JP5754933B2 - Hydroxyl group-containing aromatic vinyl polymer, process for producing the same, and polystyrene resin foamable particles, pre-expanded particles, and foam-molded product comprising the same - Google Patents
Hydroxyl group-containing aromatic vinyl polymer, process for producing the same, and polystyrene resin foamable particles, pre-expanded particles, and foam-molded product comprising the same Download PDFInfo
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Description
本発明は、側鎖に水酸基を含有する芳香族ビニル系重合体とその製造方法、及びそれからなる発泡性樹脂粒子、予備発泡粒子、発泡成形品に関する。より詳しくは、側鎖に親水性の反応性基として水酸基を含有し、疎水性有機溶媒に可溶で、高ガラス相転移温度を有する芳香族ビニル系重合体とその製造方法及びそれからなる高独立気泡率を有し、剛性と耐衝撃性に優れ、断熱性、表面外観と寸法安定性が良好である発泡成型体に関する。 The present invention relates to an aromatic vinyl-based polymer containing a hydroxyl group in a side chain, a method for producing the same, and expandable resin particles, pre-expanded particles, and a foam-molded product comprising the same. More specifically, an aromatic vinyl polymer containing a hydroxyl group as a hydrophilic reactive group in the side chain, soluble in a hydrophobic organic solvent, and having a high glass phase transition temperature, a method for producing the same, and a highly independent method comprising the same The present invention relates to a foamed molded article having a cell ratio, excellent rigidity and impact resistance, heat insulation, surface appearance and dimensional stability.
一般に、熱可塑性樹脂であるポリスチレン系樹脂の発泡成形体は、軽量であり、かつ高い断熱性、緩衝性を有していることから、食品運搬用容器、建材用断熱材、家電製品の緩衝材等に幅広く使用されている(特許文献1〜3)。しかし、ポリスチレン系樹脂発泡成形体は、衝撃などによって割れやすい、即ち、耐衝撃性が低いという短所を有しており、また、均一でかつ微細な気泡構造を得られ難いので、剛性や機械的強度、耐衝撃性、高温雰囲気下での寸法安定性、表面外観なども要求される高機能性材料にはまだ用いられていないのが現状である。 In general, a foamed molded product of a polystyrene-based resin, which is a thermoplastic resin, is lightweight and has high heat insulating properties and buffering properties. Therefore, food transport containers, heat insulating materials for building materials, and buffer materials for home appliances. (Patent documents 1 to 3). However, polystyrene-based resin foam moldings have the disadvantages of being easily cracked by impact or the like, that is, having low impact resistance, and it is difficult to obtain a uniform and fine cell structure. At present, it has not yet been used for high-functional materials that require strength, impact resistance, dimensional stability under high temperature atmosphere, surface appearance, and the like.
ポリスチレン系樹脂発泡成形体の製造方法は、主に押出発泡法と予備発泡粒子発泡法である。押出発泡法は、ポリスチレン系樹脂を押出機などにて加熱溶融し、続いて発泡剤を添加、樹脂中に分散させ、これを押出機のダイスから低圧域に押出すことにより急速に発泡、冷却させ、発泡体を連続的に製造する方法である。この方法で得られるポリスチレン系樹脂押出発泡体は、住宅や家屋の床材、壁材、天井材など断熱材として多用され、その断熱性と剛性が特に要求されている。 The manufacturing method of the polystyrene resin foam molding is mainly an extrusion foaming method and a pre-expanded particle foaming method. In the extrusion foaming method, polystyrene resin is heated and melted in an extruder, etc., followed by adding a foaming agent, dispersing it in the resin, and extruding it from the die of the extruder into a low pressure region, thereby rapidly foaming and cooling. And producing a foam continuously. The polystyrene resin extruded foam obtained by this method is frequently used as a heat insulating material such as a flooring material, a wall material, a ceiling material of a house or a house, and its heat insulating property and rigidity are particularly required.
ポリスチレン系樹脂押出発泡体の断熱性を向上させるために、ガスバリアー性樹脂としてビニルアルコール系樹脂をポリスチレン系樹脂に添加して押出発泡断熱板を製造する方法(特許文献4)、ポリスチレン系樹脂にポリアミド樹脂を配合することにより物理発泡剤の散逸が抑制され、長期間に亘り断熱性のよいポリスチレン系樹脂押出発泡体を製造する方法(特許文献5)が提案されている。しかし、ビニルアルコール系樹脂もポリアミド樹脂も親水性ポリマーであり、比較的極性の弱い疎水性ポリスチレン樹脂との相溶性が悪く、均一に分散させるためにはスチレンと(メタ)アクリル酸の共重合体を用いるか(特許文献4)、混練温度や剪断速度、溶融粘度、半結晶化時間などの精密な製造条件で制御する必要であり、製造工程が煩雑になり、製造コストが高くつくという問題がある。また、これらの方法で得られる発泡成形体は、断熱性と断熱性能保持性を向上されたものであるが、耐衝撃性が低いという問題が残されたままである。 In order to improve the heat insulation of the polystyrene resin extruded foam, a method of producing an extruded foam heat insulating plate by adding a vinyl alcohol resin as a gas barrier resin to the polystyrene resin (Patent Document 4), There has been proposed a method (Patent Document 5) for producing a polystyrene resin extruded foam that suppresses dissipation of a physical foaming agent by blending a polyamide resin and has good heat insulation over a long period of time. However, both vinyl alcohol resins and polyamide resins are hydrophilic polymers and have poor compatibility with hydrophobic polystyrene resins with relatively low polarity, and in order to disperse uniformly, a copolymer of styrene and (meth) acrylic acid (Patent Document 4), it is necessary to control under precise production conditions such as kneading temperature, shear rate, melt viscosity, semi-crystallization time, and the production process becomes complicated and the production cost is high. is there. Moreover, although the foaming molding obtained by these methods has improved heat insulation and heat insulation performance retainability, the problem that impact resistance is low remains.
一方、予備発泡粒子発泡法は、ポリスチレン系樹脂に揮発性発泡剤を含浸することで発泡性能を有するポリスチレン系樹脂の発泡性粒子を得、この発泡性粒子を予備発泡させることにより予備発泡粒子を製造し、さらに得られる予備発泡粒子を型内成型することで発泡体を製造する方法である。この予備発泡法で得られるポリスチレン系樹脂の発泡成形体は、特許文献6に記述したように、低密度で断熱性や外観が良いため、食品用保温剤、建材用断熱材などに好適に用いられる。しかし、この発泡成形体の製造に使用される原料は一定範囲の分子量と特有の溶融特性(メルトフロー測定時の膨張割合)を有するポリスチレン樹脂に限定されており、また、成形体は発泡性と気泡膜の耐破れ性が改善されたものであるが、機械的強度や耐衝撃性が低いという問題の改善手段について、言及されていなかった。 On the other hand, the pre-expanded particle foaming method obtains expandable particles of polystyrene resin having foaming performance by impregnating a polystyrene resin with a volatile foaming agent, and pre-expands the expandable particles by pre-expanding the expandable particles. This is a method for producing a foam by in-mold molding the pre-expanded particles that are produced. As described in Patent Document 6, the foamed molded product of polystyrene resin obtained by this pre-foaming method is suitable for use as a heat insulating material for food, a heat insulating material for building materials, etc. because of its low density and good heat insulation and appearance. It is done. However, the raw materials used in the production of the foamed molded product are limited to polystyrene resins having a certain range of molecular weight and specific melting characteristics (expansion ratio at the time of melt flow measurement). Although the tear resistance of the cell membrane has been improved, there has been no mention of means for improving the problem of low mechanical strength and impact resistance.
ポリスチレン系樹脂発泡成形体の耐衝撃性を改善する目的で、ポリスチレン樹脂に耐衝撃性に優れるポリオレフィン樹脂、ポリウレタン樹脂などを導入することが提案された。例えば、特許文献7では、スチレン樹脂、オレフィン樹脂、スチレン系エラストマー及び発泡逸散防止剤からなる混合樹脂の発泡性粒子を使用し、耐衝撃性や緩衝性に優れた発泡体を製造した。特許文献8では、ポリオレフィン系樹脂粒子にスチレン系モノマーを含浸重合し、得られるポリスチレン系樹脂粒子にさらに揮発性発泡剤を含有させたものを発泡性ポリスチレン系樹脂粒子として使用し、耐割れ性のよい発泡成型品を提供した。また、特許文献9では、熱可塑性ポリウレタン樹脂に特定粒子径のポリスチレン系樹脂粒子が分散された状態で存在することを特徴とするスチレン改質熱可塑性ポリウレタン樹脂粒子を使用することにより、靭性の高い発泡成形体を製造できた。 In order to improve the impact resistance of polystyrene-based resin foam moldings, it has been proposed to introduce a polyolefin resin, a polyurethane resin, or the like that has excellent impact resistance into the polystyrene resin. For example, in Patent Document 7, foamed particles of a mixed resin composed of a styrene resin, an olefin resin, a styrene-based elastomer, and an anti-foaming agent were used to produce a foam having excellent impact resistance and buffering properties. In Patent Document 8, a polyolefin resin particle is impregnated and polymerized with a styrene monomer, and the resulting polystyrene resin particle further containing a volatile foaming agent is used as the expandable polystyrene resin particle. Provided a good foam molded product. Further, in Patent Document 9, high toughness is obtained by using styrene-modified thermoplastic polyurethane resin particles characterized in that polystyrene resin particles having a specific particle diameter are dispersed in the thermoplastic polyurethane resin. A foamed molded product could be produced.
しかし、これらの方法では、ポリスチレン樹脂の脆いという短所をある程度改善されるが、ポリオレフィン樹脂とポリウレタン樹脂の発泡成形時の致命的な発泡性問題によるマイナス影響もある。それは、これらの樹脂からなる樹脂粒子が揮発性発泡剤を含浸、発泡させる際の独立発泡率が極めて低く、また、発泡後の粒子から発泡剤が逸散しやすく、良好な発泡体を作製することができないという問題である。さらに、ポリオレフィン樹脂もポリウレタン樹脂もポリスチレン樹脂とは相溶しないため、良好な発泡性、気泡保持性を有するポリスチレン樹脂を配合させても問題の解決には至らない。 However, these methods can improve the weakness of the brittleness of the polystyrene resin to some extent, but also have a negative effect due to a fatal foaming problem at the time of foam molding of the polyolefin resin and the polyurethane resin. It has a very low independent foaming rate when resin particles made of these resins are impregnated and foamed with a volatile foaming agent, and the foaming agent is easily dissipated from the foamed particles to produce a good foam. It is a problem that cannot be done. Furthermore, since neither polyolefin resin nor polyurethane resin is compatible with polystyrene resin, the problem cannot be solved even by blending polystyrene resin having good foamability and bubble retention.
特許文献7は発泡剤逸散防止剤として高級脂肪酸とアルコールの部分エステルを添加しているが、それらの極性成分がポリスチレン樹脂に相溶せず、ポリオレフィン樹脂にはさらに相溶しないので、樹脂粒子中に均一に分散されず、十分な発泡剤逸散防止効果を得ることができない。 Patent Document 7 adds a higher fatty acid and a partial ester of alcohol as a foaming agent dissipation inhibitor, but their polar components are not compatible with polystyrene resin, and are not compatible with polyolefin resin. It is not uniformly dispersed therein, and a sufficient foaming agent dissipation preventing effect cannot be obtained.
以上の記述により、高い独立気泡率を有し、剛性と耐衝撃性に優れ、かつ、断熱性、表面外観と寸法安定性が良好であるポリスチレン系樹脂の発泡成型品において、従来の技術では得られない状況である。 Based on the above description, polystyrene-based foamed molded products with high closed cell ratio, excellent rigidity and impact resistance, heat insulation, surface appearance and dimensional stability can be obtained by conventional technology. It is a situation that can not be.
本発明は、上記の問題を解決した、ポリスチレン系樹脂との相溶性に優れ、側鎖に水酸基を持ちながら疎水性であり、高ガラス転移温度を有し、少量添加で、ポリスチレン系樹脂発泡性粒子中及び/又はポリスチレン系樹脂発泡成形体中に均一に分散でき、十分な発泡剤逸散防止効果を付与できる芳香族ビニル系重合体を提供することを課題とする。
また、本発明は、このような芳香族ビニル系重合体を配合した、ポリスチレン系樹脂組成物、ポリスチレン系樹脂発泡性粒子と予備発泡粒子、押出発泡法或いは予備発泡粒子発泡法で得られる高独立気泡率を有し、剛性と耐衝撃性に優れ、断熱性、表面外観と寸法安定性、帯電防止性の良いポリスチレン系樹脂発泡成形体を提供することを課題とする。
The present invention solves the above problems, is excellent in compatibility with polystyrene resin, is hydrophobic while having a hydroxyl group in a side chain, has a high glass transition temperature, and is added in a small amount to expand polystyrene resin. It is an object of the present invention to provide an aromatic vinyl polymer that can be uniformly dispersed in particles and / or a polystyrene-based resin foam molded article, and that can provide a sufficient foaming agent escape prevention effect.
The present invention also provides a polystyrene resin composition, a polystyrene resin expandable particle and a pre-expanded particle, an extrusion foaming method or a pre-expanded particle foaming method, which contains such an aromatic vinyl polymer. It is an object of the present invention to provide a polystyrene resin foam molded article having a cell ratio, excellent rigidity and impact resistance, heat insulation, surface appearance and dimensional stability, and good antistatic properties.
