JPH03217405A - Styrene-maleic anhydride-glycidyl methacrylate copolymer - Google Patents
Styrene-maleic anhydride-glycidyl methacrylate copolymerInfo
- Publication number
- JPH03217405A JPH03217405A JP1341090A JP1341090A JPH03217405A JP H03217405 A JPH03217405 A JP H03217405A JP 1341090 A JP1341090 A JP 1341090A JP 1341090 A JP1341090 A JP 1341090A JP H03217405 A JPH03217405 A JP H03217405A
- Authority
- JP
- Japan
- Prior art keywords
- glycidyl methacrylate
- copolymer
- styrene
- maleic anhydride
- structural units
- 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
- 229920001577 copolymer Polymers 0.000 title abstract description 32
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 15
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 claims description 9
- 229920005604 random copolymer Polymers 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000011342 resin composition Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 229920006122 polyamide resin Polymers 0.000 description 11
- 229920001225 polyester resin Polymers 0.000 description 11
- 239000004645 polyester resin Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000005267 main chain polymer Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 polybutylene terephthalate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (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、高分子改良剤として、或いは高分子多成分系
の相溶性を向上させる高分子相溶化剤として使用できる
スチレン・無水マレイン酸・グリシジルメタクリレート
ランダム共重合体に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides styrene/maleic anhydride that can be used as a polymer modifier or as a polymer compatibilizer to improve the compatibility of a polymer multicomponent system. -Relating to glycidyl methacrylate random copolymer.
〔従来の技術及び発明が解決しようとする課題〕高分子
多成分系において、種類の異なる高分子は一般的に分子
次元では互いに溶け合わず、混練したポリマー相互の長
所を生かして得るためには、分散性を良くすることが必
要である。[Prior art and problems to be solved by the invention] In a multi-component polymer system, different types of polymers generally do not dissolve into each other at the molecular level, and it is necessary to take advantage of the mutual strengths of the kneaded polymers. , it is necessary to improve the dispersibility.
そこで非相溶なＡ，Ｂボリマーのブレンド系に、Ａに相
溶するポリマーとＢに相溶するボリマーとのブロックあ
るいはグラフト共重合体を少量添加することで相溶性を
起こすことができる。Therefore, compatibility can be caused by adding a small amount of a block or graft copolymer of a polymer compatible with A and a polymer compatible with B to a blend system of incompatible A and B polymers.
このようにポリマー間の界面張力を下げる働きをする高
分子改質剤を相溶化剤と称する。A polymer modifier that functions to lower the interfacial tension between polymers in this way is called a compatibilizer.
従来、反応基を有するモノマーを共重合するなどの方法
で変性されたポリオレフィンやボリスチレンは、相溶化
剤として数多く用いられてきた。例えば、ポリエステル
樹脂とポリアミド樹脂との相溶性を向上させるボリマー
として特開昭６０−２１７２６０号公報ではエチレンー
不飽和グリシジル共重合体が、特開昭６１−２１３２５
６号公報ではカルボン酸又は無水マレイン酸変性ポリオ
レフィンが、特開平１ −２２１４５３号公報ではα，
β一不飽和カルボン酸及びその誘導体等で変性されたボ
リスチレン等が利用されている。しかしこれらはすべて
の主鎖ボリマーに変性されている七ノマーが、ポリエス
テル樹脂又はボリアミド樹脂に選択的に作用するため、
両相を均一化させる効果が少なかった。Conventionally, polyolefins and polystyrenes modified by methods such as copolymerization with monomers having reactive groups have been widely used as compatibilizers. For example, in JP-A-60-217260, an ethylene-unsaturated glycidyl copolymer is used as a polymer that improves the compatibility between polyester resin and polyamide resin.
No. 6 uses carboxylic acid or maleic anhydride-modified polyolefin, and JP-A-1-221453 uses α,
Polystyrene modified with β-unsaturated carboxylic acid and derivatives thereof, etc. are used. However, these heptanomers, which are modified into all main chain polymers, act selectively on polyester resins or polyamide resins, so
The effect of homogenizing both phases was small.
〔課題を解決するための手段］
本発明者らは上記の課題を解決すべく鋭意研究の結果、
簡便且つ安価に重合でき、しかもポリエステル樹脂とボ
リアミド樹脂との相溶化剤として用いられるスチレン・
無水マレイン酸・グリシジルメタクリレート共重合体を
見出し本発明を完成するに至った。[Means for Solving the Problems] As a result of intensive research to solve the above problems, the present inventors have found that
Styrene can be easily and inexpensively polymerized and is used as a compatibilizer between polyester resin and polyamide resin.
