JP2002533480A - Method for producing styrene / acrylic water-soluble resin by continuous bulk polymerization - Google Patents
Method for producing styrene / acrylic water-soluble resin by continuous bulk polymerizationInfo
- Publication number
- JP2002533480A JP2002533480A JP2000589575A JP2000589575A JP2002533480A JP 2002533480 A JP2002533480 A JP 2002533480A JP 2000589575 A JP2000589575 A JP 2000589575A JP 2000589575 A JP2000589575 A JP 2000589575A JP 2002533480 A JP2002533480 A JP 2002533480A
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- water
- acrylic
- monomer
- soluble resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000011347 resin Substances 0.000 title claims abstract description 77
- 229920005989 resin Polymers 0.000 title claims abstract description 77
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000012662 bulk polymerization Methods 0.000 title claims description 14
- 238000000034 method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- KTADTTCBDAMZIR-UHFFFAOYSA-N 2-(2-hydroxypropoxy)propan-1-ol;hydrate Chemical compound O.CC(O)COC(C)CO KTADTTCBDAMZIR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 22
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 16
- 239000002253 acid Substances 0.000 abstract description 11
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 14
- 239000000976 ink Substances 0.000 description 9
- 239000003973 paint Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 4
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 101100321670 Fagopyrum esculentum FA18 gene Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
(57)【要約】 反応溶媒としてジプロピレングリコールメチルエ−テルと水との混合溶媒を使用し、オイルジャケットとオイルジャケット内部の冷却コイルとを用いて温度を制御するタイプの反応器を使用し、フォーリングストランド型の脱揮装置を用いて重合物中の揮発分を除去することによりなされたスチレン／アクリル系水溶性の製造方法に関する。本発明の方法で製造されたスチレン／アクリル系水溶性樹脂に比べて分子量が低く、分子量分布が狭く、高い酸価と低い含量を有する。 (57) [Abstract] A mixed solvent of dipropylene glycol methyl ether and water is used as a reaction solvent, and a type of reactor whose temperature is controlled using an oil jacket and a cooling coil inside the oil jacket is used. And a water-soluble styrene / acrylic-based production method which is performed by removing volatile components in a polymer using a falling strand type devolatilizer. It has a lower molecular weight, a narrower molecular weight distribution, a higher acid value and a lower content than the styrene / acrylic water-soluble resin produced by the method of the present invention.
Description
【０００１】 技術分野 本発明は連続バルク重合によるスチレン／アクリル系水溶性樹脂の製造方法に係
り、さらに詳しくは連続バルク重合によって、分子量が低く、分子量分布が狭く
、高い酸価と低い揮発分含量を有するスチレン／アクリル系水溶性樹脂を製造し
得る工程に関する。TECHNICAL FIELD The present invention relates to a method for producing a styrene / acrylic water-soluble resin by continuous bulk polymerization, and more particularly, to a method of producing a styrene / acrylic water-soluble resin having a low molecular weight, a narrow molecular weight distribution, a high acid value and a low volatile content by continuous bulk polymerization. A styrene / acrylic water-soluble resin having the following formula:
【０００２】 背景技術 最近、国内で使用しているインク、塗料及びコーティング材は、殆ど有機溶剤で
ある。ところが、これら有機溶剤は、使用の際に排出される有機物質によって大
気汚染の主要因と認識されていると共に、可燃性であるから火災の危険性が高い
。BACKGROUND ART In recent years, inks, paints and coating materials used in Japan are mostly organic solvents. However, these organic solvents are recognized as a main cause of air pollution due to organic substances emitted during use, and are highly flammable and therefore have a high risk of fire.
【０００３】 かかる短所を解決するための方法の一環として提案された、スチレン／アクリル
系水溶性樹脂を基材とした高固形分塗料やインクは、大気汚染の問題を生じさせ
ることなく、有機溶剤に基づいた塗料やインクとは異なり、資源、エネルギー、
作業環境などの面で要求されるコストを低減することができ、火災又は爆発の危
険もないという長所などがある。[0003] High solid content paints and inks based on styrene / acrylic water-soluble resins, proposed as part of a method for solving such disadvantages, can be used in organic solvents without causing air pollution problems. Unlike paints and inks based on
There are advantages in that costs required in terms of work environment and the like can be reduced and there is no danger of fire or explosion.