本発明者らはこれらの課題を解決するために鋭意検討を行った結果、側鎖にオキサゾリン基を有する共重合体を合成した後、有機溶媒中で水と水和反応することにより側鎖に水酸基を持ち、疎水性で有機溶媒にも可溶な、高いガラス相転移温度を有する芳香族ビニル系重合体が容易に得られることを見出した。また、芳香族ビニル系重合体がポリスチレン系樹脂に対して優れた相溶性を有し、少量添加でも高い独立気泡率と十分な発泡剤逸散防止効果を付与でき、それを配合することにより前記特性を有するポリスチレン系樹脂発泡成形体が得られることを見出し、本発明に到達した。
すなわち本発明は、
(1)側鎖に水酸基を有し、ガラス相転移温度(Tg)が50〜180℃であり、且つ溶解性パラメーター(SP値)が8〜11(cal/cm3)1/2の有機溶媒に可溶である芳香族ビニル系重合体、
(2)一般式(1)(式中、R1は水素原子又はメチル基を、R2〜R5は同一又は異なって水素原子又は炭素数1〜3の直鎖もしくは分岐鎖のアルキル基、R6、R7は同一又は異なって水素原子又はメチル基を表し、構造単位aの配合量は1〜50モル%、構造単位bの配合量は99〜50モル%である。)で示される前記(1)記載の芳香族ビニル系重合体、
(4)前記(3)記載の有機溶媒がジイソブチルアジペート等のアジピン酸エステル、ジ−2−エチルヘキシルフタレート等のフタル酸エステル、グリセリンジアセトモノラウレート等のグリセリン脂肪酸エステルであることを特徴とする、前記(1)〜(3)のいずれか一項に記載の芳香族ビニル系重合体、
(5)前記(1)〜(4)のいずれか一項に記載の芳香族ビニル系重合体が、一般式(2)(式中、R1は水素原子又はメチル基を、R2〜R5は同一又は異なって水素原子又は炭素数1〜3の直鎖もしくは分岐鎖のアルキル基、R6、R7は同一又は異なって水素原子又はメチル基を表し、構造単位cの配合量は1〜50モル%、構造単位bの配合量は99〜50モル%である。)で示される側鎖にオキサゾリン基を有する共重合体が、有機溶媒中で水との水和反応により合成されることを特徴とする製造方法、
(7)前記(1)乃至(4)のいずれか一項に記載の芳香族ビニル系重合体を0.01重量%以上含有することを特徴とするポリスチレン系樹脂発泡性粒子、予備発泡粒子及びそれらからなるポリスチレン系樹脂発泡成形体
を提供するものである。
As a result of intensive studies to solve these problems, the present inventors synthesized a copolymer having an oxazoline group in the side chain, and then hydrated it with water in an organic solvent to form a side chain. It was found that an aromatic vinyl polymer having a high glass phase transition temperature having a hydroxyl group, hydrophobic and soluble in an organic solvent can be easily obtained. In addition, the aromatic vinyl polymer has excellent compatibility with the polystyrene resin, and even when added in a small amount, it can impart a high closed cell ratio and a sufficient blowing agent dissipation preventing effect, The inventors have found that a polystyrene-based resin foam molded article having characteristics can be obtained, and have reached the present invention.
That is, the present invention
(1) An organic solvent having a hydroxyl group in a side chain, a glass phase transition temperature (Tg) of 50 to 180 ° C., and a solubility parameter (SP value) of 8 to 11 (cal / cm 3 ) 1/2 An aromatic vinyl polymer that is soluble in
(2) General formula (1) (wherein R 1 is a hydrogen atom or a methyl group, R 2 to R 5 are the same or different and are a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, R 6 and R 7 are the same or different and each represents a hydrogen atom or a methyl group. The compounding amount of the structural unit a is 1 to 50 mol%, and the compounding amount of the structural unit b is 99 to 50 mol%. The aromatic vinyl polymer according to (1),
(4) The organic solvent according to (3) is an adipic acid ester such as diisobutyl adipate, a phthalic acid ester such as di-2-ethylhexyl phthalate, or a glycerin fatty acid ester such as glycerin diacetomonolaurate. The aromatic vinyl polymer according to any one of (1) to (3),
(5) The aromatic vinyl polymer according to any one of (1) to (4) has the general formula (2) (wherein R 1 represents a hydrogen atom or a methyl group, R 2 to R 5 is the same or different and is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms; R 6 and R 7 are the same or different and each represents a hydrogen atom or a methyl group; A copolymer having an oxazoline group in the side chain represented by ˜50 mol% and the blending amount of the structural unit b is 99 to 50 mol%) is synthesized by a hydration reaction with water in an organic solvent. A production method characterized by
(7) Polystyrene resin expandable particles, pre-expanded particles, containing 0.01% by weight or more of the aromatic vinyl polymer according to any one of (1) to (4) The present invention provides a polystyrene-based resin foam molded article made of them.
本発明の芳香族ビニル系重合体は、側鎖に水酸基を有し、疎水性であり、かつ、高いガラス相転移温度を有している。該芳香族ビニル系重合体は側鎖にオキサゾリン基を有する共重合体を合成した後、有機溶媒中で水との水和反応により容易に製造することができる。また、該芳香族ビニル系重合体がポリスチレン系樹脂との相溶性に優れ、少量添加で、ポリスチレン系樹脂発泡性粒子中及び/又はポリスチレン系樹脂発泡成形体中に均一に分散でき、高い独立気泡率と十分な発泡剤逸散防止効果が得られ、押出発泡法でも予備発泡粒子発泡法でも、高独立気泡率を有し、剛性と耐衝撃性に優れ、断熱性、表面外観、寸法安定性と帯電防止性の良いポリスチレン系樹脂発泡成形体を取得することができる。
該芳香族ビニル系重合体が側鎖に水酸基を有し、気泡調整効果、発泡剤逸散防止効果、発泡性粒子と予備発泡粒子の帯電防止効果が提供でき、また、発泡成形体の金型からの離型性を改善する効果がある。さらに、水酸基の反応性を利用して、機能性官能基を導入することや、酸無水物やイソシアネート等との反応による部分架橋した高耐熱性、耐割れ性粒子、成形体を製造することができる。
同時に、該芳香族ビニル系重合体の側鎖に水酸基と同モルのアミド基を有するため、高いガラス相転移温度との相乗効果で耐熱性と寸法安定性に優れている特徴がある。
The aromatic vinyl polymer of the present invention has a hydroxyl group in the side chain, is hydrophobic, and has a high glass phase transition temperature. The aromatic vinyl polymer can be easily produced by synthesizing a copolymer having an oxazoline group in the side chain and then hydrating with water in an organic solvent. In addition, the aromatic vinyl polymer is excellent in compatibility with the polystyrene resin, and can be uniformly dispersed in the polystyrene resin foamable particles and / or the polystyrene resin foam molded article with a small amount of addition, and high closed cell And a sufficient foaming agent dissipation prevention effect, with high foaming ratio, excellent rigidity and impact resistance, heat insulation, surface appearance, and dimensional stability. And a polystyrene-based resin foam molded article with good antistatic properties can be obtained.
The aromatic vinyl polymer has a hydroxyl group in the side chain, and can provide a bubble adjusting effect, a foaming agent dissipation preventing effect, an antistatic effect of foamable particles and pre-expanded particles, and a mold for a foamed molded product There is an effect to improve the release property from the. Furthermore, by utilizing the reactivity of hydroxyl groups, it is possible to introduce functional functional groups, and to produce partially heat-resistant, crack-resistant particles and molded bodies that are partially crosslinked by reaction with acid anhydrides, isocyanates, etc. it can.
At the same time, the side chain of the aromatic vinyl polymer has an amide group having the same mole as the hydroxyl group, and thus has a feature of excellent heat resistance and dimensional stability due to a synergistic effect with a high glass phase transition temperature.
以下、本発明を詳細に説明する。
本発明の芳香族ビニル系重合体は側鎖に水酸基を有し、ガラス相転移温度(Tg)が50〜180℃であり、且つ溶解性パラメーター(SP値)が8〜11(cal/cm3)1/2の有機溶媒に可溶な重合体である。
Hereinafter, the present invention will be described in detail.
The aromatic vinyl polymer of the present invention has a hydroxyl group in the side chain, a glass phase transition temperature (Tg) of 50 to 180 ° C., and a solubility parameter (SP value) of 8 to 11 (cal / cm 3). ) Polymer soluble in 1/2 organic solvent.
本発明の芳香族ビニル系重合体中の水酸基含有量は1〜50モル%である。1モル%未満であると、気泡調整効果、発泡剤逸散防止効果と帯電防止効果などが十分に期待できず、一方、50モル%を超えると、芳香族ビニル系重合体の親水性が強くなり、ポリスチレン系樹脂との相溶性が低下し、結果は同様に気泡調整効果と発泡剤逸散防止効果が得られないため好ましくない。 The hydroxyl group content in the aromatic vinyl polymer of the present invention is 1 to 50 mol%. If the amount is less than 1 mol%, the effect of adjusting the air bubbles, the effect of preventing foaming agent dissipation and the antistatic effect cannot be sufficiently expected. On the other hand, if the amount exceeds 50 mol%, the hydrophilicity of the aromatic vinyl polymer is strong. Therefore, the compatibility with the polystyrene resin is lowered, and the result is not preferable because the effect of adjusting the bubbles and the effect of preventing the foaming agent from being diffused cannot be obtained.
本発明の芳香族ビニル系重合体は、ガラス相転移温度(Tg)が50〜180℃であり、好ましくは70〜170℃、特に好ましくは80〜150℃である。Tgが50℃未満であると、該芳香族ビニル系重合体の配合量にもよるが、それを用いた発泡成形体の耐熱性低下を招くことや、予備発泡粒子発泡法で得られる発泡性粒子又は予備発泡粒子において、成形前の粒子同士の結合が起こる可能性がある。一方、Tgが180℃越えると、高い混練、成形温度が必要となり、成形性、加工性が悪くなると共に高温下のポリスチレン系樹脂の熱分解も発生する恐れがある。なお、Tgの測定は実施例に記載してある方法で行う。 The aromatic vinyl polymer of the present invention has a glass phase transition temperature (Tg) of 50 to 180 ° C, preferably 70 to 170 ° C, particularly preferably 80 to 150 ° C. If the Tg is less than 50 ° C., it depends on the blending amount of the aromatic vinyl polymer, but it causes a decrease in heat resistance of the foamed molded product using the same, and the foamability obtained by the prefoamed particle foaming method. In the particles or the pre-expanded particles, bonding between the particles before molding may occur. On the other hand, if the Tg exceeds 180 ° C., a high kneading and molding temperature is required, the moldability and processability are deteriorated, and the thermal decomposition of the polystyrene resin at a high temperature may occur. Tg is measured by the method described in the examples.
本発明の芳香族ビニル系重合体は、溶解性パラメーター(SP値)が8〜11(cal/cm3)1/2の有機溶媒に可溶な重合体である。SP値は、Polymer Engineer Science, Vol.14, P.147,Y.1974に記載のFedorsの方法によって計算される値である。SP値が低い程、化合物の疎水性が高くなるが、11以下であると本発明に要求される疎水性が到達でき、且つ芳香族ビニル系重合体の溶解性、ポリスチレン系樹脂及び他の添加成分との相溶性、分散性が共に良好となる。 The aromatic vinyl polymer of the present invention is a polymer soluble in an organic solvent having a solubility parameter (SP value) of 8 to 11 (cal / cm 3 ) 1/2 . The SP value is a value calculated by the Fedors method described in Polymer Engineer Science, Vol. 14, P. 147, Y. 1974. The lower the SP value, the higher the hydrophobicity of the compound, but when it is 11 or less, the hydrophobicity required for the present invention can be reached, and the solubility of the aromatic vinyl polymer, polystyrene resin and other additions Both compatibility with components and dispersibility are improved.
SP値が8〜11(cal/cm3)1/2の有機溶媒とは、例えば、酢酸メチル、酢酸エチル、酢酸−n−プロピル、酢酸イソプロピル、酢酸ブチルなどの酢酸エステル、キシレン、トルエン、ベンゼン、アセトン、メチルエチルケトンなどの汎用有機溶媒、ジブチルフタレート、ブチルベンジルフタレート、ジオクチルフタレート、ジノルマルオクチルフタレート、ジ−2−エチルヘキシルフタレート等のフタル酸エステル、ジオクチルアジペート、ジイソブチルアジペート、ジイソノニルアジペートアセチルトリブチルシトレート等のアジピン酸エステル、グリセリンモノアセトモノラウレート、グリセリンジアセトモノラウレート、グリセリンモノアセトモノステアレート等のグリセリン脂肪酸エステルなどが挙げられる。中でも、高沸点で汎用な可塑剤であるジブチルアジペート(DIBA)が特に好ましい。 Examples of organic solvents having an SP value of 8 to 11 (cal / cm 3 ) 1/2 include acetates such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, and butyl acetate, xylene, toluene, and benzene. General purpose organic solvents such as acetone, methyl ethyl ketone, phthalic acid esters such as dibutyl phthalate, butyl benzyl phthalate, dioctyl phthalate, di-normal octyl phthalate, di-2-ethylhexyl phthalate, dioctyl adipate, diisobutyl adipate, diisononyl adipate acetyl tributyl citrate And glycerol fatty acid esters such as glycerol monoacetomonolaurate, glycerol diacetomonolaurate and glycerol monoacetomonostearate. Among them, dibutyl adipate (DIBA), which is a general plasticizer having a high boiling point, is particularly preferable.
本発明の芳香族ビニル系重合体はSP値8〜11(cal/cm3)1/2の有機溶媒に可溶な重合体である。可溶というのは、芳香族ビニル系重合体がと有機溶媒に対する溶解度が1(g/100g)以上、即ち、有機溶媒100gに対して芳香族ビニル系重合体が1g以上可溶であり、中でも5(g/100g)以上、特に10(g/100g)以上可溶なものが好ましい。溶解度が1(g/100g)未満の場合、芳香族ビニル系重合体の疎水性が欠けていることとなり、十分にポリスチレン系樹脂と相溶化できない。また、該芳香族ビニル系重合体をジブチルアジペート(DIBA)中に溶解してから使用される場合、十分な配合量と機能付与は期待できない。 The aromatic vinyl polymer of the present invention is a polymer soluble in an organic solvent having an SP value of 8 to 11 (cal / cm 3 ) 1/2 . Soluble means that the aromatic vinyl polymer has a solubility in an organic solvent of 1 (g / 100 g) or more, that is, 1 g or more of the aromatic vinyl polymer is soluble in 100 g of the organic solvent, It is preferably 5 (g / 100 g) or more, particularly 10 (g / 100 g) or more. When the solubility is less than 1 (g / 100 g), the aromatic vinyl polymer lacks hydrophobicity and cannot be sufficiently compatible with the polystyrene resin. In addition, when the aromatic vinyl polymer is used after being dissolved in dibutyl adipate (DIBA), a sufficient blending amount and function cannot be expected.
本発明の芳香族ビニル系重合体は、側鎖に水酸基を有する重合体であり、側鎖にオキサゾリン基を有する共重合体を合成した後、有機溶媒中で水との水和反応により製造されるものである。 The aromatic vinyl polymer of the present invention is a polymer having a hydroxyl group in the side chain, and is produced by synthesizing a copolymer having an oxazoline group in the side chain and then hydrating with water in an organic solvent. Is.
