JP2008208385A - Flame retardant composed of acrylamide-based polymer containing sulfonic acid group - Google Patents

Flame retardant composed of acrylamide-based polymer containing sulfonic acid group Download PDF

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JP2008208385A
JP2008208385A JP2008150534A JP2008150534A JP2008208385A JP 2008208385 A JP2008208385 A JP 2008208385A JP 2008150534 A JP2008150534 A JP 2008150534A JP 2008150534 A JP2008150534 A JP 2008150534A JP 2008208385 A JP2008208385 A JP 2008208385A
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Yoshio Kanzaki
吉夫 神崎
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Uni-Chemical Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant composed of acrylamide-based polymer having a high electrolytic group density. <P>SOLUTION: The flame retardant is a copolymer of (1) an acrylamidealkanesulfonate expressed by a formula (1) (wherein R<SP>1</SP>is a hydrogen or methyl group, R<SP>2</SP>and R<SP>3</SP>are hydrogen or 1-3C alkyl groups, R<SP>4</SP>is a 1-3C alkylene group, and M<SP>1</SP>is a hydrogen group, metal, or tertiary amine residue), and (2) an unsaturated compound (a) which has one or more ethylene-based unsaturated bonds but does not have any acid groups in a molecule, an unsaturated compound (b) which has one or more ethylene-based unsaturated bonds and one or more acid groups in a molecule, or their mixture. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、高い電解質基密度を有するスルホン酸基含有アクリルアミド系重合体からなる難燃剤に関する。   The present invention relates to a flame retardant comprising a sulfonic acid group-containing acrylamide polymer having a high electrolyte group density.

電解質基を有するアクリルアミド系重合体からなる難燃剤について、特開2001-11318号（特許文献１）は、スルホン酸基及び／又はその塩等のイオン基を有し、かつアクリルアミド類単位を含有する脂肪族系樹脂難燃剤を記載している。特許文献１は、この脂肪族系樹脂難燃剤の製造方法として、脂肪族系樹脂を濃硫酸で処理する方法を記載している。しかし特許文献１は、アクリルアミドアルカンスルホン酸塩と、（メタ）アクリルアミド等の不飽和化合物とを共重合してなる難燃剤を記載していない。   Regarding a flame retardant composed of an acrylamide polymer having an electrolyte group, JP-A-2001-11318 (Patent Document 1) has an ionic group such as a sulfonic acid group and / or a salt thereof, and contains an acrylamide unit. An aliphatic resin flame retardant is described. Patent Document 1 describes a method of treating an aliphatic resin with concentrated sulfuric acid as a method for producing this aliphatic resin flame retardant. However, Patent Document 1 does not describe a flame retardant obtained by copolymerizing acrylamide alkane sulfonate and an unsaturated compound such as (meth) acrylamide.

特開2001-11318号公報JP 2001-11318 A

従って、本発明の目的は、高い電解質基密度を有するアクリルアミド系重合体からなる難燃剤を提供することである。   Accordingly, an object of the present invention is to provide a flame retardant comprising an acrylamide polymer having a high electrolyte group density.

上記目的に鑑み鋭意研究の結果、本発明者は、アクリルアミドアルカンスルホン酸塩と、分子内に１個のエチレン性不飽和結合を有するが酸性基を有しない不飽和化合物(a)、分子内にエチレン性不飽和結合と酸性基とを各々１個有する不飽和化合物(b)、又はこれらの混合物とを共重合させると、高い電解質基密度を有するアクリルアミド系重合体からなる難燃剤が得られることを見出し、本発明に想到した。   As a result of diligent research in view of the above object, the present inventor has found that an acrylamide alkane sulfonate, an unsaturated compound (a) having one ethylenically unsaturated bond but no acidic group in the molecule, When an unsaturated compound (b) having one ethylenically unsaturated bond and one acidic group, or a mixture thereof, is copolymerized, a flame retardant composed of an acrylamide polymer having a high electrolyte group density is obtained. As a result, the present invention has been conceived.

本発明の難燃剤は、(1) 下記式(1)：

Figure 2008208385
（ただしR1は水素基又はメチル基であり、R2及びR3は水素基又は炭素数１〜３のアルキル基であり、R4は炭素数１〜３のアルキレン基であり、M1は水素基、金属又は３級アミン残基である。）により表されるアクリルアミドアルカンスルホン酸塩と、
(2) (i) （メタ）アクリロニトリル、（メタ）アクリルアミド、（メタ）アクリル酸エステル、アルキルアミノ基含有不飽和単量体、置換又は無置換のスチレン、ハロゲン化ビニル、脂肪酸置換ビニルエステル、及びフッ素基含有不飽和単量体からなる群から選ばれた少なくとも一種の不飽和化合物(a)、
(ii) リン酸基、ホスホン酸基、スルホン酸基、カルボン酸基及び硼酸基からなる群から選ばれた少なくとも一種の酸性基と、少なくとも１個のエチレン性不飽和結合とを有する不飽和化合物(b)、又は
(iii) 前記不飽和化合物(a)及び(b)の混合物
とを共重合してなることを特徴とする。 The flame retardant of the present invention comprises (1) the following formula (1):
Figure 2008208385
 (However, R 1 is a hydrogen group or a methyl group, R 2 and R 3 are a hydrogen group or an alkyl group having 1 to 3 carbon atoms, R 4 is an alkylene group having 1 to 3 carbon atoms, and M 1 is An acrylamide alkane sulfonate represented by a hydrogen group, a metal or a tertiary amine residue),
(2) (i) (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid ester, alkylamino group-containing unsaturated monomer, substituted or unsubstituted styrene, vinyl halide, fatty acid-substituted vinyl ester, and At least one unsaturated compound (a) selected from the group consisting of fluorine group-containing unsaturated monomers,
(ii) an unsaturated compound having at least one acidic group selected from the group consisting of a phosphoric acid group, a phosphonic acid group, a sulfonic acid group, a carboxylic acid group and a boric acid group, and at least one ethylenically unsaturated bond (b) or
(iii) It is obtained by copolymerizing a mixture of the unsaturated compounds (a) and (b).