【０００４】 しかし、このような技術を活用するためには固形分の増加による粘度上昇の問題
を解決しなければならない。つまり、スチレン／アクリル系水溶性樹脂の分子量
が増加すると、粘度が急激に増加し、結果として分子量の高い樹脂の場合には固
形分の濃度を増加させるのに限界がある。たとえば、重量平均分子量約５０，０
００〜１００，０００程度のスチレン／アクリル系水溶性樹脂を用いて水性イン
ク及び水性塗料を製造する場合、固形分の含量が最大５０％以下であるが、重量
平均分子量が５，０００〜１５，０００程度であれば、固形分の含量が７０〜８
０％程度であっても、固形分含量の高いインク又は塗料を製造するのに別に問題
がない。ところが、前記分子量を満足しても、分子量分布が広くなると、高分子
量の樹脂が含有されて粘度が高くなるので、分子量分布が狭くならなければなら
ない。However, in order to utilize such a technique, it is necessary to solve the problem of an increase in viscosity due to an increase in solid content. That is, as the molecular weight of the styrene / acrylic water-soluble resin increases, the viscosity sharply increases. As a result, in the case of a resin having a high molecular weight, there is a limit in increasing the concentration of the solid content. For example, a weight average molecular weight of about 50,0
When water-based inks and water-based paints are manufactured using styrene / acrylic water-soluble resins of about 100 to 100,000, the content of solids is at most 50% or less, but the weight average molecular weight is 5,000 to 15,500. 000, the solid content is 70-8
Even if it is about 0%, there is no problem in producing an ink or paint having a high solid content. However, even if the above-mentioned molecular weight is satisfied, if the molecular weight distribution is wide, the high molecular weight resin is contained and the viscosity becomes high, so that the molecular weight distribution must be narrow.
【０００５】 更に、樹脂に水溶性を与えるためにカルボキシル基を導入するが、通常、アクリ
ル酸又はメタクリル酸を用いて２００以上の酸価を有するように樹脂を製造する
。[0005] Further, a carboxyl group is introduced to impart water solubility to the resin. Usually, the resin is manufactured using acrylic acid or methacrylic acid so as to have an acid value of 200 or more.
【０００６】 一方、水溶性樹脂内に揮発分含量が高ければ、インク又は塗料の製造時に泡が多
く発生して作業性が悪く、泡を取り除くために消泡剤を多量使用しなければなら
ないという問題が生じる。従って、水溶性樹脂内の揮発分含量が低いほど作業性
が良くなり且つ消泡剤などの使用を減少させることが可能であって、インク及び
塗料の物性が良くなる。On the other hand, if the content of volatile components in the water-soluble resin is high, bubbles are generated during the production of ink or paint, resulting in poor workability, and a large amount of an antifoaming agent must be used to remove the bubbles. Problems arise. Therefore, the lower the volatile content in the water-soluble resin, the better the workability and the use of an antifoaming agent and the like can be reduced, and the physical properties of the ink and the coating material are improved.
【０００７】 このため、固形分含量の高い水溶性インク及び水性塗料を製造するには、分子量
が低い、分子量の分布が狭い、高い酸価及び低い揮発分含量を有する水溶性樹脂
の使用が必須である。For this reason, in order to produce a water-soluble ink and a water-based paint having a high solid content, it is essential to use a water-soluble resin having a low molecular weight, a narrow molecular weight distribution, a high acid value and a low volatile content. It is.