側鎖にオキサゾリン基を有する共重合体は一般式(2)で表され、アルケニルオキサゾリンと芳香族ビニル系単量体を主成分とするラジカル共重合体であり、式中のR1は水素原子又はメチル基を、R2〜R5は同一又は異なって水素原子又は炭素数1〜3の直鎖もしくは分岐鎖のアルキル基、R6、R7は同一又は異なって水素原子又はメチル基を表し、構造単位cの配合量は1〜50モル%、構造単位bの配合量は99〜50モル%である。
アルケニルオキサゾリンはオキサゾリン基を有するビニルモノマーであり、具体的には、2−ビニル−2−オキサゾリン、4−メチル−2−ビニル−2−オキサゾリン、5−メチル−2−ビニル−2−オキサゾリン、4−エチル−2−ビニル−2−オキサゾリン、5−エチル−2−ビニル−2−オキサゾリン、4,4−ジメチル−2−ビニル−2−オキサゾリン、4,4−ジエチル−2−ビニル−2−オキサゾリン、4,5−ジメチル−2−ビニル−2−オキサゾリン、4,5−ジエチル−2−ビニル−2−オキサゾリン、2−イソプロペニル−2−オキサゾリン、4−メチル−2−イソプロペニル−2−オキサゾリン、5−メチル−2−イソプロペニル−2−オキサゾリン、4−エチル−2−イソプロペニル−2−オキサゾリン、5−エチル−2−イソプロペニル−2−オキサゾリン、4,4−ジメチル−2−イソプロペニル−2−オキサゾリン、4,4−ジエチル−2−イソプロペニル−2−オキサゾリン、4,5−ジメチル−2−イソプロペニル−2−オキサゾリン、4,5−ジエチル−2−イソプロペニル−2−オキサゾリンなど等を例示することができる。これらアルケニルオキサゾリンの中では、水との水和反応性が高反応性という観点から、2−ビニル−2−オキサゾリン、2−イソプロペニル−2−オキサゾリン、5−メチル−2−ビニル−2−オキサゾリン、4,4−ジメチル−2−ビニル−2−オキサゾリンが好ましく、さらに2−ビニル−2−オキサゾリンが最も好ましい。これらアルケニルオキサゾリンは1種あるいは2種以上を用いることができる。 Alkenyl oxazoline is a vinyl monomer having an oxazoline group, specifically, 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4 -Ethyl-2-vinyl-2-oxazoline, 5-ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline 4,5-dimethyl-2-vinyl-2-oxazoline, 4,5-diethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline 5-methyl-2-isopropenyl-2-oxazoline, 4-ethyl-2-isopropenyl-2-oxazoline, 5-ethyl 2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4,4-diethyl-2-isopropenyl-2-oxazoline, 4,5-dimethyl-2-isopropenyl Examples include 2-oxazoline, 4,5-diethyl-2-isopropenyl-2-oxazoline, and the like. Among these alkenyl oxazolines, 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline from the viewpoint of high hydration reactivity with water. 4,4-dimethyl-2-vinyl-2-oxazoline is preferred, and 2-vinyl-2-oxazoline is most preferred. These alkenyl oxazolines can be used alone or in combination of two or more.
本発明に用いられるアルケニルオキサゾリンは、本発明者等が先に出願した下記の特許文献10等記載の方法で製造できる。 The alkenyl oxazoline used in the present invention can be produced by the method described in the following Patent Document 10 and the like filed previously by the present inventors.
特許文献10:特開2001−058986号公報、特開2002−275166号公報、特開2004−250391号公報、特開2004−238342号公報、特開2004−238343号公報、特開2004−238344号公報 Patent Document 10: JP 2001-058986 A, JP 2002-275166 A, JP 2004-250391 A, JP 2004-238342 A, JP 2004-238343 A, JP 2004-238344 A. Gazette
芳香族ビニル系単量体は、具体的には、スチレン、α−メチルスチレン、p−メチルスチレン、ビニルトルエン、t−ブチルスチレン、o−エチルスチレン、o−クロロスチレン及びo,p−ジクロロスチレン等が挙げられるが、特にスチレン、α−メチルスチレンが安価な工業品を入手しやすいため、好ましい。 Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene, and o, p-dichlorostyrene. In particular, styrene and α-methylstyrene are preferable because inexpensive industrial products are easily available.
また、アルケニルオキサゾリンと芳香族ビニル系単量体が構成単位として、他の共重合可能なビニル系単量体との多元共重合することもできる。他の共重合可能なビニル系単量体としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、(メタ)アクリルアミド、(メタ)アクリロニトリル、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレート等が挙げられる。これらの共重合可能なビニル系単量体が単独でもよく、2種以上混合使用しても良く、配合される各種他の共重合可能なビニル系単量体のモル分率の合計は、30%以下であることが好ましい。 In addition, multi-component copolymerization with other copolymerizable vinyl monomers can also be performed with alkenyl oxazoline and an aromatic vinyl monomer as constituent units. Other copolymerizable vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, hydroxyethyl (Meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like can be mentioned. These copolymerizable vinyl monomers may be used alone or in combination of two or more. The total molar fraction of various other copolymerizable vinyl monomers to be blended is 30 % Or less is preferable.
アルケニルオキサゾリンと芳香族ビニル系単量体の共重合方法としては、特に限定されるものではなく、公知のラジカル重合法により実施可能である。例えば、本発明者等が先に出願した下記の特許文献11等記載の方法を参考できる。例えばアルコール、酢酸エチルなどの有機溶媒中の溶液重合、懸濁重合、乳化重合、塊状重合法などが挙げられる。有機溶媒中の溶液重合法を採用する場合、重合溶媒としては、トルエン、キシレン、酢酸エチル、酢酸ブチル、メチルエチルケトン、メチルアルコール、エチルアルコールなどの単独もしくは混合で用いることができる。 The method for copolymerizing the alkenyl oxazoline and the aromatic vinyl monomer is not particularly limited, and can be carried out by a known radical polymerization method. For example, it is possible to refer to the method described in the following Patent Document 11 and the like filed earlier by the present inventors. Examples thereof include solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization in an organic solvent such as alcohol and ethyl acetate. When the solution polymerization method in an organic solvent is employed, as a polymerization solvent, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl alcohol, ethyl alcohol, or the like can be used alone or in combination.
特許文献11:特開2007−246615号公報、特開2009−120802号公報 Patent Document 11: JP 2007-246615 A, JP 2009-120802 A
重合開始剤としては、アゾ系、有機過酸化物系、無機過酸化物系、レドックス系など一般的に知られている重合開始剤が挙げられる。重合開始剤の使用量としては、通常重合性単量体成分総量に対して0.001〜10重量%程度である。また、連鎖移動剤による分子量の調整など通常のラジカル重合技術が適用される。 Examples of the polymerization initiator include generally known polymerization initiators such as azo, organic peroxide, inorganic peroxide, and redox. As a usage-amount of a polymerization initiator, it is about 0.001 to 10 weight% normally with respect to the polymerizable monomer component total amount. Further, a normal radical polymerization technique such as adjustment of molecular weight by a chain transfer agent is applied.
側鎖にオキサゾリン基を有する共重合体の構成単位であるアルケニルオキサゾリンは1〜50モル%、好ましいアルケニルオキサゾリン配合量は5モル%以上、さらに好ましくは10モル%以上である。1モル%未満であると、十分な水酸基を導入できず、気泡調整効果、発泡剤逸散防止効果と帯電防止効果を付与することが困難である。 The alkenyl oxazoline, which is a constituent unit of a copolymer having an oxazoline group in the side chain, is 1 to 50 mol%, and the preferred alkenyl oxazoline content is 5 mol% or more, more preferably 10 mol% or more. If it is less than 1 mol%, sufficient hydroxyl groups cannot be introduced, and it is difficult to impart a bubble adjusting effect, a blowing agent dissipation preventing effect and an antistatic effect.
側鎖にオキサゾリン基を有する共重合体の水との水和反応は、有機溶媒中で行うことができる。使用できる有機溶媒は、共重合体を溶解可能(溶解度が1(g/100g)以上)、水とは反応せず、また、水に対する溶解度が5(g/100g)以上であり、例えば、テトラヒドロフラン、酢酸エチル、酢酸ブチル、メチルアルコール、エチルアルコール、アセトン、エチルメチルケトンなどを例示することができる。これらの容器溶媒を単独もしくは混合で使用することができる。また、共重合体及び水との溶解性のバランスを考慮するとテトラヒドロフランが特に好ましい。 The hydration reaction of the copolymer having an oxazoline group in the side chain with water can be carried out in an organic solvent. The organic solvent that can be used is capable of dissolving the copolymer (solubility is 1 (g / 100 g) or more), does not react with water, and has a solubility in water of 5 (g / 100 g) or more. And ethyl acetate, butyl acetate, methyl alcohol, ethyl alcohol, acetone, ethyl methyl ketone, and the like. These container solvents can be used alone or in combination. Further, tetrahydrofuran is particularly preferable in consideration of the balance of solubility with the copolymer and water.
有機溶媒の使用量は特に限定されるものではなく、側鎖にオキサゾリン基を有する共重合体、水及び本発明の芳香族ビニル系重合体が共に溶解し、かつ攪拌可能の溶液粘度を保持できるように配合すればよい。目安として、側鎖にオキサゾリン基を有する共重合体の5〜50重量%、好ましく10〜30重量%である。 The amount of the organic solvent used is not particularly limited, and both the copolymer having an oxazoline group in the side chain, water, and the aromatic vinyl polymer of the present invention can be dissolved, and a stirrable solution viscosity can be maintained. What is necessary is just to mix | blend. As a guide, it is 5 to 50% by weight, preferably 10 to 30% by weight of the copolymer having an oxazoline group in the side chain.
水和反応に使用する水の量はオキサゾリン基に対して同モル以上、好ましくは10倍モル以上、特に好ましくは30倍モル以上である。使用する水の量はオキサゾリン基に対して同モル未満の場合、勿論のことであるが、全てのオキサゾリン基を水酸基へ変換できず、また、水和反応の速度が低くなり、所要反応時間が長くなるので、好ましくない。 The amount of water used for the hydration reaction is the same mole or more, preferably 10 times mole or more, particularly preferably 30 times mole or more with respect to the oxazoline group. Of course, when the amount of water used is less than the same mole with respect to the oxazoline group, not all oxazoline groups can be converted to hydroxyl groups, and the rate of hydration reaction is reduced, resulting in the required reaction time. Since it becomes long, it is not preferable.
水和反応時の温度は40〜100℃が十分であり、特に60〜80℃程度が好ましい。40℃より低い温度でも、水和反応が徐々に進行するが、反応時間が長く、工程効率が低い。一方、100℃を越えると、水が蒸発しやすくなり、加圧設備が必要となり、操作条件が複雑になるので好ましくない。反応時間は反応温度によって多少変わるが、5時間あれば、オキサゾリン基から水酸基への変換率が50%以上に達することができる。また、10時間以上であれば、90%以上の変換率、さらに15時間以上であれば、100%の変換率を得ることができる。 40-100 degreeC is enough for the temperature at the time of a hydration reaction, and about 60-80 degreeC is especially preferable. Even at temperatures lower than 40 ° C., the hydration reaction proceeds gradually, but the reaction time is long and the process efficiency is low. On the other hand, when the temperature exceeds 100 ° C., water tends to evaporate, a pressure facility is required, and the operation conditions are complicated, which is not preferable. Although the reaction time varies somewhat depending on the reaction temperature, if it is 5 hours, the conversion rate from the oxazoline group to the hydroxyl group can reach 50% or more. Moreover, if it is 10 hours or more, a conversion rate of 90% or more can be obtained, and if it is 15 hours or more, a conversion rate of 100% can be obtained.
側鎖にオキサゾリン基を有する共重合体及び側鎖に水酸基を有する本発明の芳香族ビニル系重合体の分子量の範囲は特に限定されないが、5000〜5000000が好ましく、10000〜1000000がさらに好ましく、50000〜500000が特に好ましい。分子量が5000未満であると、発泡成形体中の配合量が10重量%以上である場合、成形体の機械的強度、耐衝撃性などを低下させる傾向が見られ、5000000以上であると特殊の重合方法、設備を要し、製造コストがかかるため好ましくない。 The molecular weight range of the copolymer having an oxazoline group in the side chain and the aromatic vinyl polymer of the present invention having a hydroxyl group in the side chain is not particularly limited, but is preferably 5000 to 5000000, more preferably 10000 to 1000000, and 50000. ˜500000 is particularly preferred. When the molecular weight is less than 5,000, when the blending amount in the foamed molded product is 10% by weight or more, there is a tendency to decrease the mechanical strength, impact resistance, etc. of the molded product. A polymerization method and equipment are required, which is not preferable because of high production costs.
本発明の側鎖に水酸基を有する芳香族ビニル系重合体を単独或いはポリスチレン系樹脂と混合して、ポリスチレン系樹脂組成物、ポリスチレン系樹脂発泡性粒子、予備発泡粒子及びそれらからなるポリスチレン系樹脂発泡成形体を製造することができる。芳香族ビニル系重合体の配合量は0.01重量%以上であり、好ましくは0.1重量%以上、特に好ましくは1重量%以上である。0.01重量%未満である場合、十分な気泡調整効果、発泡剤逸散防止効果と帯電防止効果を付与できず、剛性、耐衝撃性、耐熱性と寸法安定性など全部満足できる発泡性成形体が得られないので、好ましくない。 The aromatic vinyl polymer having a hydroxyl group in the side chain of the present invention alone or mixed with a polystyrene resin, a polystyrene resin composition, a polystyrene resin expandable particle, a pre-expanded particle, and a polystyrene resin foam comprising the same A molded body can be produced. The blending amount of the aromatic vinyl polymer is 0.01% by weight or more, preferably 0.1% by weight or more, and particularly preferably 1% by weight or more. If it is less than 0.01% by weight, sufficient foam adjustment effect, foaming agent dissipation prevention effect and antistatic effect cannot be imparted, and foaming molding that satisfies all of rigidity, impact resistance, heat resistance and dimensional stability, etc. Since a body cannot be obtained, it is not preferable.
本発明のポリスチレン系樹脂発泡成形体は押出発泡法又は予備発泡粒子発泡法で製造することができる。 The polystyrene resin foam molded article of the present invention can be produced by an extrusion foaming method or a pre-expanded particle foaming method.
押出発泡法は、側鎖に水酸基を有する芳香族ビニル系重合体とポリスチレン系樹脂とをドライブレンドし、押出機にて溶融混練、発泡剤を続けて添加し樹脂中に分散させ、押出機のダイスから低圧域に押出すことで発泡成形体を製造する方法である。 In the extrusion foaming method, an aromatic vinyl polymer having a hydroxyl group in a side chain and a polystyrene resin are dry blended, melt kneaded in an extruder, and a foaming agent is continuously added and dispersed in the resin. This is a method for producing a foamed molded product by extruding from a die into a low pressure region.
ポリスチレン系樹脂とは、ポリスチレンを50重量%以上含む樹脂で、ポリプロピレン、ポリエチレン、ポリウレタン等の混合物又は混練樹脂組成物でもよい。 The polystyrene-based resin is a resin containing 50% by weight or more of polystyrene and may be a mixture of polypropylene, polyethylene, polyurethane, or a kneaded resin composition.
