部、メチルエチルケト
ン28部の溶液を6時間で分添した。The preparation composition and results are as follows. :゜ Shown in Table 3. Note that the conditions were the same as in Example 1. Example 5 Polybutadiene Asahi Kasei Co., Ltd. trade name “Diene NF-35R”
1 was dissolved in 7 parts of styrene and 5 parts of methyl methacrylate (hereinafter abbreviated as MMA), diluted with 7 parts of methyl ethyl ketone, heated to 80°C, and 15 parts of maleic anhydride,
Benzoyl peroxide 0. A solution of 28 parts of methyl ethyl ketone was added in portions over 6 hours.
実施例1と同じ条件で、この共重合体をイミド化した。
結果を第3表に示す。実施例6
ゴム状重合体として、スチレン23.5%のスチレンブ
タジエンゴム(以下SBR略記)日本ゼオン社製商品名
「NiPOl−1502」を10部、スチレン65部、
無水マレイン酸25部使用した以外は実施例1と同じ条
件で行つた。This copolymer was imidized under the same conditions as in Example 1.
The results are shown in Table 3. Example 6 As a rubbery polymer, 10 parts of styrene-butadiene rubber (hereinafter abbreviated as SBR) manufactured by Nippon Zeon Co., Ltd. under the trade name "NiPOl-1502" containing 23.5% styrene, 65 parts of styrene,
The same conditions as in Example 1 were used except that 25 parts of maleic anhydride was used.
実施例7
ポリブタジエン旭化成社製商品名「ジエンNF゛−55
R」15部をスチレン(4)部、アクリロニトリル(以
下訳と略記)W部に溶解した以外は実施例5と同一条件
で行つた。Example 7 Polybutadiene Product name “Diene NF-55” manufactured by Asahi Kasei Co., Ltd.
The procedure was carried out under the same conditions as in Example 5, except that 15 parts of "R" were dissolved in 4 parts of styrene and part W of acrylonitrile.
実施例8
実施例1と同一条件で無水マレイン酸共重合体・を製造
し、これに無水マレイン酸基に対して、1.05モル倍
メチルアミンとトリエチルアミン29、メチルエチルケ
トン300gを添加し、1400Cで7時間反応させた
。Example 8 A maleic anhydride copolymer was produced under the same conditions as in Example 1. To this, methylamine, triethylamine 29 and 300 g of methyl ethyl ketone were added to the maleic anhydride group in an amount of 1.05 molar times, and the mixture was heated at 1400C. The reaction was allowed to proceed for 7 hours.
実施例9
) 実施例8において、メチルアミンの代りに、n−ブ
チルアミンを使用した以外は、同一条件で行つた。Example 9) Example 8 was carried out under the same conditions except that n-butylamine was used instead of methylamine.
実施例および比較例のイミド化率(モル%)の測定はC
−13NMR(核磁気共鳴法)により行い各構造に帰属
されるスペクトルの面積比により算出したなお装置は日
本電子(株)FX−90QFTを用い次の条件で行つた
。The imidization rate (mol%) of Examples and Comparative Examples was measured using C
-13 NMR (Nuclear Magnetic Resonance Spectroscopy) was used and calculations were made based on the area ratio of spectra attributed to each structure. The apparatus used was JEOL Ltd. FX-90QFT, and the test was carried out under the following conditions.
測定条件:
周波数22S■セ
LOckDOfDMSO−4
Datap0int8192
Pukerptn10sec
PL11sewjdth8μSec(300)Freq
uencyrange45O4HzSOlventDM
SO−D6Reference39.5ppmOfDM
SOACCUmlatiOnlOOOO〜20000図
面は比較較例1および2、および実施例1の−重合体の
C−13NMRスペクトル図を参考のため示した。Measurement conditions: Frequency 22S SE LOckDOofDMSO-4 Datap0int8192 Pukerptn10sec PL11sewjdth8μSec (300) Freq
uencyrange45O4HzSolventDM
SO-D6Reference39.5ppmOfDM
SOACCUmlatiOnlOOOO~20000 The drawing shows C-13 NMR spectra of the polymers of Comparative Examples 1 and 2 and Example 1 for reference.
図中記号A,B,Cは下記化合物の領域を表わしたもの
である。Symbols A, B, and C in the figure represent the regions of the following compounds.
図面はポリマーのカルボニル領域のC一
13NMRスペクトル図であつて、aは比較例1、bは
比較例2、cは実施例1のものである。The drawings are C13 NMR spectra of the carbonyl region of the polymer, in which a shows Comparative Example 1, b shows Comparative Example 2, and c shows Example 1.