【０００８】 このように、固形分含量の高い水溶性インク及び水性塗料を製造するためには、
４，０００〜１６，０００の重量平均分子量、２.２以下の分子量分布、２００
以上の酸価及び５％以下の揮発分含量を有するスチレン／アクリル系水溶性樹脂
が必要である。しかし、このような条件を満足するスチレン／アクリル系水溶性
樹脂は、公知となっている溶液重合法もしくは乳化重合法では製造が不可能であ
る。即ち、溶液重合法では普通分子量の範囲が１０，０００〜１００，０００の
スチレン／アクリル系樹脂を製造することができ、乳化重合法では数百万程度の
分子量を有するスチレン／アクリル系水溶性樹脂を製造することができる。As described above, in order to produce a water-soluble ink and a water-based paint having a high solid content,
Weight average molecular weight of 4,000 to 16,000, molecular weight distribution of 2.2 or less, 200
A styrene / acrylic water-soluble resin having the above acid value and a volatile content of 5% or less is required. However, a styrene / acrylic water-soluble resin satisfying such conditions cannot be produced by a known solution polymerization method or emulsion polymerization method. That is, a solution polymerization method can produce a styrene / acrylic resin having a molecular weight in the range of 10,000 to 100,000, and a emulsion polymerization method can produce a styrene / acrylic water-soluble resin having a molecular weight of about several million. Can be manufactured.
【０００９】 米国特許第４，４１４，３７０号ではスチレン／アクリル系水溶性樹脂を製造す
るための連続バルク重合工程を提示しているが、これによれば、連続攪拌型反応
器で２３５〜３１０℃の反応温度にて２分以上の滞留時間を有するようにモノマ
ーを連続して注入し、重合物を脱揮装置(Devolatilizer)へ移送して揮発分を除
去し、水平均分子量１，０００〜６，０００（重量平均分子量では約２，０００
〜１２，０００）、分子量分布２．０以下のスチレン／アクリル系水溶性樹脂を
生産している。使用されたモノマーは、１：２乃至２：１のスチレン対α-メチ
ルスチレンの重量比を有する混合物とアクリル酸が６０：４０〜８０：２０の重
量比で構成されており、モノマー基準１〜１０重量部のジエチレングリコールモ
ノエチルエーテルを溶媒として用いた。一方、前記米国特許では、反応温度を調
節するために、反応器ジャケットに熱媒油(Heat Transfer Oil)を流し、反応器
の内部に冷却コイルを設けて熱媒油を流し、反応器の温度を上昇／下降するよう
にしている。US Pat. No. 4,414,370 discloses a continuous bulk polymerization process for producing a styrene / acrylic water-soluble resin. The monomer was continuously injected so as to have a residence time of 2 minutes or more at a reaction temperature of ° C., and the polymer was transferred to a devolatilizer (Devolatilizer) to remove volatile components, and a water average molecular weight of 1,000 to 6,000 (about 2,000 in weight average molecular weight)
-12,000) and a styrene / acrylic water-soluble resin having a molecular weight distribution of 2.0 or less. The monomers used consisted of a mixture having a weight ratio of styrene to α-methylstyrene of 1: 2 to 2: 1 and a weight ratio of acrylic acid of 60:40 to 80:20. 10 parts by weight of diethylene glycol monoethyl ether were used as a solvent. On the other hand, in the US patent, in order to adjust the reaction temperature, heat transfer oil (Heat Transfer Oil) is flowed into the reactor jacket, a cooling coil is provided inside the reactor to flow the heat transfer oil, and the temperature of the reactor is controlled. To rise / fall.
【００１０】 しかしながら、上述した方法は、反応温度を制御するために反応器の外部にオイ
ルジャケット、反応器の内部に冷却コイルを設けたが、このような場合、反応器
の内部と反応器の外壁との温度偏差が大きくて反応器内の均一な温度制御が容易
ではない。また、反応温度が高くて生産コストが上昇するので、低い反応温度で
もほぼ同じ水準の分子量及び分子量分布を有するスチレン／アクリル系水溶性樹
脂を生産できる工程が必要である。なお、上述の方法では、ジエチレングリコー
ルモノエチルエーテルは、反応物としてのアクリル酸とエステール反応を起こし
生成物としての水溶性樹脂の酸価を低下させ、結果的に水に対する溶解性が低く
なるので、製品の物性に影響を少なく与えながらも反応物の粘度を調節すること
が可能な物質を溶媒として使用する必要がある。However, in the above-described method, an oil jacket is provided outside the reactor to control the reaction temperature, and a cooling coil is provided inside the reactor. In such a case, the inside of the reactor and the reactor are provided. The temperature deviation from the outer wall is so large that uniform temperature control in the reactor is not easy. In addition, since the reaction temperature is high and the production cost is increased, a process is required that can produce a styrene / acrylic water-soluble resin having substantially the same molecular weight and molecular weight distribution even at a low reaction temperature. In the method described above, diethylene glycol monoethyl ether causes an ester reaction with acrylic acid as a reactant, lowers the acid value of the water-soluble resin as a product, and consequently lowers solubility in water. It is necessary to use a substance capable of controlling the viscosity of the reactant while having little effect on the physical properties of the product, as the solvent.