押出機で溶融混練する際にシリンダーの温度条件は、側鎖に水酸基を有する芳香族ビニル系重合体の融点以上であればよく、特に限定されないが、通常、170〜300℃であり、樹脂の吐出安定性が良好である点から200〜240℃がさらに好ましい。 The temperature condition of the cylinder when melt-kneading with an extruder is not particularly limited as long as it is equal to or higher than the melting point of the aromatic vinyl polymer having a hydroxyl group in the side chain, but is usually 170 to 300 ° C. 200-240 degreeC is further more preferable from the point that discharge stability is favorable.
本発明で使用する発泡剤は、特に限定されるものではなく、汎用のパラフィン系発泡剤であれば、プロパン、n−ブタン、i−ブタン、ペンタン等の脂肪族炭化水素類、シクロブタン、シクロペンタン、シクロヘキサン等の環式脂肪族炭化水素類等が挙げられるが、発泡性に優れる点から脂肪族炭化水素類が好ましく、特にn−ブタン、i−ブタンおよびペンタンが好ましい。 The foaming agent used in the present invention is not particularly limited. If it is a general-purpose paraffinic foaming agent, aliphatic hydrocarbons such as propane, n-butane, i-butane and pentane, cyclobutane and cyclopentane. And cycloaliphatic hydrocarbons such as cyclohexane and the like, and aliphatic hydrocarbons are preferred from the viewpoint of excellent foamability, and n-butane, i-butane and pentane are particularly preferred.
また、本発明において、側鎖に水酸基を有する芳香族ビニル系重合体をポリスチレン系樹脂と共に用いる際に、可塑剤を併用することで樹脂の流動性が高められ、発泡成形品の外観を一層高めることができる。可塑剤としては特に限定されるものではないが、流動パラフィン、エステル系可塑剤等が挙げられ、これらは単独で用いてもよいし、また混合物として用いてもよい。 In the present invention, when an aromatic vinyl polymer having a hydroxyl group in the side chain is used together with a polystyrene resin, the fluidity of the resin is enhanced by using a plasticizer in combination, and the appearance of the foam molded product is further enhanced. be able to. Although it does not specifically limit as a plasticizer, A liquid paraffin, an ester plasticizer, etc. are mentioned, These may be used independently and may be used as a mixture.
エステル系可塑剤としては、特に限定されるものではないが、ジブチルフタレート、ブチルベンジルフタレート、ジオクチルフタレート、ジノルマルオクチルフタレート、ジ−2−エチルヘキシルフタレート、ジオクチルアジペート、ジイソブチルアジペート、
ジイソノニルアジペートアセチルトリブチルシトレート、グリセリンモノアセトモノラウレート、グリセリンジアセトモノラウレート、グリセリンモノアセトモノステアレート等が挙げられ、高沸点で汎用な可塑剤であるジブチルアジペートが特に好ましい。また、エステル系可塑剤は発泡助剤としても使用できる。
The ester plasticizer is not particularly limited, but dibutyl phthalate, butyl benzyl phthalate, dioctyl phthalate, dinormal octyl phthalate, di-2-ethylhexyl phthalate, dioctyl adipate, diisobutyl adipate,
Examples thereof include diisononyl adipate acetyltributyl citrate, glycerin monoacetomonolaurate, glycerin diacetomonolaurate, and glycerin monoacetomonostearate. Dibutyl adipate, which is a high-boiling and general-purpose plasticizer, is particularly preferred. The ester plasticizer can also be used as a foaming aid.
可塑剤の使用量は特に限定されず、通常、芳香族ビニル系重合体及びポリスチレン系樹脂の合計100重量部に対して0.01〜10重量部で用いられるが、樹脂の流動性向上の効果が顕著である点から0.1以上添加することが特に好ましい。 The amount of the plasticizer used is not particularly limited, and is usually used in an amount of 0.01 to 10 parts by weight with respect to a total of 100 parts by weight of the aromatic vinyl polymer and polystyrene resin. It is particularly preferable to add 0.1 or more from the standpoint of the conspicuousness.
可塑剤の使用方法は特に限定されないが、溶液重合を行う際、可塑剤の存在下に重合を行い、得られた重合体を溶融混練に供するか、前記重合体を溶融混練する際にパラフィン系発泡剤と共に供するか、或いは、溶融混練後、得られた粒子状物を水中懸濁してパラフィン系発泡剤を含浸させる際に可塑剤を同時に添加する方法が挙げられる。 The method of using the plasticizer is not particularly limited, but when performing the solution polymerization, the polymerization is performed in the presence of the plasticizer, and the obtained polymer is subjected to melt kneading, or when the polymer is melt kneaded, the paraffinic type is used. Examples thereof include a method in which a plasticizer is added together with the foaming agent, or after melt-kneading, the obtained particulate matter is suspended in water and impregnated with a paraffinic foaming agent.
さらに、本発明のポリスチレン系樹脂組成物、ポリスチレン系樹脂発泡性粒子、予備発泡粒子及び発泡成形体において、本発明の効果を阻害しない範囲で、必要に応じて造核剤としてタルク、炭酸カルシウムなどの無機化合物、滑剤としてステアリン酸バリウム、ステアリン酸カルシウム、酸化防止剤や紫外線吸収剤などの安定剤、帯電防止剤、難燃剤、抗菌剤など公知の各種添加剤を含有してもよい。このような添加剤の含有量は、本発明のポリスチレン系樹脂組成物などにおいて、20重量%以下であることが好ましい。これらの添加剤は単独で用いても、複数の組み合わせでもよい。 Furthermore, in the polystyrene resin composition, polystyrene resin expandable particles, pre-expanded particles, and foamed molded article of the present invention, talc, calcium carbonate, etc. as a nucleating agent as necessary, as long as the effects of the present invention are not impaired. These inorganic compounds and lubricants may contain various known additives such as barium stearate, calcium stearate, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants and antibacterial agents. The content of such additives is preferably 20% by weight or less in the polystyrene resin composition of the present invention. These additives may be used alone or in combination.
一方、予備発泡粒子発泡法は、まず、ポリスチレン系樹脂発泡性粒子を作製し、その後得られた発泡性粒子を予備発泡させて予備発泡粒子とし、該予備発泡粒子を型内成形することで発泡成形体を製造する方法である。また、ポリスチレン系樹脂発泡性粒子の作製方法は主に2つがあり、一つは、側鎖に水酸基を有する芳香族ビニル系重合体とポリスチレン系樹脂から粒子を作り、この粒子を発泡剤に含浸させる方法であり、もう一つは、ポリスチレン系樹脂粒子を作ってから、芳香族ビニル系重合体を溶解した可塑剤溶液に含浸させ、同時に又はその後発泡剤も含浸する方法である。 On the other hand, in the pre-expanded particle foaming method, first, polystyrene-based resin expandable particles are prepared, and then the resulting expandable particles are pre-expanded into pre-expanded particles, and the pre-expanded particles are molded in-mold. This is a method for producing a molded body. There are two main methods for preparing polystyrene resin foamable particles. One is making particles from an aromatic vinyl polymer having a hydroxyl group in the side chain and a polystyrene resin, and impregnating the particles with a foaming agent. The other is a method of making polystyrene resin particles and then impregnating them with a plasticizer solution in which an aromatic vinyl polymer is dissolved, and simultaneously or thereafter impregnating a foaming agent.
ポリスチレン系樹脂粒子は、ポリスチレンを主成分として50重量%以上含み、ポリスチレン、ポリオレフィン、ポリウレタン粒子を異種、又は同種モノマー中に含浸、重合させて得られる粒子である。また、ポリスチレン、ポリオレフィン、ポリウレタン粒子をスチレンモノマー中に含浸、重合する方法が常温で含浸できるので特に好ましい。 Polystyrene resin particles are particles obtained by impregnating and polymerizing polystyrene, polyolefin, and polyurethane particles in different or similar monomers, containing 50% by weight or more of polystyrene as a main component. Further, a method of impregnating and polymerizing polystyrene, polyolefin, and polyurethane particles in a styrene monomer is particularly preferable because it can be impregnated at room temperature.
発泡性ポリスチレン系樹脂粒子の予備発泡方法は、従来公知の方法を用いることができる。例えば、円筒形の予備発泡機を使用して、水蒸気等で加熱して発泡させる等の方法等が挙げられる。 As a pre-foaming method for the expandable polystyrene resin particles, a conventionally known method can be used. For example, a method of foaming by heating with steam or the like using a cylindrical pre-foaming machine can be used.
また、予備発泡粒子を型内発泡成形させる方法も、従来公知の方法を用いることができ、例えば、金型内に予備発泡粒子を充填し、水蒸気等を吹き込んで加熱する方法等が挙げられる。 Moreover, a conventionally well-known method can be used also for the method of carrying out in-mold foam molding of the pre-expanded particle, for example, the method of filling pre-expanded particle in a metal mold | die, blowing steam etc., and heating etc. are mentioned.
本発明にかかるポリスチレン系樹脂発泡成形体の用途としては、特に限定されないが、その高独立気泡率、剛性、耐衝撃性、断熱性、表面外観と寸法安定性が良好などの特性より、緩衝材、建材用の断熱材、食品や電気製品、精密機器用の容器、電機製品の部材、および自動車のバンパー、内外装部品などの各種用途が挙げられる。 The use of the polystyrene-based resin foam molded article according to the present invention is not particularly limited, but the buffer material is characterized by its high closed cell ratio, rigidity, impact resistance, heat insulation, surface appearance and good dimensional stability. Insulating materials for building materials, food and electrical products, containers for precision equipment, members of electrical products, automobile bumpers, interior and exterior parts, and the like.
以下、実施例により本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。以下において、部及び%はそれぞれ重量部及び重量%を示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In the following, parts and% indicate parts by weight and% by weight, respectively.
合成例、実施例における各種物性の測定又は評価は以下の方法で行った。
(1)ガラス相転移温度(Tg)測定:示差走査熱量計装置(エスアイアイナノテクノロジー社製のDSC6220)を用い、測定容器に試料を10mg充填して、窒素ガス流量40ml/minのもと10℃/minの昇温速度で200℃まで昇温し10分間保持後、10℃/minの降温速度で−20℃まで降温し10分間保持した。その後、再度10℃/minの昇温速度で200℃まで昇温し、熱量の変化を測定し、吸熱ピークの中間点をガラス相転移温度とした。
(2)水酸基導入量算出方法:側鎖にオキサゾリン基を有する共重合体中のオキサゾリン基含有量の定量分析は1H−NMR(CDCl3)により行った。それを水和反応させ、得られた側鎖に水酸基を有する芳香族ビニル系重合体中のオキサゾリン基は1H−NMRのスペクトルが他の官能基のスペクトルと一部重なるため、中和滴定法で定量した。
オキサゾリン基の中和滴定法の定量:水和反応後の固形物状ポリマーをピリジンに溶解し、過剰量の酢酸と100℃で1時間反応させ、その後室温まで放冷し、フェノールフタレインを指示薬として0.25mol/L の水酸化カリウムのエタノール溶液で未反応の酢酸を滴定し、オキサゾリン基の含有率を算出した。
水酸基の定量方法:オキサゾリン基を含有しない場合、JIS K0070(1992)に準じ、水酸基の含有量(水酸基価)を定量できるが、オキサゾリン基を含有すると、JIS K0070に使用される無水酢酸と反応するため、該定量方法は適用しないことが本発明者らの検討で明らかになった。そこで、本発明では、中和滴定法で算出したオキサゾリン基の含有量は0.1mol%以上である場合、1H−NMRで得られた水和反応前のオキサゾリン基の含有量から水和反応後の中和滴定法で算出したオキサゾリン基の含有量を引き、得られる値を水和反応後の水酸基の含有量とした。一方、中和滴定法で算出したオキサゾリン基の含有量は0.1mol%未満(未検出)である場合、オキサゾリン基による影響が無視できると判断し、JIS K0070(1992)に準じ、水酸基の含有量(水酸基価)を定量した。
(3)ジイソブチルアジペート(DIBA)に対する溶解性:下記合成例で合成した水酸基含有共重合体5gをDIBA 45g中に添加し、攪拌しながら70℃で0.5時間加熱した後、室温で2時間静置し溶解性を評価した。
溶解:均一で透明、不溶解(溶解しない):不均一で白い不溶物が多い
(4)独立気泡率(%):押出発泡成形体を幅、長さ、厚さが全て25mmの立方体に切り出した後、ASTM D2856に基づいて空気比較式の乾式密度計を用いることにより測定した。
(5)発泡成形体中の残存発泡剤含有量:ガスクロマトグラフGC−14A(島津製作所製)を用いて分析することで、残存発泡剤含有量(重量%)を算出した。残存発泡剤含有量が高いほど、発泡剤の逸散防止効果が高い。
残存発泡剤含有量(重量%)=発泡体100g中の残存発泡剤量(g)/製造後の発泡体100(g)×100
(6)熱伝導率(W/m・K):製造してから30日後の発泡成形体を用いてJIS A9511に準じて測定した。熱伝導率が低いほど、発泡成形体の断熱性が高い。
(7)加熱寸法変化:得られた発泡成形体から幅、長さ、厚さが150mm、150mm、25mmの試験片を切り出し、試験片の中央部に縦及び横方向にそれぞれ互いに平行に3本の直線を50mm間隔になるよう記入し、それぞれ3本の直線の長さを測定し、その平均値を求めて加熱前の寸法とした。70℃の熱風乾燥機の中に試験片を水平に置き、22時間加熱したときの加熱前後の寸法変化率で評価した。
加熱寸法変化率(%)=(加熱後の寸法−加熱前の寸法)/加熱前の寸法×100
○:変化率3%未満、△:変化率3%以上5%未満、×:5%以上
(8)表面固有抵抗率測定:得られた発泡成形体から幅、長さ、厚さが110mm、110mm、25mmの試験片を切り出し、温度23℃、相対湿度50%に調整した恒温恒湿機に入れ、3時間静置し、表面固有抵抗率測定用試料を得た。JIS
K 6911 に基づき、デジタルエレクトロメーター(R8252型:エーディーシー社製)を用いて測定を行った。表面固有抵抗率が低いほど、発泡成形体の帯電防止性が高い。数値が高いほど圧縮強度が高いことを示す。
(9)圧縮強度(N/cm2):得られた発泡体から幅、長さ、厚みが50mm、50mm、25mmの試験片を切り出し、JIS A 9511に準じて厚み方向の圧縮強度を測定した。
(10)落球衝撃試験:発泡体の耐割れ性の強さを示す落球衝撃試験について、JISK 7211に準じて測定した。発泡体から幅、長さ、厚さが200mm、40mm、20mmの試験片を切り出し、合計20個用意する。321gの鋼球を落とし、下記の計算式により50%破壊高さを算出した。数値が高いほど耐衝撃性が高いことを示す。
H50=Hi+d[Σ(i×ni)/N±0.5]
H50:50%破壊高さ(cm)
Hi:高さ水準(i)が0のときの試験高さ(cm)で、試験片が破壊することが予測される高さを指す。
d:試験高さを上下させるときの高さ間隔(cm)
i:Hiのときを0とし、一つずつ増減する高さ水準(i=・・・−3,−2,−1,0,1,2,3,・・・)
ni:各水準において破壊した(又は破壊しなかった)試験片の数
N:破壊した(又は破壊しなかった)試験片の総数(N=Σni)
いずれか多い方のデータを使用する。なお、同数の場合はどちらを使用してもよい。
±0.5:破壊したデータを使用したときは負号を、破壊しなかったデータを使用したときは正号をとる。
Measurement or evaluation of various physical properties in Synthesis Examples and Examples was performed by the following methods.