前記アクリルアミドアルカンスルホン酸塩は、下記式(2)：

Figure 2008208385
により表されるターシャリーブチルアクリルアミドスルホン酸であるのが好ましい。(a)は（メタ）アクリルアミド、（メタ）アクリロニトリル及びN, N-ジアルキル（メタ）アクリルアミドからなる群から選ばれた少なくとも一種であるのが好ましい。(b)は（メタ）アクリル酸であるのが好ましい。 The acrylamide alkane sulfonate has the following formula (2):
Figure 2008208385
 It is preferable that it is tertiary butyl acrylamide sulfonic acid represented by these. (a) is preferably at least one selected from the group consisting of (meth) acrylamide, (meth) acrylonitrile and N, N-dialkyl (meth) acrylamide. (b) is preferably (meth) acrylic acid.

アクリルアミドアルカンスルホン酸塩系共重合体からなる本発明の難燃剤は、難燃性に優れているだけでなく、プラスチックへの溶解性又は分散性に優れているので、プラスチック用難燃剤として有用である。また本発明の難燃剤は導電性にも優れているので、難燃性のみならず帯電防止性が要求される用途にも好適である。   The flame retardant of the present invention comprising an acrylamide alkane sulfonate copolymer is not only excellent in flame retardancy, but also has excellent solubility or dispersibility in plastics, and is therefore useful as a flame retardant for plastics. is there. In addition, since the flame retardant of the present invention is excellent in conductivity, it is suitable for applications that require not only flame retardancy but also antistatic properties.

[1] アクリルアミドアルカンスルホン酸塩
アクリルアミドアルカンスルホン酸塩は、下記式(1)：

Figure 2008208385
（ただしR1は水素基又はメチル基であり、R2及びR3は水素基又は炭素数１〜３のアルキル基であり、R4は炭素数１〜３のアルキレン基であり、M1は水素基、金属又は３級アミン残基である。）により表される。 [1] Acrylamide alkanesulfonate Acrylamide alkanesulfonate is represented by the following formula (1):
Figure 2008208385
 (However, R 1 is a hydrogen group or a methyl group, R 2 and R 3 are a hydrogen group or an alkyl group having 1 to 3 carbon atoms, R 4 is an alkylene group having 1 to 3 carbon atoms, and M 1 is It is a hydrogen group, a metal or a tertiary amine residue.

アクリルアミドアルカンスルホン酸塩としては、下記式(2)：

Figure 2008208385
により表されるターシャリーブチルアクリルアミドスルホン酸が好ましい。 As the acrylamide alkane sulfonate, the following formula (2):
Figure 2008208385
 The tertiary butyl acrylamide sulfonic acid represented by is preferable.

[2] 共重合させる不飽和化合物
アクリルアミドアルカンスルホン酸塩と共重合させる不飽和化合物は、分子内に１個のエチレン性不飽和結合を有するが酸性基を有しない不飽和化合物(a)、分子内にエチレン性不飽和結合と酸性基とを各々１個有する不飽和化合物(b)、又はこれらの混合物である。 [2] Unsaturated compound to be copolymerized Unsaturated compound to be copolymerized with acrylamide alkanesulfonate is an unsaturated compound (a), molecule having one ethylenically unsaturated bond but no acidic group in the molecule. The unsaturated compound (b) having one ethylenically unsaturated bond and one acidic group therein, or a mixture thereof.

(a) 酸性基を含有しない不飽和化合物
酸性基非含有不飽和化合物は、（メタ）アクリロニトリル、（メタ）アクリルアミド、（メタ）アクリル酸エステル、アルキルアミノ基含有不飽和単量体、置換又は無置換のスチレン、ハロゲン化ビニル（例えば塩化ビニル等）、脂肪酸置換ビニルエステル（例えば酢酸ビニル等）、及びフッ素基含有不飽和単量体からなる群から選ばれた少なくとも一種である。 (a) Unsaturated compound not containing acidic group Unsaturated compound not containing acidic group is (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid ester, alkylamino group-containing unsaturated monomer, substituted or non-substituted. It is at least one selected from the group consisting of substituted styrene, vinyl halide (such as vinyl chloride), fatty acid-substituted vinyl ester (such as vinyl acetate), and fluorine group-containing unsaturated monomer.

（メタ）アクリル酸エステルとして、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート等のアルキル（メタ）アクリレートが挙げられる。   Examples of (meth) acrylic acid esters include alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate.