【００１１】 更に、連続工程において、未反応モノマーと溶媒を生産された樹脂から除去する
工程、即ち脱揮工程は、全工程の効率性の面だけではなく、揮発分含量など製品
の物性の面においても重要な役割を果たす部分であるにも拘わらず、前記の方法
ではこれに対する詳細な言及がないのが実情である。Furthermore, in the continuous process, the step of removing the unreacted monomer and the solvent from the produced resin, that is, the devolatilization step, is not only in terms of the efficiency of the entire process, but also in terms of the physical properties of the product such as the volatile content. In fact, despite the fact that it plays an important role in the above, there is no detailed description of this in the above method.
【００１２】 従って、本発明の目的は、従来の技術の問題点である、温度制御方式と反応温度
、粘度調節物質として用いられた溶媒、揮発分含量などを改善し得る連続バルク
重合によるスチレン／アクリル系水溶性樹脂の製造工程を介して、分子量が少な
い、分子量分布が狭い、高い酸価及び低い揮発分含量を有する水溶性樹脂を製造
することができる方法を提供することにある。[0012] Accordingly, an object of the present invention is to provide a method of controlling styrene / styrene by continuous bulk polymerization that can improve the temperature control method and reaction temperature, the solvent used as a viscosity controlling substance, the volatile content, and the like, which are problems of the prior art. An object of the present invention is to provide a method for producing a water-soluble resin having a low molecular weight, a narrow molecular weight distribution, a high acid value and a low volatile content through a process for producing an acrylic water-soluble resin.
【００１３】 発明の開示 上記目的を達成するための本発明は、スチレン／アクリル系水溶性樹脂を製造し
得る連続バルク重合工程において、モノマー、開始剤及びモノマー１００重量部
に対して５〜１５重量部のジプロピレングリコールメチルエーテルと水との混合
溶媒を反応器に連続して注入し、オイルジャケットとオイルジャケット内の冷却
コイルを用いて温度を制御することが可能な反応器で、反応温度１５０〜２２０
℃、１０〜２０分の滞留時間にて重合が行われ、これをフォーリングストランド
(falling strand)型脱揮装置に移送し、１８０〜２１０℃の温度と−５００〜−
７５０ｍｍＨｇの圧力条件で運転して揮発分を除去させることを特徴とする。DISCLOSURE OF THE INVENTION In order to achieve the above object, the present invention provides a method for producing a styrene / acrylic water-soluble resin in a continuous bulk polymerization step, wherein 5 to 15 parts by weight based on 100 parts by weight of a monomer, an initiator and a monomer are used. Part of a mixed solvent of dipropylene glycol methyl ether and water is continuously injected into the reactor, and the temperature can be controlled using an oil jacket and a cooling coil in the oil jacket. ~ 220
The polymerization is carried out at a residence time of 10 to 20 minutes at a temperature of 10 ° C.
(falling strand) type devolatilizer, and the temperature of 180 ~ 210 ℃ and -500 ~-
It is characterized by operating under a pressure condition of 750 mmHg to remove volatile components.
【００１４】 本発明の実施するための最良の形態 以下、本発明を更に具体的に説明する。 本発明によるスチレン／アクリル系水溶性樹脂の製造方法は、溶媒としてジプロ
ピレングリコールメチルエーテル（ＤＰＭ）と水との混合溶媒を使用し、スチレ
ン系モノマーとアクリル系モノマー（以下、「モノマー」という）を低い反応温
度、即ち約１５０〜２２０℃の低温でバルク連続重合法を用いてスチレン／アク
リル系水溶性樹脂を製造する。選択的に、本発明は分子量調節剤としてα-メチ
ルスチレンオリゴマーを更に含むことができる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically. The method for producing a styrene / acrylic water-soluble resin according to the present invention uses a mixed solvent of dipropylene glycol methyl ether (DPM) and water as a solvent, and forms a styrene monomer and an acrylic monomer (hereinafter, referred to as “monomer”). A styrene / acrylic water-soluble resin is produced using a bulk continuous polymerization method at a low reaction temperature, that is, a low temperature of about 150 to 220 ° C. Alternatively, the present invention may further include an α-methylstyrene oligomer as a molecular weight modifier.