(1) Measurement of glass phase transition temperature (Tg): Using a differential scanning calorimeter (DSC 6220 manufactured by SII Nano Technology), 10 mg of a sample was filled in a measurement container, and a nitrogen gas flow rate of 40 ml / min was used. The temperature was raised to 200 ° C. at a temperature raising rate of ° C./min and held for 10 minutes, and then the temperature was lowered to −20 ° C. at a temperature lowering rate of 10 ° C./min and held for 10 minutes. Thereafter, the temperature was raised again to 200 ° C. at a rate of 10 ° C./min, the change in calorie was measured, and the midpoint of the endothermic peak was taken as the glass phase transition temperature.
(2) Hydroxyl group introduction amount calculation method: The quantitative analysis of the content of the oxazoline group in the copolymer having an oxazoline group in the side chain was carried out by 1 H-NMR (CDCl 3 ). The oxazoline group in the aromatic vinyl polymer having a hydroxyl group in the obtained side chain is subjected to hydration reaction, and the 1 H-NMR spectrum partially overlaps with the spectrum of other functional groups. Quantified with.
Quantification of neutralization titration method of oxazoline group: Dissolve solid polymer after hydration reaction in pyridine, react with excess acetic acid at 100 ° C for 1 hour, then allow to cool to room temperature, phenolphthalein as indicator The unreacted acetic acid was titrated with an ethanol solution of potassium hydroxide of 0.25 mol / L to calculate the content of oxazoline groups.
Quantification method of hydroxyl group: When no oxazoline group is contained, the hydroxyl group content (hydroxyl value) can be quantified according to JIS K0070 (1992), but when it contains an oxazoline group, it reacts with acetic anhydride used in JIS K0070. Therefore, it became clear by the present inventors that the quantification method is not applied. Therefore, in the present invention, when the content of the oxazoline group calculated by the neutralization titration method is 0.1 mol% or more, the hydration reaction is determined from the content of the oxazoline group before hydration obtained by 1 H-NMR. The content of the oxazoline group calculated by the subsequent neutralization titration method was subtracted, and the obtained value was used as the content of the hydroxyl group after the hydration reaction. On the other hand, when the content of the oxazoline group calculated by the neutralization titration method is less than 0.1 mol% (undetected), it is judged that the influence of the oxazoline group can be ignored, and the content of the hydroxyl group according to JIS K0070 (1992) The amount (hydroxyl value) was quantified.
(3) Solubility in diisobutyl adipate (DIBA): 5 g of the hydroxyl group-containing copolymer synthesized in the following synthesis example was added to 45 g of DIBA, heated at 70 ° C. for 0.5 hours with stirring, and then at room temperature for 2 hours. It was allowed to stand and the solubility was evaluated.
Dissolution: Uniform and transparent, Insoluble (not dissolved): Uneven and many white insolubles
(4) Closed-cell ratio (%): Measured by using an air-comparative dry density meter based on ASTM D2856 after cutting an extruded foam molded body into a cube having a width, length and thickness of 25 mm. .
(5) Residual foaming agent content in the foamed molded article: The residual foaming agent content (% by weight) was calculated by analysis using a gas chromatograph GC-14A (manufactured by Shimadzu Corporation). The higher the residual foaming agent content, the higher the effect of preventing the foaming agent from escaping.
Residual foaming agent content (% by weight) = residual foaming agent amount in 100 g of foam (g) / foam after production 100 (g) × 100
(6) Thermal conductivity (W / m · K): Measured according to JIS A9511 using a foamed molded product 30 days after production. The lower the thermal conductivity, the higher the heat insulating property of the foamed molded product.
(7) Change in heating dimension: Cut out test pieces having widths, lengths and thicknesses of 150 mm, 150 mm, and 25 mm from the obtained foamed molded article, and three in parallel to each other in the vertical and horizontal directions at the center of the test piece. The straight lines were entered at intervals of 50 mm, the length of each of the three straight lines was measured, and the average value was obtained as the dimension before heating. The test piece was placed horizontally in a hot air dryer at 70 ° C. and evaluated by the dimensional change rate before and after heating when heated for 22 hours.
Heating dimensional change rate (%) = (dimension after heating−dimension before heating) / dimension before heating × 100
○: Change rate of less than 3%, Δ: Change rate of 3% or more and less than 5%, ×: 5% or more
(8) Measurement of surface specific resistivity: A test piece having a width, length and thickness of 110 mm, 110 mm, and 25 mm was cut out from the obtained foamed molded article, and the temperature and humidity controlled by adjusting the temperature to 23 ° C. and relative humidity 50%. And left for 3 hours to obtain a sample for measuring the surface resistivity. JIS
Based on K6911, the measurement was performed using a digital electrometer (R8252 type: manufactured by ADC Corporation). The lower the surface resistivity, the higher the antistatic property of the foamed molded product. The higher the value, the higher the compressive strength.
(9) Compressive strength (N / cm 2 ): Specimens having a width, length, and thickness of 50 mm, 50 mm, and 25 mm were cut out from the obtained foam, and the compressive strength in the thickness direction was measured according to JIS A 9511. .
(10) Falling ball impact test: A falling ball impact test indicating the strength of crack resistance of a foam was measured in accordance with JISK 7211. Test pieces having a width, length, and thickness of 200 mm, 40 mm, and 20 mm are cut out from the foam, and a total of 20 test pieces are prepared. A 321 g steel ball was dropped, and the 50% fracture height was calculated by the following formula. Higher values indicate higher impact resistance.
H 50 = H i + d [Σ (i × n i ) /N±0.5]
H 50 : 50% fracture height (cm)
H i : Test height (cm) when the height level (i) is 0, and indicates the height at which the test piece is expected to break.
d: Height interval when moving the test height up and down (cm)
i: Height when H i is 0, and the height level is increased or decreased by 1 (i =... -3, -2, -1, 0, 1, 2, 3,...)
n i : number of test pieces destroyed (or not destroyed) at each level N: total number of test pieces destroyed (or not destroyed) (N = Σn i )
Use whichever data is greater. In the case of the same number, either may be used.
± 0.5: A negative sign is used when destroyed data is used, and a positive sign is used when data that is not destroyed is used.
(合成例1)
2−ビニル−2−オキサゾリンとスチレンの共重合体(PolyVOZO−St−1の合成
撹拌装置、温度計、冷却器および乾燥窒素導入管を備えた容量300mLの反応容器に2−ビニル−2−オキサゾリン(VOZO)5.0g(51.5mmol)、スチレン(St)48.3g(463.9mmol)、重合開始剤としてアゾビスイソブチロニトリル(AIBN)0.85g(5.2mmol)とエタノール54.2gを仕込んだ。乾燥窒素気流下、反応液を30℃で1時間撹拌しながら窒素置換した後、60℃で10時間重合反応を行った。反応終了後、溶媒と残存モノマーを減圧下で留去し、50℃において減圧下で乾燥し、白色粉末状固形物51.0gを得た(収率=95.7%)。
本固形物は、赤外吸収スペクトル(IR)により、コポリマーPolyVOZO−Stの生成を確認した。
本コポリマーの組成は1H−NMR(CDCl3)分析により、VOZO由来ユニット/St由来ユニット=1.00/8.86と確認した。
(Synthesis Example 1)
Copolymer of 2-vinyl-2-oxazoline and styrene (Synthesis of PolyVOZO-St-1) In a reaction vessel having a capacity of 300 mL equipped with a stirrer, a thermometer, a cooler and a dry nitrogen introduction tube, 2-vinyl-2-oxazoline (VOZO) 5.0 g (51.5 mmol), styrene (St) 48.3 g (463.9 mmol), azobisisobutyronitrile (AIBN) 0.85 g (5.2 mmol) and ethanol 54. In a dry nitrogen stream, the reaction solution was purged with nitrogen while stirring at 30 ° C. for 1 hour, and then subjected to a polymerization reaction for 10 hours at 60 ° C. After completion of the reaction, the solvent and residual monomer were distilled under reduced pressure. And dried under reduced pressure at 50 ° C. to obtain 51.0 g of a white powdery solid (yield = 95.7%).
This solid matter confirmed the production | generation of copolymer PolyVOZO-St by the infrared absorption spectrum (IR).
The composition of this copolymer was confirmed by 1 H-NMR (CDCl 3 ) analysis to be VOZO-derived unit / St-derived unit = 1.00 / 8.86.
(合成例2)
PolyVOZO−Stの水和反応によるPolyOH−St−1、PolyOH−St−2の合成
撹拌装置を備えた容量300mLの反応容器に合成例1で得られたPolyVOZO−St−1 20.0g、溶媒としてテトラヒドロフラン(THF)180.0gを仕込み室温で30分撹拌することで溶解させた後、水10.6g(589mmol、オキサゾリン基に対して30倍mol)を仕込み、均一に混合してかた2当分に分けた。片方は撹拌装置、温度計、冷却器を備えた200mLの容量に加え、撹拌しながら80℃で8時間反応させ、もう一方は同様に200mLの容量中で撹拌しながら80℃で15時間反応させた。反応終了後、室温に戻し、それぞれの反応液をエバポレーターに仕込み、70℃、減圧下でTHF、水を留去した。得られた固形物を70℃において減圧下で乾燥し、それぞれ白色粉末状固形物10.0g、10.1gを得た(収率=98.3%、99.2%)。
得られた固形物中のオキサゾリン基と水酸基を定量し、8時間反応させて得られたPolyOH−St−1、15時間反応させて得られたPolyOH−St−2のユニット比はそれぞれ、VOZO/OH/St=3.0/7.1/89.9、OH/St=10.1/89.9であった。なお、PolyOH−St−2は、オキサゾリン基を定量した結果、検出できなかったので全て水酸基になっていると判断した。
また、得られたPolyOH−St−1、PolyOH−St−2のTgはそれぞれ91、96℃であり、ジイソブチルアジペート(以下、DIBAと略称する。)に10%以上溶解することを確認した。
(Synthesis Example 2)
Synthesis of PolyOH-St-1 and PolyOH-St-2 by hydration reaction of PolyVOZO-St 20.0 g of PolyVOZO-St-1 obtained in Synthesis Example 1 in a reaction vessel with a capacity of 300 mL equipped with a stirrer, as a solvent After adding 180.0 g of tetrahydrofuran (THF) and stirring for 30 minutes at room temperature, 10.6 g of water (589 mmol, 30 times mol with respect to the oxazoline group) was charged and mixed uniformly for 2 minutes. Divided into. One side is added to a 200 mL volume equipped with a stirrer, thermometer, and condenser, and allowed to react at 80 ° C. for 8 hours with stirring, and the other is similarly reacted at 80 ° C. for 15 hours with stirring in a 200 mL volume. It was. After completion of the reaction, the temperature was returned to room temperature, each reaction solution was charged into an evaporator, and THF and water were distilled off at 70 ° C. under reduced pressure. The obtained solid was dried at 70 ° C. under reduced pressure to obtain 10.0 g and 10.1 g of a white powdery solid, respectively (yield = 98.3%, 99.2%).
The unit ratio of PolyOH-St-1 obtained by quantifying the oxazoline group and hydroxyl group in the obtained solid and reacting for 8 hours and reacting for 15 hours is VOZO / OH / St = 3.0 / 7.1 / 89.9, OH / St = 10.1 / 89.9. Since PolyOH-St-2 was not detected as a result of quantifying the oxazoline group, it was judged that all of it was a hydroxyl group.
Moreover, Tg of obtained PolyOH-St-1 and PolyOH-St-2 is 91 and 96 degreeC, respectively, It confirmed that 10% or more melt | dissolves in diisobutyl adipate (henceforth DIBA).
(合成例3)
2−ビニル−2−オキサゾリンとスチレンの共重合体PolyVOZO−St−2の合成
合成例1において、VOZO
15.0g(154.6mmol)、St 37.5g(360.8mmol)、エタノール53.4gを用いた以外は合成例1と同様に重合を行い、白色粉末状固形物50.1gを得た(収率=95.4%)。
本固形物は、赤外吸収スペクトル(IR)により、コポリマーPolyVOZO−Stの生成を確認した。
本コポリマーの組成は1H−NMR(CDCl3)分析により、VOZO由来ユニット/St由来ユニット=1.00/2.30と確認した。
(Synthesis Example 3)
Synthesis of 2-vinyl-2-oxazoline and styrene copolymer PolyVOZO-St-2 In Synthesis Example 1, VOZO
Polymerization was performed in the same manner as in Synthesis Example 1 except that 15.0 g (154.6 mmol), St 37.5 g (360.8 mmol), and ethanol 53.4 g were used, to obtain 50.1 g of a white powdery solid ( Yield = 95.4%).
This solid matter confirmed the production | generation of copolymer PolyVOZO-St by the infrared absorption spectrum (IR).
The composition of this copolymer was confirmed by 1 H-NMR (CDCl 3 ) analysis as VOZO-derived unit / St-derived unit = 1.00 / 2.30.
(合成例4)
PolyVOZO−Stの水和反応によるPolyOH−St−3とPolyOH−St−4の合成
合成例3で合成したPolyVOZO−St−2 20.0g、水を32.1g(1.784mol、オキサゾリン基に対して30倍mol)使用し、合成例2と同様に溶媒THF中で水和反応を行い、白色粉末状固形物10.4g、10.5gを得た(収率=98.7%、99.7%)。
得られた固形物中のオキサゾリン基と水酸基を定量し、8時間反応させて得られたPolyOH−St−3、15時間反応させて得られたPolyOH−St−4のユニット比はそれぞれ、VOZO/OH/St=12.4/17.9/69.7、OH/St=30.3/69.7であった。なお、PolyOH−St−4は、オキサゾリン基を定量した結果、検出できなかったので全て水酸基になっていると判断した。
また、得られたPolyOH−St−3、PolyOH−St−4のTgはそれぞれ93、98℃であり、DIBAに10%以上溶解することを確認した。
(Synthesis Example 4)
Synthesis of PolyOH-St-3 and PolyOH-St-4 by hydration reaction of PolyVOZO-St 20.0 g of PolyVOZO-St-2 synthesized in Synthesis Example 3, 32.1 g of water (1.784 mol, based on the oxazoline group) Hydration reaction was performed in a solvent THF in the same manner as in Synthesis Example 2 to obtain 10.4 g and 10.5 g of a white powdery solid (Yield = 98.7%, 99.99). 7%).