They discovered a maleic anhydride/glycidyl methacrylate copolymer and completed the present invention.
構造単位８０〜９９重量％と、
一←Ｃｌ｛
ＣＨ→−
で示
０
される構造単位０．５〜１９重量％と、Ｃ｝１３
一←ＣＨｚ Ｃ→一 で示される構造単位０
．５〜１９重量％とからなる、数平均分子量５，０００
〜１００． ０００のスチレン・無水マレイン酸・グリ
シジルメタクリレートランダム共重合体を提供するもの
である。80 to 99% by weight of structural units, 0.5 to 19% by weight of structural units represented by 1←Cl{ CH→-, and 0 structural units represented by C}13 1←CHz C→1
．． 5-19% by weight, number average molecular weight 5,000
~100. 000 styrene/maleic anhydride/glycidyl methacrylate random copolymer.
本発明の三元共重合体に含まれる酸無水物基はボリアミ
ド樹脂の末端アミノ基とすばやく反応する。また同じ三
元共重合体中に含まれるグリシジルメタクリレートのエ
ボキシ基は、ポリエステル樹脂に対して極めて良好な相
溶性を有している。このため本発明の三元共重合体をポ
リエステル樹脂とポリアミド樹脂との混合物に特定量、
均一に混合すると均一な分散が実現された。The acid anhydride group contained in the terpolymer of the present invention quickly reacts with the terminal amino group of the polyamide resin. Furthermore, the epoxy group of glycidyl methacrylate contained in the same terpolymer has extremely good compatibility with polyester resin. For this purpose, a specific amount of the terpolymer of the present invention is added to a mixture of polyester resin and polyamide resin.
Uniform dispersion was achieved by uniform mixing.
本発明の共重合体を得るための重合方法としては、いわ
ゆる公知のラジカル共重合が用いられる。このラジカル
共重合の具体的な方法としては、更に溶液重合、乳化重
合、塊状重合、懸濁重合等から適宜選ばれる。As a polymerization method for obtaining the copolymer of the present invention, a so-called known radical copolymerization is used. The specific method for this radical copolymerization is further appropriately selected from solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and the like.
得られる共重合体のゲルパーミエーションク口マトグラ
フィーにより求められる標準ボリスチレンに換算した数
平均分子量としては、およそ５ ， ０００〜ｔｏｏ，
ｏｏｏの範囲が好ましい。数平均分子量が５，０００
を下廻るとその溶融粘度が低すぎるため、ポリエステル
樹脂、及びボリアミド樹脂との混練が困難となり好まし
くない。また数平均分子量が１００， ０００を上廻る
共重合体は、重合条件がきびしいため重合に困難を伴い
相溶化剤として好ましくない。The number average molecular weight of the obtained copolymer calculated by gel permeation chromatography in terms of standard polystyrene is approximately 5,000 to 5,000.
A range of ooo is preferred. Number average molecular weight is 5,000
If the melt viscosity is too low, it becomes difficult to knead with polyester resins and polyamide resins, which is not preferable. Furthermore, copolymers having a number average molecular weight of more than 100,000 are not preferred as compatibilizers because they are difficult to polymerize due to severe polymerization conditions.
本発明の共重合体中の各成分の割合としては、一←ＣＨ
２ＣＨ→ー
で示されるスチレン構造単位が
８０〜９９重量％であり、
−｛−Ｃ｝ｌ−ＣＨ→−
及び
０
ＣＨ３
イン酸及びグリシジルメタクリレート構成単位は各々必
須で０．５〜１９重量％の範囲である。The ratio of each component in the copolymer of the present invention is 1←CH
The styrene structural unit represented by 2CH→- is 80 to 99% by weight, and the -{-C}l-CH→- and 0CH3 inoic acid and glycidyl methacrylate structural units are each essential and 0.5 to 19% by weight. range.