【００１５】 図１はスチレン／アクリル系水溶性樹脂を製造するために考案された連続バルク
重合工程を示す。図１に示すように、本発明で考案された連続バルク重合工程は
、２つのモノマー攪拌タンク（１及び２）、反応器３、フォーリングストランド
型の脱揮装置４、蒸留塔５、モノマーリサイクルタンク６などから構成される。FIG. 1 shows a continuous bulk polymerization process devised for producing a styrene / acrylic water-soluble resin. As shown in FIG. 1, the continuous bulk polymerization process devised in the present invention comprises two monomer stirring tanks (1 and 2), a reactor 3, a falling strand type devolatilizer 4, a distillation column 5, a monomer recycle. It is composed of a tank 6 and the like.
【００１６】 モノマーをモノマー攪拌タンク（１又は２）から一定の速度で反応器３に注入し
、反応器で１０〜２０分の滞留時間を有するように反応器の水位を調節する。こ
の際、反応器の容量は７５リットルであり、連続バルク重合の反応温度を効率よ
く制御するために熱媒油が流れ得るジャケットを設け、ジャケットの内部に低温
の熱媒油が流れ得る冷却コイルを設けた。その結果、反応温度の制御が容易にな
り、低い温度１５０〜２２０℃の反応温度で重量平均分子量３，０００〜１０，
０００、分子量分布２.０以下のスチレン／アクリル系水溶性樹脂を製造するこ
とができた。The monomer is injected into the reactor 3 at a constant rate from the monomer stirring tank (1 or 2), and the reactor water level is adjusted so that the reactor has a residence time of 10 to 20 minutes. At this time, the capacity of the reactor is 75 liters, a jacket through which a heat transfer oil can flow is provided in order to efficiently control the reaction temperature of the continuous bulk polymerization, and a cooling coil through which a low-temperature heat transfer oil can flow inside the jacket. Was provided. As a result, the reaction temperature can be easily controlled, and the weight average molecular weight is 3,000 to 10, at a low reaction temperature of 150 to 220 ° C.
A styrene / acrylic water-soluble resin having a molecular weight distribution of 2,000 or less could be produced.
【００１７】 反応器を経由することにより重合が完了した水溶性樹脂は、樹脂内の揮発成分を
除去するために、フォーリングストランド型の脱揮装置４へ移送される。脱揮装
置に熱媒油が流れ得るジャケットを設け、一定の温度が維持できるようにし、真
空ポンプ７を用いて脱揮装置に一定の真空を保つことができるようにした。その
結果、２％以下の揮発分含量を有するスチレン／アクリル系水溶性樹脂を製造す
ることができた。The water-soluble resin that has been polymerized by passing through the reactor is transferred to a falling-strand type devolatilizer 4 in order to remove volatile components in the resin. The devolatilizer was provided with a jacket through which the heat medium oil could flow, so that a constant temperature could be maintained, and the vacuum pump 7 could be used to maintain a constant vacuum in the devolatilizer. As a result, a styrene / acrylic water-soluble resin having a volatile content of 2% or less could be produced.