フッ素基含有不飽和単量体としては、例えば特開2005-11789号に記載のものが挙げられる。具体的には、パーフロロオクチルエチル（メタ）アクリレート等のハイドロフルオロアルキル基含有（メタ）アクリル酸エステル；パーフルオロアルキル基含有（メタ）アクリル酸エステル；α-（トリフルオロメチル）アクリル酸等のハイドロフルオロアルキル基含有（メタ）アクリル酸；パーフルオロブチルエチレン、パーフルオロヘキシルエチレン、パーフルオロオクチルエチレン、パーフルオロデシルエチレン等のパーフルオロアルキル基含有ビニル；ハイドロフルオロアルキル基含有ビニル等が好ましい。フッ素基含有不飽和単量体を共重合成分として含むことにより、重合体の耐熱性及び耐水性が一層向上する。   Examples of the fluorine group-containing unsaturated monomer include those described in JP-A-2005-11789. Specifically, hydrofluoroalkyl group-containing (meth) acrylic acid esters such as perfluorooctylethyl (meth) acrylate; perfluoroalkyl group-containing (meth) acrylic acid esters; α- (trifluoromethyl) acrylic acid, etc. Hydrofluoroalkyl group-containing (meth) acrylic acid; perfluoroalkyl group-containing vinyl such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene; hydrofluoroalkyl group-containing vinyl and the like are preferable. By including a fluorine group-containing unsaturated monomer as a copolymerization component, the heat resistance and water resistance of the polymer are further improved.

(b) 酸性基を含有する不飽和化合物
酸性基は、リン酸基、ホスホン酸基、スルホン酸基、カルボン酸基及び硼酸基からなる群から選ばれた少なくとも一種である。中でもリン酸基、ホスホン酸基、スルホン酸基及びカルボン酸基からなる群から選ばれた少なくとも一種が好ましい。エチレン性不飽和結合を有する骨格としては、（メタ）アクリレート骨格、（メタ）アリルエステル骨格、置換又は無置換の不飽和脂肪族炭化水素骨格、不飽和基により置換された芳香族炭化水素骨格等を挙げることができる。 (b) Unsaturated compound containing acidic group The acidic group is at least one selected from the group consisting of a phosphoric acid group, a phosphonic acid group, a sulfonic acid group, a carboxylic acid group, and a boric acid group. Among these, at least one selected from the group consisting of a phosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group is preferable. Examples of the skeleton having an ethylenically unsaturated bond include a (meth) acrylate skeleton, a (meth) allyl ester skeleton, a substituted or unsubstituted unsaturated aliphatic hydrocarbon skeleton, and an aromatic hydrocarbon skeleton substituted with an unsaturated group. Can be mentioned.

(i) リン酸基を含有する不飽和単量体
リン酸基含有不飽和単量体は下記一般式(3)：

Figure 2008208385
（ただしR5は水素基又はアルキル基であり、R6は置換又は無置換のアルキレン基であり、xは１〜６の整数である。）により表すことができる。R5は−H基又は−CH3基であるのが好ましい。アルキレン基R6について、「置換又は無置換」であるとは、直鎖状又は分岐状であることも含む。アルキレン基R6の炭素数は２〜４が好ましい。 (i) Unsaturated monomer containing phosphate group The phosphate group-containing unsaturated monomer is represented by the following general formula (3):
Figure 2008208385
 Wherein R 5 is a hydrogen group or an alkyl group, R 6 is a substituted or unsubstituted alkylene group, and x is an integer of 1 to 6. R 5 is preferably a —H group or a —CH 3 group. As for the alkylene group R 6 , “substituted or unsubstituted” includes linear or branched. The alkylene group R 6 preferably has 2 to 4 carbon atoms.

式(3)により表されるリン系酸残基含有不飽和単量体は、下記一般式(4)：

Figure 2008208385
（ただしR5は水素基又はアルキル基であり、R6'は水素基又は置換もしくは無置換のアルキル基であり、xは１〜６の整数である。）により表される化合物、及び下記一般式(5)：
Figure 2008208385
 （ただしR5は水素基又はアルキル基であり、R6''は直鎖状又は分岐状のブチレン基であり、xは１〜６の整数である。）により表される化合物が好ましい。式(4)により表されるリン系酸残基含有不飽和単量体において、R6'はH、CH3又はCH2Clであるのが好ましい。式(5)により表されるリン系酸残基含有不飽和単量体において、R6''はテトラメチレン基であるのが好ましい。 The phosphoric acid residue-containing unsaturated monomer represented by the formula (3) is represented by the following general formula (4):
Figure 2008208385
 Wherein R 5 is a hydrogen group or an alkyl group, R 6 ′ is a hydrogen group or a substituted or unsubstituted alkyl group, and x is an integer of 1 to 6, and the following general formula Formula (5):
Figure 2008208385
 (Wherein R 5 is a hydrogen group or an alkyl group, R 6 ″ is a linear or branched butylene group, and x is an integer of 1 to 6). In the phosphoric acid residue-containing unsaturated monomer represented by the formula (4), R 6 ′ is preferably H, CH 3 or CH 2 Cl. In the phosphoric acid residue-containing unsaturated monomer represented by the formula (5), R 6 ″ is preferably a tetramethylene group.