この共重合体を相溶化剤としてポリエステル樹脂とボリ
アミド樹脂の混合物と溶融混練する際、共重合体中の無
水マレイン酸構成単位とグリシジルメタクリレート構成
単位の合計の全共重合体中に占める割合が２０重量％を
越えると、一部架橋反応を含む高分子間の反応が顕著と
なり、気泡を生じたり流動性が低下したりして、成形加
工性を著しく損なう事となり、好ましくない。また、逆
にこの割合が１重量％を下廻るとポリエステル樹脂とポ
リアミド樹脂との間の分散状態が不均一になり、得られ
る成形品の機械的性質も満足でなく表面の層状剥離等の
外観上の欠陥も生じる。When this copolymer is melt-kneaded with a mixture of polyester resin and polyamide resin as a compatibilizer, the total proportion of maleic anhydride constitutional units and glycidyl methacrylate constitutional units in the total copolymer is 20%. If it exceeds % by weight, reactions between polymers, including some crosslinking reactions, will become significant, resulting in the formation of bubbles and a decrease in fluidity, which will significantly impair moldability, which is not preferable. On the other hand, if this ratio is less than 1% by weight, the dispersion state between the polyester resin and polyamide resin will become non-uniform, and the mechanical properties of the resulting molded product will not be satisfactory, resulting in appearance such as delamination on the surface. The above defects also occur.
以下に実施例を挙げて本発明を更に詳細に説明するが、
本発明はこれらの実施例に限定されるものではない。The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these examples.
実施例１
（スチレン・無水マレイン酸・グリシジルメタクリレー
ト共重合体（１）の製造）
滴下ロ一ト、窒素導入管、温度計、冷却管、撹はん棒を
備えた４つ口フラスコに、スチレン（以下Ｓｔと記す）
６００ｇ及びグリシジルメタクリレート（以下ＧＭＡ
と記す）７０ｇからなるモノマー混合物を溶媒であるメ
チルエチルケトン（以下ＭＥＫと記す） １０００ｇに
溶解し、７０゜Ｃに昇温した。その後、重合開始剤であ
るアゾビスイソブチルニトリル（以下ＡＩＢＮと記す）
１５ｇと、Ｓｔ２６０ｇ、無水マレイン酸（以下ＭＡＲ
と記す）７０ｇ、及びＭＥＫ ２８０ｇからなるモノマ
ー混合物を逐次滴下し、重合を進めた。１０時間後フラ
スコを室温まで冷却すると同時に、大量のメタノール中
に投入し、析出してくるポリマーをデカントにより分取
し、さらに真空乾燥器中で減圧乾燥し、粉砕粉末化して
スチレン・無水マレイン酸・グリシジルメタクリレート
共重合体（１）８７０ｇを得た。Example 1 (Production of styrene/maleic anhydride/glycidyl methacrylate copolymer (1)) Styrene was placed in a four-necked flask equipped with a dropping funnel, nitrogen introduction tube, thermometer, cooling tube, and stirring bar. (hereinafter referred to as St)
600g and glycidyl methacrylate (hereinafter referred to as GMA)
A monomer mixture consisting of 70 g (hereinafter referred to as MEK) was dissolved in 1000 g of methyl ethyl ketone (hereinafter referred to as MEK) as a solvent, and the temperature was raised to 70°C. After that, azobisisobutylnitrile (hereinafter referred to as AIBN) which is a polymerization initiator
15g, St260g, maleic anhydride (hereinafter MAR
A monomer mixture consisting of 70 g of MEK and 280 g of MEK was sequentially added dropwise to proceed with polymerization. After 10 hours, the flask was cooled to room temperature and at the same time poured into a large amount of methanol, the precipitated polymer was collected by decant, dried under reduced pressure in a vacuum dryer, and ground into powder to form styrene/maleic anhydride. - 870 g of glycidyl methacrylate copolymer (1) was obtained.
ＧＰＣの測定によれば、共重合体（１）のボリスチレン
に換算した数平均分子量は１５，０００であった。According to GPC measurements, the number average molecular weight of copolymer (1) in terms of polystyrene was 15,000.
この共重合体（１）の赤外線吸収スペクトルを第１図に
示す。The infrared absorption spectrum of this copolymer (1) is shown in FIG.
第１図において、１８６０． １７８０ｃｍ−’に無水
物基の特性吸収ピークが見られるのをはじめグリシジル
メタクリレートに帰属されるエステル基の特性吸収（１
７３０ｃｍ− ’ ）及びスチレンのピーク（１６００
， ７６０， ７００ｃｍ−’等）が確認できる。また
共重合体（１）の１３Ｃ一核磁気共鳴吸収スペクトルを
第２図に示す。In FIG. 1, 1860. In addition to the characteristic absorption peak of the anhydride group at 1780 cm-', the characteristic absorption peak of the ester group assigned to glycidyl methacrylate (1
730 cm-') and the styrene peak (1600 cm-')
, 760, 700 cm-', etc.) can be confirmed. Furthermore, the 13C nuclear magnetic resonance absorption spectrum of copolymer (1) is shown in FIG.