The unit ratio of PolyOH-St-3 obtained by quantifying the oxazoline group and hydroxyl group in the obtained solid and reacting for 8 hours, and PolyOH-St-4 obtained by reacting for 15 hours was VOZO / They were OH / St = 12.4 / 17.9 / 69.7 and OH / St = 30.3 / 69.7. Since PolyOH-St-4 was not detected as a result of quantifying the oxazoline group, it was judged that all of it was a hydroxyl group.
Moreover, Tg of obtained PolyOH-St-3 and PolyOH-St-4 is 93 and 98 degreeC, respectively, It confirmed that 10% or more melt | dissolves in DIBA.
(合成例5)
2−ビニル−2−オキサゾリンとスチレンの共重合体PolyVOZO−St−3の合成
合成例1において、VOZO 25.0g(257.7mmol)、St 26.8g(257.7mmol)、エタノール52.7gを用いた以外は合成例1と同様に行い、白色粉末状固形物49.5gを得た(収率=95.6%)。
本固形物は、赤外吸収スペクトル(IR)により、コポリマーPolyVOZO−Stの生成を確認した。
本コポリマーの組成は1H−NMR(CDCl3)分析により、VOZO由来ユニット/St由来ユニット=1.00/0.97と確認した。
(Synthesis Example 5)
Synthesis of 2-vinyl-2-oxazoline and styrene copolymer PolyVOZO-St-3 In Synthesis Example 1, VOZO 25.0 g (257.7 mmol), St 26.8 g (257.7 mmol), and ethanol 52.7 g were added. The procedure was the same as in Synthesis Example 1 except for using, to obtain 49.5 g of a white powdery solid (yield = 95.6%).
This solid matter confirmed the production | generation of copolymer PolyVOZO-St by the infrared absorption spectrum (IR).
The composition of this copolymer was confirmed by 1 H-NMR (CDCl 3 ) analysis to be VOZO-derived unit / St-derived unit = 1.00 / 0.97.
(合成例6)
PolyVOZO−Stの水和反応によるPolyOH−St−5の合成
合成例5で合成したPolyVOZO−St−3
20.0g、水を54.6g(3.032mol、オキサゾリン基に対して30倍mol)を用い、反応を80℃で15時間のみ行うこと以外は合成例2と同様に行い、白色粉末状固形物21.6gを得た(収率=99.0%)。
得られた固形物中のオキサゾリン基と水酸基を定量し、得られたPolyOH−St−5のユニット比は、OH/St=50.8/49.2であった。なお、PolyOH−St−5は、オキサゾリン基を定量した結果、検出できなかったので全て水酸基になっていると判断した。
また、得られたPolyOH−St−5のTgは102℃であり、DIBAに10%以上溶解することを確認した。
(Synthesis Example 6)
Synthesis of PolyOH-St-5 by hydration reaction of PolyVOZO-St PolyVOZO-St-3 synthesized in Synthesis Example 5
20.0 g, 54.6 g of water (3.032 mol, 30 times mol with respect to the oxazoline group) were used, and the reaction was carried out in the same manner as in Synthesis Example 2 except that the reaction was carried out at 80 ° C. for 15 hours. 21.6 g of the product was obtained (Yield = 99.0%).
The oxazoline group and the hydroxyl group in the obtained solid were quantified, and the unit ratio of PolyOH-St-5 obtained was OH / St = 50.8 / 49.2. Since PolyOH-St-5 was not detected as a result of quantitative determination of the oxazoline group, it was judged that it was all hydroxyl groups.
Moreover, Tg of obtained PolyOH-St-5 was 102 degreeC, and it confirmed that 10% or more melt | dissolved in DIBA.
(合成例7)
2−イソプロペニル−2−オキサゾリンとスチレンの共重合体PolyIPOZO−Stの合成
合成例1において、VOZOにかえてイソプロペニルオキサゾリン(IPOZO)5.7g(51.5mmol)、エタノール54.9gを用いた以外は、合成例1と同様に行い、白色粉末状固形物49.8gを得た(収率=92.2%)。
本固形物は、赤外吸収スペクトル(IR)により、コポリマーPolyIPOZO−Stの生成を確認した。
本コポリマーの組成は1H−NMR(CDCl3)分析により、IPOZO由来ユニット/St由来ユニット=1.00/8.73と確認した。
(Synthesis Example 7)
Synthesis of 2-Isopropenyl-2-oxazoline and Styrene Copolymer PolyIPOZO-St In Synthesis Example 1, 5.7 g (51.5 mmol) of isopropenyloxazoline (IPOZO) and 54.9 g of ethanol were used instead of VOZO. Was performed in the same manner as in Synthesis Example 1 to obtain 49.8 g of a white powdery solid (yield = 92.2%).
This solid matter confirmed the production | generation of copolymer PolyIPOZO-St by the infrared absorption spectrum (IR).
The composition of this copolymer was confirmed by 1 H-NMR (CDCl 3 ) analysis to be IPOZO-derived units / St-derived units = 1.00 / 8.73.
(合成例8)
PolyIPOZO−Stの水和反応によるPolyOH−St−6の合成
合成例7で得られたPolyVOZO−St−3 20.0g、水10.6g(589mmol、オキサゾリン基に対して30倍mol)を用い、合成例6と同様に溶媒THF中で水和反応を行い、白色粉末状固形物19.8g(収率=97.3%)。
得られた固形物中のオキサゾリン基と水酸基を定量し、PolyOH−St−6のユニット比は、OH/St=10.3/89.7であった。なお、PolyOH−St−6は、オキサゾリン基を定量した結果、検出できなかったので全て水酸基になっていると判断した。
また、得られたPolyOH−St−6のTgは88℃であり、DIBAに10%以上溶解することを確認した。
(Synthesis Example 8)
Synthesis of PolyOH-St-6 by hydration reaction of PolyIPOZO-St 20.0 g of PolyVOZO-St-3 obtained in Synthesis Example 7 and 10.6 g of water (589 mmol, 30 times mol with respect to the oxazoline group) A hydration reaction was performed in the solvent THF in the same manner as in Synthesis Example 6 to obtain 19.8 g of a white powdery solid (yield = 97.3%).
The oxazoline group and hydroxyl group in the obtained solid were quantified, and the unit ratio of PolyOH-St-6 was OH / St = 10.3 / 89.7. Since PolyOH-St-6 was not detected as a result of quantifying the oxazoline group, it was judged that all of it was a hydroxyl group.
Moreover, Tg of obtained PolyOH-St-6 was 88 degreeC, and it confirmed that 10% or more melt | dissolved in DIBA.
(合成例9)
PolyVOZO−Stの水和反応によるPolyOH−St−7の合成
合成例2において、PolyVOZO−St−1を溶解させる溶媒として酢酸エチル180.0g、反応を80℃で15時間のみを行う以外は合成例2と同様に行い、白色粉末状固形物20.0gを得た(収率=98.3%)。
得られた固形物中のオキサゾリン基と水酸基を定量し、15時間反応させて得られたPolyOH−St−7のユニット比は、VOZO/OH/St=5.2/4.9/89.9であった。
また、得られたPolyOH−St−7のTgは88℃であり、DIBAに10%以上溶解することを確認した。
(Synthesis Example 9)
Synthesis of PolyOH-St-7 by hydration reaction of PolyVOZO-St In Synthesis Example 2, Synthesis Example except that 180.0 g of ethyl acetate was used as a solvent for dissolving PolyVOZO-St-1 and the reaction was carried out at 80 ° C. for only 15 hours. 2 to obtain 20.0 g of a white powdery solid (yield = 98.3%).
The unit ratio of PolyOH-St-7 obtained by quantifying the oxazoline group and hydroxyl group in the obtained solid and reacting for 15 hours was VOZO / OH / St = 5.2 / 4.9 / 89.9. Met.
Moreover, Tg of obtained PolyOH-St-7 was 88 degreeC, and it confirmed that 10% or more melt | dissolved in DIBA.
(合成例10)
5−メチル−2−ビニル−2−オキサゾリンとスチレンの共重合体PolyMVOZO−Stの合成
合成例1において、VOZOにかえて5−メチル−2−ビニル−2−オキサゾリン(MVOZO)5.7g(51.5mmol)、エタノール54.9gを用いた以外は、合成例1と同様に行い、白色粉末状固形物50.0gを得た(収率=92.6%)。
本固形物は、赤外吸収スペクトル(IR)により、コポリマーPolyMVOZO−Stの生成を確認した。
本コポリマーの組成は1H−NMR(CDCl3)分析により、MVOZO由来ユニット/St由来ユニット=1.00/8.77と確認した。
(Synthesis Example 10)
Synthesis of 5-methyl-2-vinyl-2-oxazoline and styrene copolymer PolyMVOZO-St In Synthesis Example 1, 5.7 g of 5-methyl-2-vinyl-2-oxazoline (MVOZO) instead of VOZO (51 0.5 mmol) and 54.9 g of ethanol were used in the same manner as in Synthesis Example 1 to obtain 50.0 g of a white powdery solid (yield = 92.6%).
This solid matter confirmed the production | generation of copolymer PolyMVOZO-St by the infrared absorption spectrum (IR).
The composition of this copolymer was confirmed by 1 H-NMR (CDCl 3 ) analysis to be MVOZO-derived unit / St-derived unit = 1.00 / 8.77.
(合成例11)
PolyMVOZO−Stの水和反応によるPolyOH−St−8の合成
合成例6において、PolyVOZO−St−3にかえてPolyMVOZO−St20.0g、水10.6g(587mmol、オキサゾリン基に対して30倍mol)を用いた以外は、合成例6と同様に行い、白色粉末状固形物19.9g(収率=97.8%)。
得られた固形物中のオキサゾリン基と水酸基を定量し、PolyOH−St−8のユニット比は、OH/St=10.2/89.8であった。なお、PolyOH−St−8は、オキサゾリン基を定量した結果、検出できなかったので全て水酸基になっていると判断した。
また、得られたPolyOH−St−8のTgは87℃であり、DIBAに10%以上溶解することを確認した。
(Synthesis Example 11)
Synthesis of PolyOH-St-8 by hydration reaction of PolyMVOZO-St In Synthesis Example 6, instead of PolyVOZO-St-3, 20.0 g of PolyMVOZO-St, 10.6 g of water (587 mmol, 30 times mol with respect to the oxazoline group) 19.9 g (yield = 97.8%) of the white powdery solid.
The oxazoline group and hydroxyl group in the obtained solid were quantified, and the unit ratio of PolyOH-St-8 was OH / St = 10.2 / 89.8. Since PolyOH-St-8 was not detected as a result of quantitative determination of the oxazoline group, it was judged that all were hydroxyl groups.
Moreover, Tg of obtained PolyOH-St-8 was 87 degreeC, and it confirmed that 10% or more melt | dissolved in DIBA.
(合成例12)
4,4’−ジメチル−2−ビニル−2−オキサゾリンとスチレンの共重合体PolyDMVOZO−Stの合成
合成例1において、VOZOにかえて4,4’−ジメチル−2−ビニル−2−オキサゾリン(DMVOZO)6.4g(51.5mmol)、エタノール55.6gを用いた以外は、合成例1と同様に行い、白色粉末状固形物50.1gを得た(収率=91.6%)。
本固形物は、赤外吸収スペクトル(IR)により、コポリマーPolyDMVOZO−Stの生成を確認した。
本コポリマーの組成は1H−NMR(CDCl3)分析により、DMVOZO由来ユニット/St由来ユニット=1.00/8.82と確認した。
(Synthesis Example 12)
Synthesis of 4,4'-dimethyl-2-vinyl-2-oxazoline and styrene copolymer PolyDMVOZO-St In Synthesis Example 1, 4,4'-dimethyl-2-vinyl-2-oxazoline (DMVOZO) was used instead of VOZO. ) Except having used 6.4g (51.5mmol) and 55.6g of ethanol, it carried out similarly to the synthesis example 1, and obtained 50.1g of white powdery solid (yield = 91.6%).
This solid matter confirmed the production | generation of copolymer PolyDMVOZO-St by the infrared absorption spectrum (IR).
The composition of this copolymer was confirmed by 1 H-NMR (CDCl 3 ) analysis to be DMVOZO-derived unit / St-derived unit = 1.00 / 8.82.
(合成例13)
PolyDMVOZO−Stの水和反応によるPolyOH−St−9の合成
合成例6において、PolyVOZO−St−3にかえてPolyDMVOZO−St 20.0g、水10.4g(576mmol、オキサゾリン基に対して30倍mol)を用いた以外は、合成例6と同様に行い、白色粉末状固形物19.7g(収率=96.9%)。
得られた固形物中のオキサゾリン基と水酸基を定量し、PolyOH−St−9のユニット比は、OH/St=10.2/89.8であった。なお、PolyOH−St−9は、オキサゾリン基を定量した結果、検出できなかったので全て水酸基になっていると判断した。
また、得られたPolyOH−St−9のTgは88℃であり、DIBAに10%以上溶解することを確認した。
(Synthesis Example 13)
Synthesis of PolyOH-St-9 by hydration reaction of PolyDMVOZO-St In Synthesis Example 6, instead of PolyVOZO-St-3, 20.0 g of PolyDMVOZO-St, 10.4 g of water (576 mmol, 30 times mol to the oxazoline group) ) Was used in the same manner as in Synthesis Example 6 to obtain 19.7 g of a white powdery solid (yield = 96.9%).
The oxazoline group and hydroxyl group in the obtained solid were quantified, and the unit ratio of PolyOH-St-9 was OH / St = 10.2 / 89.8. In addition, since PolyOH-St-9 was not detected as a result of quantifying the oxazoline group, it was judged that all were hydroxyl groups.
Moreover, Tg of obtained PolyOH-St-9 was 88 degreeC, and it confirmed that 10% or more melt | dissolved in DIBA.