一般式(3)により表されるリン酸基含有不飽和単量体のうち代表的なものの構造式及び物性をそれぞれ表１及び表２に示す。これらの単量体はユニケミカル株式会社から商品名Phosmer（登録商標）として販売されている。ただし本発明に使用できるリン酸基含有不飽和単量体はこれらに限定されるものではない。一般式(3)により表されるリン酸基含有不飽和単量体は単独で用いることができるが、２種以上を併用しても良い。   Tables 1 and 2 show the structural formulas and physical properties of representative ones of the phosphate group-containing unsaturated monomers represented by the general formula (3), respectively. These monomers are sold by Unichemical Corporation under the trade name Phosmer (registered trademark). However, the phosphate group-containing unsaturated monomer that can be used in the present invention is not limited to these. The phosphate group-containing unsaturated monomer represented by the general formula (3) can be used alone, but two or more kinds may be used in combination.

Figure 2008208385
Figure 2008208385

Figure 2008208385
Figure 2008208385

一般式(3)により表されるリン酸基含有不飽和単量体のうち、アシッド・ホスホオキシブチルアクリレートもユニケミカル株式会社から商品名Phosmer BAとして入手可能である。   Of the phosphoric acid group-containing unsaturated monomers represented by the general formula (3), acid phosphooxybutyl acrylate is also available from Unichemical Co., Ltd. under the trade name “Phosmer BA”.

リン酸基は解離していてもよいし、錯塩を形成していても良い。錯塩を形成する場合、電荷を中和させるため、例えば第１級、第２級、第３級又は第４級のアルキル基、アリル基、アラルキル基等を含有するアンモニウムイオンと錯塩を形成するのが好ましい。   The phosphoric acid group may be dissociated or may form a complex salt. When forming a complex salt, in order to neutralize the charge, for example, a complex salt is formed with an ammonium ion containing a primary, secondary, tertiary or quaternary alkyl group, allyl group, aralkyl group or the like. Is preferred.

(ii) スルホン酸基を含有する不飽和単量体
スルホン酸基を含有する不飽和単量体としては、例えば特開2004-179154号に記載のものが挙げられる。具体的には、アリルスルホン酸、メタアリルスルホン酸、ビニルスルホン酸、p-スチレンスルホン酸、（メタ）アクリル酸ブチル-4-スルホン酸、（メタ）アクリロオキシベンゼンスルホン酸等が好ましい。これらは単独でもよいし、又は２種以上を併用しても良い。 (ii) Unsaturated monomer containing sulfonic acid group Examples of the unsaturated monomer containing a sulfonic acid group include those described in JP-A-2004-179154. Specifically, allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, p-styrene sulfonic acid, (meth) acrylic acid butyl-4-sulfonic acid, (meth) acrylooxybenzene sulfonic acid and the like are preferable. These may be used alone or in combination of two or more.

(iii) カルボン酸基を含有する不飽和単量体
カルボン酸基を含有する不飽和単量体の例示化合物としては、（メタ）アクリル酸、クロトン酸、イタコン酸等が挙げられる。これらは単独で用いてもよいし、２種以上を併用しても良い。 (iii) Unsaturated monomer containing carboxylic acid group Examples of the unsaturated monomer containing a carboxylic acid group include (meth) acrylic acid, crotonic acid, itaconic acid and the like. These may be used alone or in combination of two or more.

(C) 配合割合
アクリルアミドアルカンスルホン酸塩(1)と、共重合させる不飽和化合物（(a)，(b)又はこれらの混合物）(2)との質量比(1)／(2)は特に制限されないが、その下限は30／70であるのがより好ましく、40／60であるのがさらに好ましい。 (C) Mixing ratio The mass ratio (1) / (2) between the acrylamide alkanesulfonate (1) and the unsaturated compound ((a), (b) or a mixture thereof) (2) to be copolymerized is particularly Although not limited, the lower limit is more preferably 30/70, and still more preferably 40/60.

[3] 難燃剤の製造方法
難燃剤は、アクリルアミドアルカンスルホン酸塩と、共重合させる不飽和化合物（不飽和化合物(a)，(b)又はこれらの混合物）との混合物を、重合開始剤の存在下、ケトン類及びアルコール類溶媒中でラジカル重合することにより製造できる（以下特段の断りがない限り、「アクリルアミドアルカンスルホン酸塩と、共重合させる不飽和化合物との混合物」をまとめて「不飽和原料」と呼ぶ。）。 [3] Flame Retardant Production Method A flame retardant comprises a mixture of an acrylamide alkane sulfonate and an unsaturated compound to be copolymerized (unsaturated compound (a), (b) or a mixture thereof) as a polymerization initiator. It can be produced by radical polymerization in the presence of ketones and alcohol solvents in the presence (hereinafter, unless otherwise specified, the “mixture of acrylamide alkane sulfonate and unsaturated compound to be copolymerized” is Called "saturated raw material").