【００１８】 脱揮装置で除去された揮発成分は、未反応モノマー、高沸点物質、及び溶媒とし
て用いられたジプロピレングリコールメチルエーテルと水との混合物から構成さ
れている。前記揮発物質は、精製のために蒸留塔５へ移送されて高沸点物質が分
離された後、モノマーリサイクルタンク６に蓄えられ、一定の比率が反応器に注
入されてスチレン／アクリル系水溶性樹脂の製造に再活用される。The volatile component removed by the devolatilizer is composed of an unreacted monomer, a high-boiling substance, and a mixture of dipropylene glycol methyl ether used as a solvent and water. The volatile substances are transferred to a distillation column 5 for purification to separate high-boiling substances, and then stored in a monomer recycle tank 6. A certain ratio is injected into a reactor and a styrene / acrylic water-soluble resin is added. Reused in the manufacture of
【００１９】 一方、水溶性樹脂の製造に際して、反応熱吸収及び反応物の粘度調節のために
、米国特許第４，４１４，３７０号では、ジエチレングリコールモノエチルエー
テルを溶媒として用いた。しかし、この物質はヒドロキシ基をもっているため、
水溶性樹脂のカルボキシル基とエステール化反応を起こして水溶性樹脂の分子内
に化学的に結合することにより、溶媒としての機能を喪失して、反応物の粘度が
上昇し、反応器の内部温度の調節が難しくなり、なお且つ水溶性樹脂の酸価を落
として製品の物性を低下させたりもする。On the other hand, in the production of a water-soluble resin, diethylene glycol monoethyl ether was used as a solvent in US Pat. No. 4,414,370 to absorb reaction heat and adjust the viscosity of the reaction product. However, since this substance has a hydroxy group,
By causing an esterification reaction with the carboxyl group of the water-soluble resin and chemically bonding in the molecule of the water-soluble resin, the function as a solvent is lost, the viscosity of the reactant increases, and the internal temperature of the reactor increases. This makes it difficult to control the properties of the water-soluble resin and lowers the physical properties of the product by lowering the acid value of the water-soluble resin.
【００２０】 従って、本発明では、モノマー１００重量部に対して５〜１５重量部のジプロピ
レングリコールメチルエーテルと水との混合物を溶媒として、反応物の粘度を調
節することができると共に、アクリル酸とエステール反応を減らして、２００〜
２３０の酸価を有するスチレン／アクリル系水溶性樹脂を製造することができた
。この際、前記溶媒混合物中の水の含量は２０〜４５重量％が好ましいが、前記
水の含量が２０重量％未満であれば、ジプロピレングリコールメチルエーテルと
アクリル酸との間にエステール化反応がたくさん起こることになり、最終製品の
酸価が低下するという問題が生じ、４５重量％を超過すれば、水の蒸発量が多く
なって反応器の内部圧力が上昇し、反応物の粘度を効果的に調節できないという
問題が生じる。Therefore, in the present invention, the viscosity of the reactant can be adjusted while using a mixture of 5 to 15 parts by weight of dipropylene glycol methyl ether and water with respect to 100 parts by weight of the monomer as a solvent, and acrylic acid can be adjusted. And reduce the Esther reaction, 200 ~
A styrene / acrylic water-soluble resin having an acid value of 230 could be produced. At this time, the content of water in the solvent mixture is preferably 20 to 45% by weight, but if the content of water is less than 20% by weight, an esterification reaction between dipropylene glycol methyl ether and acrylic acid may occur. If it exceeds 45% by weight, the evaporation of water will increase and the internal pressure of the reactor will increase, which will increase the viscosity of the reactants. A problem arises in that the adjustment cannot be performed.
【００２１】 一方、本発明で用いられるモノマーは、スチレン系モノマー及びアクリル系モノ
マーを６０〜８０：２０〜４０の重量比で混合してなされるが、前記スチレン系
モノマーは、スチレン単独或いは混合重量比５０〜９０：１０〜５０のスチレン
及びα-メチルスチレンモノマーを含み、前記アクリル系モノマーはアクリル酸
単独、或いは２０重量％以下のアルキルアクリラートモノマーとアクリル酸との
組合せを含む。On the other hand, the monomer used in the present invention is obtained by mixing a styrene monomer and an acrylic monomer in a weight ratio of 60 to 80:20 to 40, and the styrene monomer is styrene alone or a mixed weight of styrene. The acrylic monomer includes acrylic acid alone or a combination of acrylic acid and alkyl acrylate monomer in an amount of 20% by weight or less, including styrene and α-methylstyrene monomer in a ratio of 50 to 90:10 to 50.