Claims (1)
50〜80重量%、無水マレイン酸5〜40重量%、お
よびこれらと共重合可能なビニル単量体0〜30重量%
からなる単量体混合物60〜95重量部をグラフト重合
させた共重合体を(イ)溶液(ロ)炭化水素溶媒中懸濁
(ハ)塊状溶融のいずれかの状態でアンモニアおよび/
または第1級アミンと温度80〜350℃で反応させる
ことを特徴とするイミド基を有する熱可塑性重合体の製
造方法。 2 ゴム状重合体がブタジエン単独重合体またはこれと
共重合可能なビニル単量体からなる重合体、アクリル酸
エステル単独重合体またはこれと共重合可能なビニル単
量体からなる重合体から選ばれた1種以上である特許請
求の範囲第1項記載の方法。 3 芳香族ビニル単量体がスチレンおよび/またはα−
メチルスチレンである特許請求の範囲第1項または第2
項記載の方法。 4 共重合可能なビニル単量体がアクリロニトリル、ア
クリル酸エステルおよびメタクリル酸エステルより選ば
れた1種以上の単量体である特許請求の範囲第1項、第
2項または第3項記載の方法。[Scope of Claims] 1. 5 to 40 parts by weight of a rubbery polymer, 50 to 80% by weight of an aromatic vinyl monomer, 5 to 40% by weight of maleic anhydride, and 0 vinyl monomer copolymerizable with these. ~30% by weight
A copolymer obtained by graft polymerization of 60 to 95 parts by weight of a monomer mixture consisting of: (a) a solution, (b) a suspension in a hydrocarbon solvent, and (c) a lump-like melting state is treated with ammonia and/or
Alternatively, a method for producing a thermoplastic polymer having an imide group, which comprises reacting with a primary amine at a temperature of 80 to 350°C. 2. The rubbery polymer is selected from a butadiene homopolymer, a polymer consisting of a vinyl monomer copolymerizable with this, an acrylic ester homopolymer, or a polymer consisting of a vinyl monomer copolymerizable with this. 2. The method according to claim 1, wherein the method is one or more of the following. 3 The aromatic vinyl monomer is styrene and/or α-
Claim 1 or 2 which is methylstyrene
The method described in section. 4. The method according to claim 1, 2 or 3, wherein the copolymerizable vinyl monomer is one or more monomers selected from acrylonitrile, acrylic esters and methacrylic esters. .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP55176202A JPS6046122B2 (en) | 1980-12-13 | 1980-12-13 | Method for producing thermoplastic polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP55176202A JPS6046122B2 (en) | 1980-12-13 | 1980-12-13 | Method for producing thermoplastic polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57100104A JPS57100104A (en) | 1982-06-22 |
JPS6046122B2 true JPS6046122B2 (en) | 1985-10-14 |
Family
ID=16009402
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP55176202A Expired JPS6046122B2 (en) | 1980-12-13 | 1980-12-13 | Method for producing thermoplastic polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6046122B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0546148Y2 (en) * | 1987-03-05 | 1993-12-01 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5993747A (en) * | 1982-11-19 | 1984-05-30 | Toray Ind Inc | Thermoplastic resin composition |
JPS5996106A (en) * | 1982-11-24 | 1984-06-02 | Kuraray Co Ltd | Modified cis-1,4-polyisoprene rubber, its production, and composition containing the same |
JPS62151465A (en) * | 1985-12-26 | 1987-07-06 | Denki Kagaku Kogyo Kk | Light-resistant thermoplastic resin composition |
US4866136A (en) * | 1987-08-12 | 1989-09-12 | Pennwalt Corporation | Process for producing polymer bound hindered amine light stabilizers |
US5418289A (en) * | 1988-10-31 | 1995-05-23 | Ube Cycon Ltd. | Process for producing a thermoplastic resin composition and a graft copolymer |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3428596A (en) * | 1966-09-12 | 1969-02-18 | Sinclair Research Inc | Rubber composition of conjugated diene rubber containing a non-reinforcing filler material and a nitrogen functional styrene-maleic anhydride resin bridging agent |
US3652726A (en) * | 1964-04-21 | 1972-03-28 | Ici Ltd | Thermoplastic compositions |
US3679640A (en) * | 1969-09-25 | 1972-07-25 | Dow Chemical Co | Method for making hydrazine derivatives of copolymers of vinyl aromatic compounds and alpha,beta-unsaturated dicarboxylic acids or anhydrides |
JPS4842091A (en) * | 1971-09-22 | 1973-06-19 | ||
JPS4912576A (en) * | 1972-05-18 | 1974-02-04 | ||
JPS4963782A (en) * | 1972-08-29 | 1974-06-20 | ||
US3998907A (en) * | 1972-08-29 | 1976-12-21 | Arco Polymers, Inc. | Rubber-modified dicarboxylic acid imide copolymers |
JPS52125161A (en) * | 1976-04-09 | 1977-10-20 | Ciba Geigy Ag | Preparation of maleimide |
-
1980
- 1980-12-13 JP JP55176202A patent/JPS6046122B2/en not_active Expired
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3652726A (en) * | 1964-04-21 | 1972-03-28 | Ici Ltd | Thermoplastic compositions |
US3428596A (en) * | 1966-09-12 | 1969-02-18 | Sinclair Research Inc | Rubber composition of conjugated diene rubber containing a non-reinforcing filler material and a nitrogen functional styrene-maleic anhydride resin bridging agent |
US3679640A (en) * | 1969-09-25 | 1972-07-25 | Dow Chemical Co | Method for making hydrazine derivatives of copolymers of vinyl aromatic compounds and alpha,beta-unsaturated dicarboxylic acids or anhydrides |
JPS4842091A (en) * | 1971-09-22 | 1973-06-19 | ||
JPS4912576A (en) * | 1972-05-18 | 1974-02-04 | ||
JPS4963782A (en) * | 1972-08-29 | 1974-06-20 | ||
US3998907A (en) * | 1972-08-29 | 1976-12-21 | Arco Polymers, Inc. | Rubber-modified dicarboxylic acid imide copolymers |
JPS52125161A (en) * | 1976-04-09 | 1977-10-20 | Ciba Geigy Ag | Preparation of maleimide |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0546148Y2 (en) * | 1987-03-05 | 1993-12-01 |
Also Published As
Publication number | Publication date |
---|---|
JPS57100104A (en) | 1982-06-22 |
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