ラジカル重合反応は、不飽和原料が溶解する溶媒中で、アセチルパーオキサイド、イソプロピルハイドロパーオキサイド等の有機過酸化物系開始剤、2, 2’-アゾビスイソブチロニトリル、2, 2 ’-アゾビス（2, 4-ジメチルバレロニトリル）、ジメチル2, 2 ’-アゾビス（2-メチルプロピオネート）、ジメチル2, 2 ’-アゾビスイソブチレート等のアゾ系開始剤、あるいはラウリルパーオキシド、ベンゾイルパーオキシド、tert-ブチルパーオキシ・ピバレート等の過酸化物系重合開始剤を用いることにより行う。 Radical polymerization reaction is carried out in a solvent in which unsaturated raw materials are dissolved, organic peroxide initiators such as acetyl peroxide and isopropyl hydroperoxide, 2, 2'-azobisisobutyronitrile, 2, 2 '-Azobis (2,4-dimethylvaleronitrile), dimethyl 2, 2 '-Azobis (2-methylpropionate), dimethyl 2, 2 It is carried out by using an azo initiator such as' -azobisisobutyrate or a peroxide polymerization initiator such as lauryl peroxide, benzoyl peroxide, tert-butyl peroxy pivalate or the like.

溶媒としてはケトン及び／又はアルコールを使用する。これら溶媒の炭素数は６以下であるのが好ましい。炭素数６以下の脂肪族アルコールとしては、メタノール、エタノール、イソプロピルアルコール、ブタノール、ペンチルアルコール及びヘキサノールからなる群から選ばれた少なくとも一種が特に好ましい。アルコールは一種のみを用いてもよいし、二種以上を併用してもよい。ケトンとしては例えばアセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等が好ましい。また不飽和原料に対する溶解性を損なわない範囲でケトン及び／又はアルコールにアミド系溶媒（DMAc、DMF等）、エステル、ジオキサン、エーテル等を共存させてもよい。   A ketone and / or alcohol is used as the solvent. These solvents preferably have 6 or less carbon atoms. The aliphatic alcohol having 6 or less carbon atoms is particularly preferably at least one selected from the group consisting of methanol, ethanol, isopropyl alcohol, butanol, pentyl alcohol, and hexanol. Alcohol may use only 1 type and may use 2 or more types together. As the ketone, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like are preferable. Further, amide solvents (DMAc, DMF, etc.), esters, dioxane, ethers, etc. may coexist with ketones and / or alcohols as long as solubility in unsaturated raw materials is not impaired.

重合手順について述べる。まず攪拌器、還流冷却器付き反応器に（不飽和原料＋溶媒）からなる溶液を投入し、反応器内を窒素ガス雰囲気とした後、添加する重合開始剤の分解温度である40℃〜70℃に昇温する。好ましい重合温度は50℃〜70℃である。所定温度到達直後に重合開始剤を添加する。このとき若干の発熱があり、重合開始を確認することができる。所定温度に到達してから約１時間間隔で重合開始剤を２〜３回添加した後、１時間程度重合反応を継続する。反応温度は最初から最後まで一定である必要はなく、重合末期に温度を上げて未反応単量体を極力少なくする方法をとってもよい。重合溶液は不飽和原料の初期固形分濃度が8〜25質量％であるのが好ましい。重合開始剤のトータル使用量は、不飽和原料を100とした場合に質量比で0.1〜５であるのが好ましく、0.1〜２であるのがより好ましい。   The polymerization procedure is described. First, a solution composed of (unsaturated raw material + solvent) is put into a reactor equipped with a stirrer and a reflux condenser, and after the inside of the reactor is made a nitrogen gas atmosphere, the decomposition temperature of the polymerization initiator to be added is 40 ° C to 70 ° C The temperature is raised to ° C. A preferable polymerization temperature is 50 ° C to 70 ° C. A polymerization initiator is added immediately after reaching the predetermined temperature. At this time, there is slight heat generation, and the start of polymerization can be confirmed. After reaching a predetermined temperature, a polymerization initiator is added 2 to 3 times at intervals of about 1 hour, and then the polymerization reaction is continued for about 1 hour. The reaction temperature does not need to be constant from the beginning to the end, and a method of increasing the temperature at the end of the polymerization to minimize the unreacted monomer may be used. The polymerization solution preferably has an initial solid content concentration of the unsaturated raw material of 8 to 25% by mass. The total amount of polymerization initiator used is preferably 0.1 to 5 and more preferably 0.1 to 2 in terms of mass ratio when the unsaturated raw material is 100.

重合速度が異なる２種以上の不飽和単量体を共重合させる場合、各単量体を個別に重合開始剤とともに粘度低下に必要な溶剤に溶解させた複数の溶液を調製し、これらを同時に十分な時間をかけて溶媒に滴下しながら共重合させるのが好ましい。重合温度は上記と同じでよい。   When two or more unsaturated monomers having different polymerization rates are copolymerized, a plurality of solutions are prepared by dissolving each monomer individually in a solvent necessary for viscosity reduction together with a polymerization initiator, It is preferable to carry out the copolymerization while dripping into the solvent over a sufficient time. The polymerization temperature may be the same as described above.

ラジカル重合は、(a) 不飽和原料及び生成する重合体の双方がケトン類及び／又はアルコール類溶媒に溶解する溶液重合、又は(b) ケトン類及びアルコール類溶媒に不飽和原料は溶解するが、生成する重合体は溶解しない析出重合のいずれであってもよい。   In radical polymerization, (a) solution polymerization in which both the unsaturated raw material and the resulting polymer are dissolved in ketones and / or alcohol solvents, or (b) the unsaturated raw material is dissolved in ketones and alcohol solvents. The produced polymer may be any of precipitation polymerization that does not dissolve.