【００２２】 本発明で分子量調節剤として用いられるα-メチルスチレンオリゴマーは、モ
ノマー１００重量部に対して２〜６重量部とする。この際、２重量部未満であれ
ば、高分子量及び分子量分布の広い樹脂が生成され、６重量部を超過すれば、所
望の分子量より低い分子量を有する樹脂が生成されて物性が低下する虞がある。The amount of the α-methylstyrene oligomer used as a molecular weight modifier in the present invention is 2 to 6 parts by weight based on 100 parts by weight of the monomer. At this time, if the amount is less than 2 parts by weight, a resin having a high molecular weight and a wide molecular weight distribution is generated, and if the amount exceeds 6 parts by weight, a resin having a molecular weight lower than a desired molecular weight is generated and the physical properties may be deteriorated. is there.
【００２３】 前記α-メチルスチレンモノマーは、樹脂の分子量と分子量分布を調節する役割
を果たすが、多量のα-メチルスチレンの含有は、樹脂の顔料分散性を低下させ
るという短所をもっている(Surface Phenomena and Latexes in Waterborn Coat
ings and Printing Technologies, Edited by M. K. Sharma, Plenum Press, Ne
w York, 1995, p139-151)。多量のα-メチルスチレンモノマーの代わりに分子量
調節剤として少量のα-メチルスチレンオリゴマー、たとえばTekchem Corporati
on社のTechlon M21 Extraを使用することにより、顔料分散性に優れており且つ
匂いも色も問題にならないスチレン／アクリル水溶性樹脂を製造することができ
る。Although the α-methylstyrene monomer plays a role in controlling the molecular weight and molecular weight distribution of the resin, the content of a large amount of α-methylstyrene has the disadvantage of lowering the pigment dispersibility of the resin (Surface Phenomena). and Latexes in Waterborn Coat
ings and Printing Technologies, Edited by MK Sharma, Plenum Press, Ne
w York, 1995, p139-151). Instead of a large amount of α-methylstyrene monomer, a small amount of α-methylstyrene oligomer such as Tekchem Corporati
By using Techlon M21 Extra manufactured by on, a styrene / acrylic water-soluble resin excellent in pigment dispersibility and having no problem in odor and color can be produced.
【００２４】 更に、本発明における開始剤としては、反応が低温で起こるため、低温開始剤が
用いられるが、ｔ-ブチルペルオキシベンゾアート(t-butyl peroxy benzoate)が
好ましく、その使用量は前記モノマーの総量に対して３〜６重量部が好ましい。Further, as the initiator in the present invention, a low-temperature initiator is used because the reaction takes place at a low temperature. However, t-butyl peroxybenzoate is preferable, and the amount of the initiator is the same as that of the monomer. Is preferably 3 to 6 parts by weight based on the total amount of
【００２５】 本発明では重合物中の揮発分を取り除くためにフォーリングストランド型の脱揮
装置を使用したが、前記方法は、米国特許第４，４１４，３７０号で用いた攪拌
タンク(Stirred Tank)型の脱揮装置を使用した場合より、樹脂の表面積を大きく
して樹脂内の揮発分を容易に除去し得るという点において有利である。In the present invention, a falling strand type devolatilizer is used to remove volatile components in the polymer. However, the above method uses a stirring tank (Stirred Tank) used in US Pat. No. 4,414,370. This is advantageous in that the surface area of the resin can be increased and volatile components in the resin can be easily removed as compared with the case of using a devolatilizing device of the type).
【００２６】 一方、本発明のフォーリングストランド型脱揮装置の温度条件は１８０〜２１０
℃が好ましく、前記温度が１８０℃未満であれば、樹脂内の揮発分を充分に除去
し難いという問題が生じ、２１０℃を超えれば、樹脂が劣化して物性が低下する
という問題が生ずる。On the other hand, the temperature condition of the falling strand type devolatilizer of the present invention is 180 to 210.
C. is preferable. If the temperature is lower than 180.degree. C., there arises a problem that it is difficult to sufficiently remove volatile components in the resin, and if it exceeds 210.degree. C., there occurs a problem that the resin is deteriorated and physical properties are deteriorated.