(合成例14)
オキサゾリン基含有スチレン系共重合体(エポクロスRPS−1005)の水和反応によるPolyOH−St−10の合成
合成例6において、PolyVOZO−St−3にかえて市販品であるエポクロスRPS−1005(オキサゾリン基含有量3モル%、日本触媒株式会社製)
20.0g、水4.9g(270mmol、オキサゾリン基に対して30倍mol)を用いた以外は、合成例6と同様に行い、白色粉末状固形物19.8g(収率=98.2%)
得られた固形物中のオキサゾリン基と水酸基を定量し、PolyOH−St−10のユニット比は、OH/St=3.0/97.0であった。なお、PolyOH−St−10は、オキサゾリン基を定量した結果、検出できなかったので全て水酸基になっていると判断した。
また、得られたPolyOH−St−10のTgは82℃であり、DIBAに10%以上溶解することを確認した。
(Synthesis Example 14)
Synthesis of PolyOH-St-10 by hydration reaction of oxazoline group-containing styrene-based copolymer (Epocross RPS-1005) Content 3 mol%, Nippon Shokubai Co., Ltd.)
Except that 20.0 g and 4.9 g of water (270 mmol, 30 times mol with respect to the oxazoline group) were used, the same procedure as in Synthesis Example 6 was performed, and 19.8 g of white powdery solid (yield = 98.2%). )
The oxazoline group and hydroxyl group in the obtained solid were quantified, and the unit ratio of PolyOH-St-10 was OH / St = 3.0 / 97.0. Since PolyOH-St-10 was not detected as a result of quantitative determination of the oxazoline group, it was judged that all of it was a hydroxyl group.
Moreover, Tg of obtained PolyOH-St-10 was 82 degreeC, and it confirmed that 10% or more melt | dissolved in DIBA.
(合成例15)
2−ビニル−2−オキサゾリン、スチレンとメタクリル酸メチルの共重合体PolyVOZO−St−MMAの合成
合成例1において、VOZO 5.0g(51.5mmol)、St 42.9g(412.4mmol)、メタクリル酸メチル(MMA)5.2g(51.5mmol)、エタノール54.0gを用いた以外は合成例1と同様に行い、白色粉末状固形物51.0gを得た(収率=96.0%)。
本固形物は、赤外吸収スペクトル(IR)により、コポリマーPolyVOZO−St−MMAの生成を確認した。
本ポリマーの組成は1H−NMR(CDCl3)分析により、VOZO由来ユニット/St由来ユニット/MMA由来ユニット=10.3/80.2/9.5と確認した。
(Synthesis Example 15)
Synthesis of 2-vinyl-2-oxazoline, copolymer of styrene and methyl methacrylate PolyVOZO-St-MMA In Synthesis Example 1, VOZO 5.0 g (51.5 mmol), St 42.9 g (412.4 mmol), methacryl The procedure was the same as in Synthesis Example 1 except that 5.2 g (MMA) of methyl acid (MMA) and 54.0 g of ethanol were used to obtain 51.0 g of a white powdery solid (yield = 96.0%). ).
This solid substance confirmed the production | generation of copolymer PolyVOZO-St-MMA by the infrared absorption spectrum (IR).
The composition of this polymer was confirmed by 1 H-NMR (CDCl 3 ) analysis to be VOZO-derived unit / St-derived unit / MMA-derived unit = 10.3 / 80.2 / 9.5.
(合成例16)
PolyVOZO−St−MMAの水和反応によるPolyOH−St−11の合成
合成例6において、PolyVOZO−St−3にかえてPolyVOZO−St−MMA20.0g、水10.8g(601mmol、オキサゾリン基に対して30倍mol)を用いた以外は合成例6と同様に行い、白色粉末状固形物19.9gを得た。(収率=97.7%)
得られた固形物中のオキサゾリン基と水酸基を定量し、PolyOH−St−11のユニット比は、OH/St/MMA=10.3/80.2/9.5であった。なお、PolyOH−St−11は、オキサゾリン基を定量した結果、検出できなかったので全て水酸基になっていると判断した。
また、得られたPolyOH−St−11のTgは86℃であり、DIBAに10%以上溶解することを確認した。
(Synthesis Example 16)
Synthesis of PolyOH-St-11 by hydration reaction of PolyVOZO-St-MMA In Synthesis Example 6, instead of PolyVOZO-St-3, 20.0 g of PolyVOZO-St-MMA, 10.8 g of water (601 mmol, relative to the oxazoline group) The same procedure as in Synthesis Example 6 was performed except that 30 mol) was used to obtain 19.9 g of a white powdery solid. (Yield = 97.7%)
The oxazoline group and hydroxyl group in the obtained solid were quantified, and the unit ratio of PolyOH-St-11 was OH / St / MMA = 10.3 / 80.2 / 9.5. Since PolyOH-St-11 was not detected as a result of quantifying the oxazoline group, it was judged that it was all hydroxyl groups.
Moreover, Tg of obtained PolyOH-St-11 was 86 degreeC, and it confirmed that 10% or more melt | dissolved in DIBA.
(合成例17)
2−ビニル−2−オキサゾリン、スチレンとアクリル酸ブチルの共重合体PolyVOZO−St−BAの合成
合成例1において、VOZO 5.0g(51.5mmol)、St 42.9g(412.4mmol)、アクリル酸ブチル(BA)6.6g(51.5mmol)、エタノール55.4gを用いた以外は合成例1と同様に行い、白色粉末状固形物51.9gを得た(収率=95.2%)。
本固形物は、赤外吸収スペクトル(IR)により、コポリマーPolyVOZO−St−BAの生成を確認した。
本ポリマーの組成は1H−NMR(CDCl3)分析により、VOZO由来ユニット/St由来ユニット/BA由来ユニット=10.1/80.0/9.9と確認した。
(Synthesis Example 17)
Synthesis of 2-vinyl-2-oxazoline, copolymer of styrene and butyl acrylate PolyVOZO-St-BA In Synthesis Example 1, VOZO 5.0 g (51.5 mmol), St 42.9 g (412.4 mmol), acrylic Except that 6.6 g (51.5 mmol) of butyl acid (BA) and 55.4 g of ethanol were used, the same procedure as in Synthesis Example 1 was performed to obtain 51.9 g of a white powdery solid (yield = 95.2%). ).
This solid matter confirmed the production | generation of copolymer PolyVOZO-St-BA by the infrared absorption spectrum (IR).
The composition of this polymer was confirmed by 1 H-NMR (CDCl 3 ) analysis to be VOZO-derived unit / St-derived unit / BA-derived unit = 10.1 / 80.0 / 9.9.
(合成例18)
PolyVOZO−St−BAの水和反応によるPolyOH−St−12の合成
合成例6において、PolyVOZO−St−3にかえてPolyVOZO−St−BA 20.0g、水10.5g(581mmol、オキサゾリン基に対して30倍mol)を用いた以外は合成例6と同様に行い、白色粉末状固形物20.0gを得た。(収率=98.3%)
得られた固形物中のオキサゾリン基と水酸基を定量し、15時間反応させて得られたPolyOH−St−12のユニット比は、OH/St/BA=10.1/80.0/9.9であった。なお、PolyOH−St−11は、オキサゾリン基を定量した結果、検出できなかったので全て水酸基になっていると判断した。
また、得られたPolyOH−St−12のTgは68℃であり、DIBAに10%以上溶解することを確認した。
(Synthesis Example 18)
Synthesis of PolyOH-St-12 by hydration reaction of PolyVOZO-St-BA In Synthesis Example 6, instead of PolyVOZO-St-3, 20.0 g of PolyVOZO-St-BA, 10.5 g of water (581 mmol, based on the oxazoline group) This was carried out in the same manner as in Synthesis Example 6 except that 30 mol was used to obtain 20.0 g of a white powdery solid. (Yield = 98.3%)
The unit ratio of PolyOH-St-12 obtained by quantifying the oxazoline group and hydroxyl group in the obtained solid and reacting for 15 hours was OH / St / BA = 10.1 / 80.0 / 9.9. Met. Since PolyOH-St-11 was not detected as a result of quantifying the oxazoline group, it was judged that it was all hydroxyl groups.
Moreover, Tg of obtained PolyOH-St-12 was 68 degreeC, and it confirmed that 10% or more melt | dissolved in DIBA.
(比較合成例1)
2−ヒドロキシエチルアクリルアミドとスチレンの共重合体PolyHEAA−St−1の合成
合成例1において、VOZOにかえて2−ヒドロキシエチルアクリルアミド(HEAA)5.9g(51.5mmol)、溶媒としてエタノール55.0gを用いた以外は、合成例1と同様に重合を行い、さらに、生成物をメタノールで沈殿、洗浄し、残存するHEAA及び副生成するHEAAのホモポリマーを除去し、白色粉末状固形物8.02gを得た(収率=14.8%)。
本コポリマーの組成は1H−NMR(CDCl3)分析により、HEAA由来ユニット/St由来ユニット=2.7/97.3と確認した。
また、得られたPolyHEAA−StのTgは87℃であり、DIBAに溶解しないことを確認した。
(Comparative Synthesis Example 1)
Synthesis of Copolymer of 2-hydroxyethylacrylamide and styrene PolyHEAA-St-1 In Synthesis Example 1, 5.9 g (51.5 mmol) of 2-hydroxyethylacrylamide (HEAA) instead of VOZO, and 55.0 g of ethanol as a solvent Polymerization is carried out in the same manner as in Synthesis Example 1, except that the product is precipitated and washed with methanol, and the remaining HEAA and by-product HEAA homopolymer are removed to obtain a white powdery solid. 02 g was obtained (yield = 14.8%).
The composition of this copolymer was confirmed by 1 H-NMR (CDCl 3 ) analysis to be HEAA-derived unit / St-derived unit = 2.7 / 97.3.
Moreover, Tg of obtained PolyHEAA-St was 87 degreeC, and it confirmed that it did not melt | dissolve in DIBA.
(比較合成例2)
2−ヒドロキシエチルアクリルアミドとスチレンの共重合体PolyHEAA−St−2の合成
合成例1において、VOZOにかえてHEAA 1.2g(10.3mmol)、St 52.5g(505.2mmol)、溶媒としてDIBA 54.6gを用いた以外は、合成例1と同様に重合を行ったが、重合中に析出物が見られたため中止し、ポリマーの分析は行わなかった。
(Comparative Synthesis Example 2)
Synthesis of 2-Hydroxyethylacrylamide and Styrene Copolymer PolyHEAA-St-2 In Synthesis Example 1, 1.2 g (10.3 mmol) of HEAA instead of VOZO, 52.5 g (505.2 mmol) of StAA, and DIBA as a solvent Polymerization was carried out in the same manner as in Synthesis Example 1 except that 54.6 g was used. However, since a precipitate was observed during the polymerization, the polymerization was stopped and the polymer was not analyzed.
(比較合成例3)
4−ヒドロキシブチルアクリレートとスチレンの共重合体Poly4HBA−St−1の合成
合成例1において、VOZOにかえて4−ヒドロキシブチルアクリレート(4HBA)14.9g(103.0mmol)、St 42.9g(412.4mmol)、溶媒としてエタノール58.6gを用いた以外は合成例1と同様に行い、白色粉末状固形物52.8gを得た(収率=91.3%)。
Poly4HBA−St−1の組成は1H−NMR(CDCl3)分析により、4HBA由来ユニット/St由来ユニット=23.6/76.4と確認した。
また、得られたPoly4HBA−St−1のTgは26℃であり、DIBAに溶解しないことを確認した。
(Comparative Synthesis Example 3)
Synthesis of 4-hydroxybutyl acrylate and styrene copolymer Poly4HBA-St-1 In Synthesis Example 1, 14.9 g (103.0 mmol) of 4-hydroxybutyl acrylate (4HBA) instead of VOZO, 42.9 g of St (412) 0.4 mmol), and the same procedure as in Synthesis Example 1 was carried out except that 58.6 g of ethanol was used as a solvent to obtain 52.8 g of a white powdery solid (yield = 91.3%).
The composition of Poly4HBA-St-1 was confirmed by 1 H-NMR (CDCl 3 ) analysis to be 4HBA-derived unit / St-derived unit = 23.6 / 76.4.
Moreover, Tg of obtained Poly4HBA-St-1 was 26 degreeC, and it confirmed that it did not melt | dissolve in DIBA.
(比較合成例4)
4−ヒドロキシブチルアクリレートとスチレンの共重合体Poly4HBA−St−2の合成
合成例1において、VOZOにかえて4HBA 7.4g(51.5mmol)、エタノールにかえて溶媒としてDIBA 56.6gを用いた以外は合成例1と同様に行い、白色粉末状固形物50.6gを得た(収率=90.8%)。
Poly4HBA−St−2の組成は1H−NMR(CDCl3)分析により、4HBA由来ユニット/St由来ユニット=11.4/88.6と確認した。
また、得られたPoly4HBA−St−2のTgは30℃であり、DIBAに10%以上溶解することを確認した。
(Comparative Synthesis Example 4)
Synthesis of 4-hydroxybutyl acrylate and styrene copolymer Poly4HBA-St-2 In Synthesis Example 1, 7.4 g (51.5 mmol) of 4HBA was used instead of VOZO, and 56.6 g of DIBA was used as a solvent instead of ethanol. Was performed in the same manner as in Synthesis Example 1 to obtain 50.6 g of a white powdery solid (yield = 90.8%).
The composition of Poly4HBA-St-2 was confirmed by 1 H-NMR (CDCl 3 ) analysis to be 4HBA-derived unit / St-derived unit = 11.4 / 88.6.
Moreover, Tg of obtained Poly4HBA-St-2 is 30 degreeC, It confirmed that 10% or more melt | dissolves in DIBA.
合成例及び比較合成例の結果より、側鎖に水酸基を有し、Tgが50℃以上で、かつ、DIBA等の疎水性有機溶媒に可溶である本発明の芳香族ビニル系重合体は、側鎖にオキサゾリン基を有する共重合体の水和反応でのみ得られることが明らかである。 From the results of the synthesis examples and comparative synthesis examples, the aromatic vinyl polymer of the present invention having a hydroxyl group in the side chain, having a Tg of 50 ° C. or higher, and being soluble in a hydrophobic organic solvent such as DIBA, It is clear that it can be obtained only by a hydration reaction of a copolymer having an oxazoline group in the side chain.