不飽和原料が(i) アクリルアミドアルカンスルホン酸塩と、(ii) （メタ）アクリロニトリル、（メタ）アクリルアミド、（メタ）アクリル酸及びN, N-ジアルキル（メタ）アクリルアミドからなる群から選ばれた少なくとも一種とからなる場合、通常は析出重合となる。   The unsaturated raw material is at least selected from the group consisting of (i) acrylamide alkane sulfonate and (ii) (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid and N, N-dialkyl (meth) acrylamide When it consists of one type, it is usually precipitation polymerization.

析出重合により得られた反応液から、アクリルアミドアルカンスルホン酸塩系共重合体を単離する場合、析出した重合体を濾別するのみでよい。このように、析出重合の場合、溶液重合に比べて重合体の単離が格段に容易であるという利点がある。濾別により得られた重合体は、上記貧溶媒を用いて洗浄するのが好ましい。   When isolating an acrylamide alkane sulfonate copolymer from the reaction solution obtained by precipitation polymerization, it is only necessary to filter the precipitated polymer. Thus, precipitation polymerization has the advantage that the isolation of the polymer is much easier than solution polymerization. The polymer obtained by filtration is preferably washed using the above poor solvent.

溶液重合により得られたポリマーはアミン塩にすることにより析出させる。使用可能なアミンとしては、下記式(6)：

Figure 2008208385
（但し、R7〜R9はそれぞれ独立に水素、アルキル基又は芳香族基である）により表される第一級〜第三級アミン類が挙げられる。具体的には、例えばトリエチルアミン等が挙げられる。析出したアミン変性重合体は濾別すればよい。 The polymer obtained by solution polymerization is precipitated by making it into an amine salt. Usable amines include the following formula (6):
Figure 2008208385
 However, primary to tertiary amines represented by the formula (wherein R 7 to R 9 are each independently hydrogen, an alkyl group, or an aromatic group). Specific examples include triethylamine and the like. The precipitated amine-modified polymer may be filtered off.

析出（共）重合により得られた反応液から単離したアクリルアミドアルカンスルホン酸塩系共重合体、又は溶液重合により得られた反応溶液にアミン類を添加することによりアミン塩として析出させた重合体は、減圧下100〜120℃の温度で６〜10時間加熱し、乾燥させる。析出（共）重合により得られた重合体は、乾燥させるのみで白色粉末状となる。このように析出重合の場合、粉末状の重合体が容易に得られ、粉砕を要しないという利点もある。アミン塩として析出させた重合体が塊状である場合、粉砕すればよい。   Acrylamide alkane sulfonate copolymer isolated from reaction solution obtained by precipitation (co) polymerization, or polymer precipitated as amine salt by adding amines to reaction solution obtained by solution polymerization Is heated at a temperature of 100 to 120 ° C. under reduced pressure for 6 to 10 hours and dried. The polymer obtained by precipitation (co) polymerization becomes a white powder only by drying. Thus, in the case of precipitation polymerization, there is an advantage that a powdery polymer can be easily obtained and pulverization is not required. What is necessary is just to grind | pulver, when the polymer precipitated as amine salt is a lump.

[4] 使用対象及び使用方法
難燃剤の使用対象として、プラスチック、紙製品（障子紙、襖紙、壁紙、板紙、合成紙等）等のセルロース系材料、布等の繊維材料、木材系建築材料等が挙げられる。本発明の難燃剤は白色粉末状であり、プラスチック中に容易に溶解又は分散するので、特にプラスチック用難燃剤として有用である。特にアミン変性したものは耐熱性が高く、耐熱性プラスチック用難燃剤に好適である。プラスチックは特に限定されず、熱可塑性及び熱硬化性のいずれの合成樹脂でもよいが、熱可塑性樹脂への使用が一般的である。熱可塑性樹脂として、例えばポリエチレン、ポリプロピレン、ポリブタジエン、エチレン−プロピレン共重合体等のポリオレフィン；ポリ（スチレン）；ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル；ポリアセタール；ポリアミド等が挙げられる。熱硬化性樹脂として、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂等が挙げられる。 [4] Targets and methods of use The flame retardants are targeted for the use of cellulosic materials such as plastic and paper products (such as shoji paper, paperboard, wallpaper, paperboard, and synthetic paper), textile materials such as cloth, and wood-based building materials. Etc. The flame retardant of the present invention is in the form of white powder and is easily dissolved or dispersed in the plastic, so that it is particularly useful as a flame retardant for plastics. In particular, the amine-modified one has high heat resistance and is suitable as a flame retardant for heat-resistant plastics. The plastic is not particularly limited, and any synthetic resin that is thermoplastic and thermosetting may be used. However, the plastic is generally used. Examples of the thermoplastic resin include polyolefin such as polyethylene, polypropylene, polybutadiene, and ethylene-propylene copolymer; poly (styrene); polyester such as polyethylene terephthalate and polybutylene terephthalate; polyacetal; polyamide and the like. Examples of the thermosetting resin include an epoxy resin, a phenol resin, and an unsaturated polyester resin.