これによると（ＣＤＣＩ．， ４６． ４９ｐｐｍ （
／’σ７），０
００
１１
５４ｐｐｍ （ Ｃｏ ＣＨ２ ）， １７０
〜１７４１）ｐｌｌｌ （ Ｃ −０ ）υ
ルメタクリレート、無水マレイン酸に帰属されるピーク
が確認できる。その他、ポリスチレンと同様なピークが
現れている。According to this (CDCI., 46.49ppm (
/'σ7), 0 00 11 54ppm (Co CH2), 170
~1741) Pllll(C-0)vl methacrylate and a peak attributed to maleic anhydride can be confirmed. Other peaks similar to those of polystyrene appear.
なお、′Ｈ一核磁気共鳴吸収スペクトルではスチレンに
帰属されるピークが大きく、グリシジルメタクリレート
の吸収ピークの積分強度が明確でないためその構成比は
分析できなかった。In addition, in the 'H nuclear magnetic resonance absorption spectrum, the peak attributed to styrene was large, and the integrated intensity of the absorption peak of glycidyl methacrylate was not clear, so the composition ratio could not be analyzed.
また、共重合体（１）の元素分析結果を表１に示す。こ
の表１の計算値は重合反応に用いた開始剤、モノマーが
全部ボリマーとして重合されたと仮定した時の値である
。これを比較すると、ほぼモノマーの仕込みどおりに重
合されていることがわかる。Table 1 also shows the results of elemental analysis of copolymer (1). The calculated values in Table 1 are based on the assumption that the initiators and monomers used in the polymerization reaction are all polymerized as polymers. Comparing this, it can be seen that the polymerization was carried out almost as the monomers were prepared.
表
■．
共重合体（１）の元素分析表
実施例２
（スチレン・無水マレイン酸・グリシジルメタクリレー
ト共重合体（２）の製造）
実施例１と同様な装置にＳｔ１３６０ｇ及びＧＭＡ ２
０ｇからなるモノマー混合物をＭＥＫ ６５０ｇに溶解
し、７０゜Ｃに昇温した。その後ＡＩＢＮ ３０ｇと、
ｓｔ６００ｇ、ＭＡＲ２０ｇ及びＭＥＫ ２８０ｇから
なるモノマー混合物を逐次滴下し、重合を進めた。Table ■． Elemental analysis table of copolymer (1) Example 2 (Production of styrene/maleic anhydride/glycidyl methacrylate copolymer (2)) 1360 g of St and GMA 2 were placed in the same apparatus as in Example 1.
A monomer mixture consisting of 0 g was dissolved in 650 g of MEK and the temperature was raised to 70°C. After that, with 30g of AIBN,
A monomer mixture consisting of 600 g of st, 20 g of MAR, and 280 g of MEK was successively added dropwise to proceed with polymerization.
１０時間後フラスコを室温まで冷却すると同時に、大量
のメタノール中に投入し、析出してくるポリマーをデカ
ントにより分取し、更に真空乾燥器中で減圧乾燥し、粉
砕粉末化してスチレン・無水マレイン酸・グリシジルメ
タクリレート共重合体（２） １８００ｇを得た。ＧＰ
Ｃの測定によれば、本樹脂のボリスチレンに換算した数
平均分子量は２１，０００であった。After 10 hours, the flask was cooled to room temperature and simultaneously poured into a large amount of methanol, the precipitated polymer was collected by decant, dried under reduced pressure in a vacuum dryer, and ground into powder to form styrene/maleic anhydride. - 1800 g of glycidyl methacrylate copolymer (2) was obtained. G.P.
According to the measurement of C, the number average molecular weight of this resin in terms of polystyrene was 21,000.
この共重合体（２）を用いて後述の実験例１で相溶化効
果を評価した。Using this copolymer (2), the compatibilization effect was evaluated in Experimental Example 1 described below.
比較例ｌ
（スチレン・無水マレイン酸共重合体の製造）実施例１
と同様な装置にｓｔ８００ｇ及びＭＡＲ１０ｇからなる
モノマー混合物をＭＥＫ ５００ｇに溶解し、７０゜Ｃ
に昇温した。その後ＡＩＢＮ １５ｇとＳｔ １８０ｇ
，台＾Ｈ Ｌｏｇ， ＭＥＫ １００ｇの混合モノマー
を逐次滴下し重合を進めた。Comparative Example 1 (Production of styrene/maleic anhydride copolymer) Example 1
A monomer mixture consisting of 800 g of st and 10 g of MAR was dissolved in 500 g of MEK in a similar apparatus, and heated at 70°C.