実施例A 押出発泡法によるポリスチレン系樹脂発泡成形体の製造
実施例A−1
スチレン系樹脂としてポリスチレン99部、合成例2で得られた水酸基含有の芳香族ビニル系重合体PolyOH−St−1 1部、造核剤としてタルク0.5部、ステアリン酸バリウム0.25部をドライブレンドし、タンデム型押出機へ供給した。第1押出機(口径65mm)のホッパーよりに供給した樹脂混合物を200℃に加熱して溶融混練した後、発泡剤としてイソブタン4部を第1押出機の先端付近で樹脂中に圧入した。続いて、第2押出機(口径90mm)で樹脂を混練しながら120℃に冷却し、第2押出機先端に設置した成形金型(幅、長さ、厚さが200mm、150mm、25mm)の口金部より大気圧下で押出し、ポリスチレン系樹脂発泡成形体を得た。得られた発泡成形体の外観観察と各種物性測定を行い、結果を表1に示した。
Example A Production of Polystyrene Resin Foam Molded Body by Extrusion Foaming Example A-1
99 parts of polystyrene as a styrene resin, 1 part of a hydroxyl group-containing aromatic vinyl polymer PolyOH-St-1 obtained in Synthesis Example 2, 0.5 part of talc as a nucleating agent, and 0.25 part of barium stearate Dry blended and fed to a tandem extruder. After the resin mixture supplied from the hopper of the first extruder (caliber 65 mm) was heated to 200 ° C. and melt-kneaded, 4 parts of isobutane as a foaming agent was pressed into the resin near the tip of the first extruder. Subsequently, while the resin was kneaded with the second extruder (caliber 90 mm), it was cooled to 120 ° C., and the molding die (width, length, thickness 200 mm, 150 mm, 25 mm) installed at the tip of the second extruder was used. Extrusion was performed from the base part under atmospheric pressure to obtain a polystyrene-based resin foam molded article. Appearance observation and various physical property measurements of the obtained foamed molded article were performed, and the results are shown in Table 1.
実施例A−2〜A−17
スチレン系樹脂及び水酸基含有の芳香族ビニル系重合体の品種、添加量を表1に示す値とした以外は実施例A−1と同様に実施した。
Examples A-2 to A-17
The same procedure as in Example A-1 was carried out except that the styrene resin and hydroxyl group-containing aromatic vinyl polymer varieties and addition amounts were set to the values shown in Table 1.
比較例A−18〜A−25
水酸基含有の芳香族ビニル系重合体を配合せず(比較例A−18)、又は水酸基含有の重合体としてPolyHEAA−St、Poly4HBA−St或いはエチレン−ビニルアルコール共重合体、ポリビニルアルコールを配合し(比較例A−19〜A−25)、実施例A−1と同様に押出発泡成形により成形体を製造した。得られた発泡成形体の外観観察と各種物性測定を行い、結果を表2に示した。
Comparative Examples A-18 to A-25
No hydroxyl group-containing aromatic vinyl polymer is blended (Comparative Example A-18), or PolyHEAA-St, Poly4HBA-St or ethylene-vinyl alcohol copolymer, polyvinyl alcohol is blended as a hydroxyl group-containing polymer ( Comparative Examples A-19 to A-25) and molded bodies were produced by extrusion foam molding in the same manner as in Example A-1. Appearance observation and various physical property measurements of the obtained foamed molded article were performed, and the results are shown in Table 2.
実施例B 予備発泡粒子発泡法によるポリスチレン系樹脂発泡成形体の製造−1
実施例B−1
ポリオレフィン系樹脂としてエチレン−酢酸ビニルの共重合体99部、水酸基含有の芳香族ビニル系重合体としてPolyOH−St−1 1部、造核剤としてタルク0.5部、ステアリン酸バリウム0.25部をドライブレンドし、二軸押出機のホッパーより供給し、220℃で溶融混練して押出機からストランド状に押出し、ペレタイザーにより切断してポリオレフィン系樹脂粒子を作製した。
次に、撹拌機付き耐圧重合容器に、水100部、ポリオレフィン系樹脂粒子30部、懸濁剤としてピロリン酸マグネシウム0.0175部、ドデシルベンゼンスルホン酸カルシウム0.0175部を入れ、撹拌しながら90℃に昇温した。さらに、ベンゾイルパーオキサイド0.1部、t−ブチルパーオキシベンゾエート0.05部をスチレン70部に溶解させた溶液を4時間かけて添加して重合した。さらに、130℃で3時間重合を行った後、冷却してポリスチレン系樹脂粒子を得た。続いて、耐圧重合容器内に可塑剤としてジイソブチルアジペート1部、発泡剤としてイソブタン7.5部を圧入し、90℃に昇温して3時間保持後、冷却して脱水、乾燥させてポリスチレン系樹脂発泡性粒子を得た。このポリスチレン系樹脂発泡性粒子を100℃の水蒸気で加熱して予備発泡粒子とし、得られたポリスチレン系樹脂予備発泡粒子を室温雰囲気下で24時間保持した後、このポリスチレン系樹脂予備発泡粒子を密閉金型に充填して水蒸気で加熱し、予備発泡粒子を2次発泡させてポリスチレン系樹脂発泡成形体を製造した。得られたポリスチレン系樹脂発泡成形体の物性を評価した結果を表3に示した。
Example B Production of Polystyrene Resin Foam Molded Article by Prefoamed Particle Foaming Method-1
Example B-1
99 parts of ethylene-vinyl acetate copolymer as polyolefin resin, 1 part of PolyOH-St-1 as aromatic vinyl polymer containing hydroxyl group, 0.5 part of talc as nucleating agent, 0.25 part of barium stearate Were fed from a hopper of a twin screw extruder, melt kneaded at 220 ° C., extruded into a strand from the extruder, and cut by a pelletizer to produce polyolefin resin particles.
Next, 100 parts of water, 30 parts of polyolefin resin particles, 0.0175 part of magnesium pyrophosphate and 0.0175 part of calcium dodecylbenzenesulfonate as a suspending agent are placed in a pressure-resistant polymerization vessel equipped with a stirrer and stirred while stirring. The temperature was raised to ° C. Further, 0.1 part of benzoyl peroxide and 0.05 part of t-butyl peroxybenzoate were dissolved in 70 parts of styrene for polymerization for 4 hours. Further, polymerization was performed at 130 ° C. for 3 hours, and then cooled to obtain polystyrene resin particles. Subsequently, 1 part of diisobutyl adipate as a plasticizer and 7.5 parts of isobutane as a foaming agent are press-fitted into a pressure-resistant polymerization vessel, heated to 90 ° C., held for 3 hours, cooled, dehydrated and dried, and polystyrene-based Resin expandable particles were obtained. The polystyrene-based resin expandable particles are heated with 100 ° C. water vapor to form pre-expanded particles. The obtained polystyrene-based resin pre-expanded particles are held in a room temperature atmosphere for 24 hours, and then the polystyrene-based resin pre-expanded particles are sealed. The mold was filled and heated with water vapor, and the pre-expanded particles were secondarily expanded to produce a polystyrene-based resin foam molded article. Table 3 shows the results of evaluating the physical properties of the obtained polystyrene resin foam molded article.
実施例B−2〜B−16
ポリオレフィン系樹脂及び水酸基含有の芳香族ビニル系重合体の品種、添加量を表3に示す値とした以外は実施例B−1と同様に実施した。
Examples B-2 to B-16
The same procedure as in Example B-1 was carried out except that the types and addition amounts of the polyolefin resin and the hydroxyl group-containing aromatic vinyl polymer were changed to the values shown in Table 3.
比較例B−17〜B−22
水酸基含有の芳香族ビニル系重合体を配合せず(比較例B−17)、又は水酸基含有の重合体としてPolyHEAA−St、Poly4HBA−St或いはエチレン−ビニルアルコール共重合体、ポリビニルアルコールを配合し(比較例B−18〜B−22)、実施例B−1と同様にポリスチレン系樹脂発泡性粒子、ポリスチレン系樹脂予備発泡粒子及びポリスチレン系樹脂発泡成形体を製造した。得られた発泡成形体の外観観察と各種物性測定を行い、結果を表4に示した。
Comparative Examples B-17 to B-22
A hydroxyl group-containing aromatic vinyl polymer is not blended (Comparative Example B-17), or a polyHEAA-St, Poly4HBA-St, ethylene-vinyl alcohol copolymer, or polyvinyl alcohol is blended as a hydroxyl group-containing polymer ( Comparative Example B-18 to B-22) and polystyrene-based resin foamable particles, polystyrene-based resin pre-expanded particles, and polystyrene-based resin foamed molded articles were produced in the same manner as in Example B-1. Appearance observation and various physical property measurements of the obtained foamed molded article were performed, and the results are shown in Table 4.
実施例C 予備発泡粒子発泡法によるポリスチレン系樹脂発泡成形体の製造−2
実施例C−1
ポリオレフィン系樹脂としてエチレン−酢酸ビニルの共重合体100部、造核剤としてタルク0.5部、ステアリン酸バリウム0.25部をドライブレンドし、二軸押出機のホッパーより供給し、220℃で溶融混練して押出機からストランド状に押出し、ペレタイザーにより切断してポリオレフィン系樹脂粒子を作製した。
次に、撹拌機付き耐圧重合容器に、水100部、ポリオレフィン系樹脂粒子30部、懸濁剤としてピロリン酸マグネシウム0.0175部、ドデシルベンゼンスルホン酸カルシウム0.0175部を入れ、撹拌しながら90℃に昇温した。さらに、ベンゾイルパーオキサイド0.1部、t−ブチルパーオキシベンゾエート0.05部をスチレン70部に溶解させた溶液を4時間かけて添加して重合した。さらに、130℃で3時間重合を行った後、冷却してポリスチレン系樹脂粒子を得た。続いて、耐圧重合容器内に水酸基含有の芳香族ビニル系重合体を溶解したジイソブチルアジペート溶液(10%)1部、発泡剤としてイソブタン7.5質量部を圧入し、90℃に昇温して3時間保持後、冷却して脱水、乾燥させてポリスチレン系樹脂発泡性粒子を得た。このポリスチレン系樹脂発泡性粒子を100℃の水蒸気で加熱して予備発泡粒子とし、得られたポリスチレン系樹脂予備発泡粒子を室温雰囲気下で24時間保持した後、このポリスチレン系樹脂予備発泡粒子を密閉金型に充填して水蒸気で加熱し、予備発泡粒子を2次発泡させてポリスチレン系樹脂発泡成形体を製造した。得られたポリスチレン系樹脂発泡成形体の物性を評価した結果を表5に示した。
Example C Production of Polystyrene Resin Foam Molded Body by Prefoamed Particle Foaming Method-2
Example C-1
100 parts of ethylene-vinyl acetate copolymer as polyolefin resin, 0.5 part of talc and 0.25 part of barium stearate as nucleating agent are dry blended and supplied from the hopper of a twin screw extruder at 220 ° C. It was melt-kneaded, extruded from an extruder into a strand, and cut by a pelletizer to produce polyolefin resin particles.
Next, 100 parts of water, 30 parts of polyolefin resin particles, 0.0175 part of magnesium pyrophosphate and 0.0175 part of calcium dodecylbenzenesulfonate as a suspending agent are placed in a pressure-resistant polymerization vessel equipped with a stirrer and stirred while stirring. The temperature was raised to ° C. Further, 0.1 part of benzoyl peroxide and 0.05 part of t-butyl peroxybenzoate were dissolved in 70 parts of styrene for polymerization for 4 hours. Further, polymerization was performed at 130 ° C. for 3 hours, and then cooled to obtain polystyrene resin particles. Subsequently, 1 part of a diisobutyl adipate solution (10%) in which a hydroxyl group-containing aromatic vinyl polymer was dissolved in a pressure-resistant polymerization vessel and 7.5 parts by mass of isobutane as a foaming agent were injected and the temperature was raised to 90 ° C. After holding for 3 hours, it was cooled, dehydrated and dried to obtain polystyrene-based resin expandable particles. The polystyrene-based resin expandable particles are heated with 100 ° C. water vapor to form pre-expanded particles. The obtained polystyrene-based resin pre-expanded particles are held in a room temperature atmosphere for 24 hours, and then the polystyrene-based resin pre-expanded particles are sealed. The mold was filled and heated with water vapor, and the pre-expanded particles were secondarily expanded to produce a polystyrene-based resin foam molded article. Table 5 shows the results of evaluating the physical properties of the obtained polystyrene-based resin foam molded article.
実施例C−2〜C−16
ポリオレフィン系樹脂及び水酸基含有の芳香族ビニル系重合体の品種、添加量を表5に示す値とした以外は実施例C−1と同様に実施した。
Examples C-2 to C-16
The same procedure as in Example C-1 was carried out except that the types and addition amounts of the polyolefin resin and the hydroxyl group-containing aromatic vinyl polymer were changed to the values shown in Table 5.
比較例C−17〜C−22
水酸基含有の芳香族ビニル系重合体を配合せず(比較例C−17)、又は水酸基含有の重合体としてPoly4HBA−St−2を配合し(比較例C−18〜B−22)、実施例C−1と同様にポリスチレン系樹脂発泡性粒子、ポリスチレン系樹脂予備発泡粒子及びポリスチレン系樹脂発泡成形体を製造した。得られた発泡成形体の外観観察と各種物性測定を行い、結果を表6に示した。なお、PolyHEAA−St、Poly4HBA−St−1及びエチレン−ビニルアルコール共重合体、ポリビニルアルコールはDIBAに溶解しないため、DIBAの10%溶液が得られなかった。
Comparative Examples C-17 to C-22
Example: No hydroxyl group-containing aromatic vinyl polymer was blended (Comparative Example C-17), or Poly4HBA-St-2 was blended as a hydroxyl group-containing polymer (Comparative Examples C-18 to B-22). Similarly to C-1, polystyrene-based resin foamable particles, polystyrene-based resin pre-expanded particles, and polystyrene-based resin foamed molded articles were produced. Appearance observation and various physical property measurements of the obtained foamed molded article were performed, and the results are shown in Table 6. PolyHEAA-St, Poly4HBA-St-1, ethylene-vinyl alcohol copolymer, and polyvinyl alcohol were not dissolved in DIBA, and thus a 10% solution of DIBA was not obtained.
以上説明してきたように、本発明の側鎖に水酸基を持ち、疎水性で有機溶媒にも可溶な、高いガラス相転移温度を有する芳香族ビニル系重合体が、ポリスチレン系樹脂に対して優れた相溶性を有し、それを配合することにより得られるポリスチレン系樹脂発泡成形体は、該重合体の少量添加でも高い独立気泡率と十分な発泡剤逸散防止効果を付与でき、剛性、耐衝撃性に優れ、断熱性、表面外観と寸法安定性、帯電防止性に優れた発泡体として使用できる。
As described above, the aromatic vinyl polymer having a high glass phase transition temperature, having a hydroxyl group in the side chain of the present invention, being hydrophobic and soluble in an organic solvent, is superior to a polystyrene resin. The polystyrene-based resin foam molded article obtained by blending it with a high degree of closed cell ratio and sufficient foaming agent dissipation prevention effect even when added in a small amount of the polymer. It can be used as a foam with excellent impact, heat insulation, surface appearance and dimensional stability, and antistatic properties.
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