難燃剤のプラスチックへの配合量は特に制限されず、プラスチックの特性を低下させない限り、任意に設定できる。通常は難燃剤添加後のプラスチックの質量を100質量％として、3〜50質量％、好ましくは30〜50質量％の配合量とすれば、十分な難燃性が得られる。   The blending amount of the flame retardant into the plastic is not particularly limited, and can be arbitrarily set as long as the properties of the plastic are not deteriorated. Usually, sufficient flame retardancy can be obtained if the mass of the plastic after addition of the flame retardant is 100% by mass and the blending amount is 3 to 50% by mass, preferably 30 to 50% by mass.

熱可塑性樹脂に本発明の難燃剤を添加するには、原料熱可塑性樹脂とともに難燃剤を溶融混練した後、成形すればよく、配合が容易である。必要に応じて、本発明の難燃剤を溶媒に溶解又は分散した上で、原料熱可塑性樹脂に添加してもよい。熱硬化性樹脂に本発明の難燃剤を添加するには、未硬化の樹脂に、本発明の難燃剤を溶解又は分散した後硬化させればよい。必要に応じて、本発明の難燃剤を溶媒に溶解又は分散した上で、未硬化の熱硬化性樹脂に添加すればよい。   In order to add the flame retardant of the present invention to a thermoplastic resin, the flame retardant may be melt-kneaded together with the raw material thermoplastic resin and then molded, and blending is easy. If necessary, the flame retardant of the present invention may be dissolved or dispersed in a solvent and then added to the raw thermoplastic resin. In order to add the flame retardant of the present invention to a thermosetting resin, the flame retardant of the present invention may be dissolved or dispersed in an uncured resin and then cured. If necessary, the flame retardant of the present invention may be dissolved or dispersed in a solvent and then added to the uncured thermosetting resin.

セルロース系材料、繊維材料、木材系建築材料等の基材に本発明の難燃剤を使用するには、例えば基材を難燃剤の水溶液に浸漬後乾燥する方法、難燃剤の水溶液を用いてサイズプレスする方法、難燃剤の水溶液を塗布する方法等が挙げられる。   In order to use the flame retardant of the present invention on a substrate such as a cellulosic material, a fiber material, a wood building material, etc. The method of pressing, the method of apply | coating the aqueous solution of a flame retardant etc. are mentioned.

本発明の難燃剤は、必要に応じてその他の公知の有機又は無機の難燃性化合物を難燃助剤として含んでもよい。公知の難燃性化合物として、例えば上記リン酸基含有不飽和単量体の重合体が挙げられる。   The flame retardant of the present invention may contain other known organic or inorganic flame retardant compounds as flame retardant aids as necessary. Examples of known flame retardant compounds include polymers of the above-mentioned phosphate group-containing unsaturated monomers.

本発明を以下の実施例によりさらに詳細に説明するが、本発明はこれらの例に限定されるものではない。   The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

実施例１
［ターシャリーブチルアクリルアミドスルホン酸（以下「TBAS」と表記する）とアクリルアミドからなる共重合体の調製］
TBAS粉末品18.63 g（0.09モル）とアクリルアミド結晶品19.17 g（0.27モル）を、63 gのメタノールに溶解し、上記と同型の自動合成器に入れた。さらにメチルエチルケトン230 gを自動合成器に入れた。N2ガスの流通下、60〜65℃に保温しながら、１時間攪拌した（攪拌回転数：60〜90 rpm）。その後、2, 2 ’-アゾビス（2, 4-ジメチルバレロニトリル）（商品名「V-65」、和光純薬株式会社製）の１質量％イソプロパノール液（触媒液）を９ mL調製し、分割投入した。まず３mLの触媒液を、攪拌下60℃で反応溶液に滴下すると、反応溶液は一時的に67℃まで上昇し白濁した。60〜65℃で１時間攪拌を持続した。次いで攪拌下60℃で３mLの触媒液を滴下し、１時間後同条件下でさらに同量の触媒液を滴下した。触媒液全量を滴下後、70℃で２時間熟成反応を持続した。得られた反応溶液は上澄み液と樹脂沈降物とに分離した。 Example 1
[Preparation of a copolymer comprising tertiary butyl acrylamide sulfonic acid (hereinafter referred to as “TBAS”) and acrylamide]
18.63 g (0.09 mol) of the TBAS powder product and 19.17 g (0.27 mol) of the acrylamide crystal product were dissolved in 63 g of methanol and placed in an automatic synthesizer of the same type as above. Further, 230 g of methyl ethyl ketone was placed in an automatic synthesizer. The mixture was stirred for 1 hour while maintaining a temperature of 60 to 65 ° C. under a flow of N 2 gas (stirring rotation speed: 60 to 90 rpm). Then 2, 2 9 mL of a 1% by mass isopropanol solution (catalyst solution) of '-azobis (2,4-dimethylvaleronitrile) (trade name “V-65”, manufactured by Wako Pure Chemical Industries, Ltd.) was prepared and charged in portions. First, 3 mL of the catalyst solution was dropped into the reaction solution at 60 ° C. with stirring, and the reaction solution temporarily rose to 67 ° C. and became cloudy. Stirring was continued at 60 to 65 ° C. for 1 hour. Next, 3 mL of the catalyst solution was added dropwise at 60 ° C. with stirring, and an additional amount of the catalyst solution was added dropwise under the same conditions after 1 hour. After dropping the entire amount of the catalyst solution, the aging reaction was continued at 70 ° C. for 2 hours. The obtained reaction solution was separated into a supernatant and a resin precipitate.