The temperature rose to . Then AIBN 15g and St 180g
, H Log, MEK 100 g of mixed monomers were sequentially added dropwise to proceed with polymerization.
１０時間後、実施例１と同様な操作により粉末化したス
チレン・無水マレイン酸共重合体９２０ｇを得た。ＧＰ
Ｃの測定によれば本樹脂のボリスチレンに換算した数平
均分子量は２８，０００であった。After 10 hours, 920 g of a powdered styrene/maleic anhydride copolymer was obtained by the same operation as in Example 1. G.P.
According to the measurement of C, the number average molecular weight of this resin in terms of polystyrene was 28,000.
比較例２
（スチレン・グリシジルメタクリレート共重合体の製造
）
実施例１と同様な装置にＳｔ ９８０ｇ， ＧＭＡ ２
０ｇからなる七ノマー混合物をＭＥＫ ６００ｇに溶解
し、７０゜Ｃに昇温した。その後、ＡＩＢＮ １５ｇを
滴下し重合を進めた。１０時間後実施例１と同様な操作
により粉末化したスチレン・グリシジルメタクリレート
共重合体９１０ｇを得た。Comparative Example 2 (Manufacture of styrene/glycidyl methacrylate copolymer) 980 g of St and 2 GMA were placed in the same apparatus as in Example 1.
A heptanomer mixture consisting of 0 g was dissolved in 600 g of MEK and the temperature was raised to 70°C. Thereafter, 15 g of AIBN was added dropwise to proceed with polymerization. After 10 hours, 910 g of powdered styrene/glycidyl methacrylate copolymer was obtained by the same operation as in Example 1.
ＧＰＣの測定によれば、本樹脂のポリスチレンに換算し
た数平均分子量は２５．０００であった。According to GPC measurements, the number average molecular weight of this resin in terms of polystyrene was 25.000.
実験例１
ナイロン６樹脂（宇部興産■製ナイロン６１０１３Ｂ，
以下ナイロン６と記す） ３４．２ｇ及びポリブチレン
テレフタレート（ポリプラスチック■製ジュラネフクス
２０００，以下ＰＢＴと記す） ２２．８ｇの混合物に
イ）実施例２で得られたスチレン・無水マレイン酸・グ
リシジルメタクリレート共重合体（２）３ｇ
口）比較例１で得られたスチレン・無水マレイン酸共重
合体１．５ｇと比較例２で得られたスチレン・グリシジ
ルメタクリレート共重合体１．５ｇとの混合物
イ），口）をそれぞれ加え、プラベンダー（２４０゜Ｃ
、５０回転／分）で５分間溶融混練を行った。Experimental example 1 Nylon 6 resin (Nylon 61013B manufactured by Ube Industries, Ltd.)
A) Styrene, maleic anhydride, and glycidyl methacrylate obtained in Example 2 were added to a mixture of 34.2 g (hereinafter referred to as nylon 6) and 22.8 g of polybutylene terephthalate (Juranefux 2000 manufactured by Polyplastic ■, hereinafter referred to as PBT). Polymer (2) 3 g A) A mixture of 1.5 g of the styrene/maleic anhydride copolymer obtained in Comparative Example 1 and 1.5 g of the styrene/glycidyl methacrylate copolymer obtained in Comparative Example 2. Add pravendar (240°C
, 50 rotations/min) for 5 minutes.
その後それぞれのサンプルを用いて２４０゜Ｃ、２００
ｋｇ／Ｃ４で厚さ３ｍｌｌ１のプレス板を作り、このプ
レス板を破断し、その破断面を走査型電子顕微鏡にて邊
影した．それぞれの写真のＰＢＴ ，ナイロン６の分散
粒子の大きさを測定した。その結果を表２に示す。After that, each sample was heated at 240°C and 200°C.
A press plate with a thickness of 3 ml1 was made using kg/C4, this press plate was fractured, and the fractured surface was imaged using a scanning electron microscope. The sizes of the dispersed particles of PBT and nylon 6 in each photograph were measured. The results are shown in Table 2.
表 ２．ＰＢＴ，ナイロン６０分散粒子の大きさこの結
果から無水マレイン酸及びグリシジルメタクリレートは
同じ共重合体中に必須であることが確認できた。Table 2. Size of PBT, Nylon 60 Dispersed Particles From these results, it was confirmed that maleic anhydride and glycidyl methacrylate are essential in the same copolymer.