得られた白濁沈殿物を濾過し、アセトンによる洗浄を２回繰り返した後、８時間加熱減圧乾燥し（温度：100℃、真空度：10 mmHg以下）、白色の粉末重合体（35 g、理論収量：92質量％）を得た。得られた白色粉末重合体の５質量％水溶液は低粘性であり、かつ透明であった。この重合体の酸価は132 mg／g（スルホン酸当量：424.2 g／eq.）であり、ほぼ理論酸価（133.3 mg／g、理論スルホン当量：420 g／eq.）であることから、生成した重合体はほぼ仕込みモル比（TBAS／アクリルアミド＝1／3）に近いTBAS／アクリルアミド共重合体であると考えられる。   The resulting cloudy precipitate was filtered, washed with acetone twice, and then dried under reduced pressure by heating for 8 hours (temperature: 100 ° C., vacuum: 10 mmHg or less), and a white powder polymer (35 g, theoretical Yield: 92% by mass). The obtained 5% by mass aqueous solution of a white powder polymer had low viscosity and was transparent. The acid value of this polymer is 132 mg / g (sulfonic acid equivalent: 424.2 g / eq.), Which is almost the theoretical acid value (133.3 mg / g, theoretical sulfone equivalent: 420 g / eq.). The produced polymer is considered to be a TBAS / acrylamide copolymer that is close to the charged molar ratio (TBAS / acrylamide = 1/3).

（不燃性の評価）
得られた白色粉末重合体をガスバーナーの先端に設置し、炎に20秒間曝し、着火の有無を調べたが（検体数：３個）、炭化しただけで着火しなかった。 (Evaluation of nonflammability)
The obtained white powder polymer was placed at the tip of a gas burner, exposed to flame for 20 seconds, and examined for the presence or absence of ignition (number of specimens: 3), but only carbonized and did not ignite.

Claims (3)

(1) 下記式(1)：
Figure 2008208385
 （ただしR1は水素基又はメチル基であり、R2及びR3は水素基又は炭素数１〜３のアルキル基であり、R4は炭素数１〜３のアルキレン基であり、M1は水素基、金属又は３級アミン残基である。）により表されるアクリルアミドアルカンスルホン酸塩と、
(2) (i) （メタ）アクリロニトリル、（メタ）アクリルアミド、（メタ）アクリル酸エステル、アルキルアミノ基含有不飽和単量体、置換又は無置換のスチレン、ハロゲン化ビニル、脂肪酸置換ビニルエステル、及びフッ素基含有不飽和単量体からなる群から選ばれた少なくとも一種の不飽和化合物(a)、
(ii) リン酸基、ホスホン酸基、スルホン酸基、カルボン酸基及び硼酸基からなる群から選ばれた少なくとも一種の酸性基と、少なくとも１個のエチレン性不飽和結合とを有する不飽和化合物(b)、又は
(iii) 前記不飽和化合物(a)及び(b)の混合物
とを共重合してなることを特徴とする難燃剤。 (1) The following formula (1):
Figure 2008208385
 (However, R 1 is a hydrogen group or a methyl group, R 2 and R 3 are a hydrogen group or an alkyl group having 1 to 3 carbon atoms, R 4 is an alkylene group having 1 to 3 carbon atoms, and M 1 is An acrylamide alkane sulfonate represented by a hydrogen group, a metal or a tertiary amine residue),
(2) (i) (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid ester, alkylamino group-containing unsaturated monomer, substituted or unsubstituted styrene, vinyl halide, fatty acid substituted vinyl ester, and At least one unsaturated compound (a) selected from the group consisting of fluorine group-containing unsaturated monomers,
(ii) an unsaturated compound having at least one acidic group selected from the group consisting of a phosphoric acid group, a phosphonic acid group, a sulfonic acid group, a carboxylic acid group and a boric acid group, and at least one ethylenically unsaturated bond (b) or
(iii) A flame retardant obtained by copolymerizing a mixture of the unsaturated compounds (a) and (b). 請求項１に記載の難燃剤において、前記アクリルアミドアルカンスルホン酸塩は、下記式(2)：
Figure 2008208385
 により表されるターシャリーブチルアクリルアミドスルホン酸であることを特徴とする難燃剤。 The flame retardant according to claim 1, wherein the acrylamide alkane sulfonate is represented by the following formula (2):
Figure 2008208385
 A flame retardant, characterized in that it is a tertiary butyl acrylamide sulfonic acid represented by: 請求項１又は２に記載の難燃剤において、(a)は（メタ）アクリルアミド、（メタ）アクリロニトリル及びN, N-ジアルキル（メタ）アクリルアミドからなる群から選ばれた少なくとも一種であり、(b)は（メタ）アクリル酸であることを特徴とする難燃剤。 The flame retardant according to claim 1 or 2, wherein (a) is at least one selected from the group consisting of (meth) acrylamide, (meth) acrylonitrile, and N, N-dialkyl (meth) acrylamide, (b) Is a (meth) acrylic acid, a flame retardant.
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JP2012197645A (en) * 2011-03-23 2012-10-18 Sekisui Chem Co Ltd Daylighting heat-insulating material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012197645A (en) * 2011-03-23 2012-10-18 Sekisui Chem Co Ltd Daylighting heat-insulating material

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