一般に異種重合物同志の混合は相溶性が極めて悪く、均
一な海一島構造を得る事は困難であり、得られる混合系
組成物の成形片外観及び機械的物理化学的性能に好まし
からざる影響を与える。しかるに本発明のスチレン・無
水マレイン酸・グリシジルメタクリレート共重合体を高
分子多成分系、特にポリエステル系樹脂及びボリアミド
系樹脂の混合物に配合する事によって、極めて優れた分
散を可能にする事が出来、相溶性を向上させることがで
きる。In general, mixing different types of polymers has extremely poor compatibility, making it difficult to obtain a uniform island-in-the-sea structure, and causing unfavorable effects on the appearance and mechanical and physicochemical properties of molded pieces of the resulting mixed composition. give. However, by blending the styrene/maleic anhydride/glycidyl methacrylate copolymer of the present invention into a polymer multicomponent system, particularly a mixture of polyester resin and polyamide resin, extremely excellent dispersion can be achieved. Compatibility can be improved.
しかも、かかる本発明の共重合体を配合されたポリエス
テル樹脂・ポリアミド樹脂混合物はポリエステル系樹脂
及びボリアミド樹脂本来の諸性能を失う事なく、しかも
耐水性能の点で格段に改良された高い耐衝撃性を有する
成形用樹脂組成物となり得る。Moreover, the polyester resin/polyamide resin mixture blended with the copolymer of the present invention does not lose the properties inherent to polyester resins and polyamide resins, and has high impact resistance with markedly improved water resistance. It can be a molding resin composition having the following properties.
第１図はスチレン・無水マレイン酸・グリシジルメタク
リレート共重合体（１）の赤外線吸収スペクトル、第２
図は共重合体（１）のＩＩＣ一核磁気丑鳴吸収スペクト
ルを示す図である。
／）Figure 1 shows the infrared absorption spectrum of styrene/maleic anhydride/glycidyl methacrylate copolymer (1);
The figure shows the IIC mononuclear magnetic resonance absorption spectrum of copolymer (1). /)
Claims (1)
単位８０〜９９重量％と、 ▲数式、化学式、表等があります▼で示される構造単位
０．５〜１９ 重量％と、 ▲数式、化学式、表等があります▼で示される構造単 位０．５〜１９重量％とからなる、数平均分子量５，０
００〜１００，０００のスチレン・無水マレイン酸・グ
リシジルメタクリレートランダム共重合体。[Scope of Claims] 1 80 to 99% by weight of structural units represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 0.5 to 19% by weight of structural units represented by ▼ There are mathematical formulas, chemical formulas, tables, etc. % and a number average molecular weight of 5.0, consisting of 0.5 to 19% by weight of the structural unit indicated by ▲Formula, chemical formula, table, etc.▼
00 to 100,000 styrene/maleic anhydride/glycidyl methacrylate random copolymer.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013410A JP2801721B2 (en) | 1990-01-23 | 1990-01-23 | Polymer compatibilizer |
| DE1990607190 DE69007190T2 (en) | 1989-07-20 | 1990-07-16 | Resin composition and copolymer. |
| EP19900113624 EP0409152B1 (en) | 1989-07-20 | 1990-07-16 | Resin composition and copolymer |
| US08/027,924 US5373057A (en) | 1989-07-20 | 1993-03-08 | Resin composition and copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013410A JP2801721B2 (en) | 1990-01-23 | 1990-01-23 | Polymer compatibilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03217405A true JPH03217405A (en) | 1991-09-25 |
| JP2801721B2 JP2801721B2 (en) | 1998-09-21 |
Family
ID=11832364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013410A Expired - Fee Related JP2801721B2 (en) | 1989-07-20 | 1990-01-23 | Polymer compatibilizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2801721B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948688A (en) * | 2018-08-22 | 2018-12-07 | 中广核俊尔（上海）新材料有限公司 | A kind of fiber glass reinforced PBT/PET material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6055054A (en) * | 1983-09-06 | 1985-03-29 | Dainippon Ink & Chem Inc | Thermoplastic resin composition |
-
1990
- 1990-01-23 JP JP2013410A patent/JP2801721B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6055054A (en) * | 1983-09-06 | 1985-03-29 | Dainippon Ink & Chem Inc | Thermoplastic resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948688A (en) * | 2018-08-22 | 2018-12-07 | 中广核俊尔（上海）新材料有限公司 | A kind of fiber glass reinforced PBT/PET material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2801721B2 (en) | 1998-09-21 |
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