【００２７】 また、前記フォーリングストランド型脱揮装置の圧力条件は、−７５０〜−５０
０ｍｍＨｇが好ましく、前記圧力が−７５０ｍｍＨｇ未満であれば、樹脂の流れ
性が急激に悪くなり樹脂の移送が極めて難しくなるという問題が発生し、−５０
０ｍｍＨｇを超えれば、樹脂内の揮発分を充分に除去し難くなる。The pressure condition of the falling strand type devolatilizer is −750 to −50.
The pressure is preferably 0 mmHg, and if the pressure is less than -750 mmHg, the flowability of the resin rapidly deteriorates and the transfer of the resin becomes extremely difficult.
If it exceeds 0 mmHg, it will be difficult to sufficiently remove volatile components in the resin.
【００２８】 以下、実施例によって本発明を更に具体的に説明するが、この実施例によって本
発明が限定されるものではない。Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.
【００２９】 実施例１〜５ 外部にオイルジャケットが設けられており、オイルジャケットの内部に冷却コイ
ルが設けられている、温度が制御できる連続攪拌型反応器に、次の表１に記載の
量だけスチレン系モノマー（スチレン及びα-メチルスチレン）とアクリル系モ
ノマー（アクリル酸）を入れてスチレン／アクリル系水溶性樹脂を製造した。Examples 1 to 5 In a continuously stirred reactor capable of controlling the temperature in which an oil jacket was provided outside and a cooling coil was provided inside the oil jacket, the amount shown in the following Table 1 was added. Only a styrene monomer (styrene and α-methylstyrene) and an acrylic monomer (acrylic acid) were added to produce a styrene / acrylic water-soluble resin.
【００３０】 この際、用いられた重合開始剤はｔ-ブチルペルオキシベンゾアートであり、
その使用量はモノマーの総量に対して３.５重量部であった。また、溶媒として
は、ジプロピレングリコールメチルエーテルと水との混合物をモノマー１００重
量部に対して１５重量部だけ使用した。この際、混合溶媒中の水の含量は３５％
であった。反応温度は１５０℃〜２２０℃に変化させた。一方、製造された水溶
性樹脂の揮発分を除去するためにフォーリングストランド型の脱揮装置を通過さ
せて、揮発分の除去された水溶性樹脂を最終的に得た。この際、前記脱揮装置の
運転条件は１９５°、−７５０ｍｍＨｇであった。At this time, the polymerization initiator used is t-butylperoxybenzoate,
The amount used was 3.5 parts by weight based on the total amount of the monomers. As the solvent, a mixture of dipropylene glycol methyl ether and water was used in an amount of only 15 parts by weight based on 100 parts by weight of the monomer. At this time, the content of water in the mixed solvent was 35%.
Met. The reaction temperature was varied from 150C to 220C. On the other hand, the produced water-soluble resin was passed through a falling-strand type devolatilization device to remove volatile components, thereby finally obtaining a water-soluble resin from which volatile components had been removed. At this time, the operating conditions of the devolatilizer were 195 ° and -750 mmHg.
【００３１】[0031]
【表１】 [Table 1]
【００３２】 比較例１〜３ 本発明で利用された反応器がいかに効果的に反応器の内部温度を制御するかを裏
付けるために、前記実施例２、４と５と同一の条件下で、反応器オイルジャケッ
ト内部の冷却コイルには熱媒油が流れないようにし、反応器の内部に臨時に冷却
コイルを設け、スチレン／アクリル系水溶性樹脂を製造した。これに対する結果
を次の表２に示す。Comparative Examples 1-3 To confirm how effectively the reactor used in the present invention controls the internal temperature of the reactor, under the same conditions as in Examples 2, 4 and 5, Heat medium oil was prevented from flowing into the cooling coil inside the reactor oil jacket, and a temporary cooling coil was provided inside the reactor to produce a styrene / acrylic water-soluble resin. The results are shown in Table 2 below.
【００３３】[0033]
【表２】 [Table 2]
【００３４】 前記表１と表２に示すように、通常の反応器により同一の反応温度で調節したス
チレン／アクリル系水溶性樹脂の分子量分布は本発明による反応器により得たス
チレン／アクリル系水溶性樹脂の分子量分布よりも広い。これは反応器内部の温
度偏差により、平均的な反応温度が同一であっても、部分的には反応温度が異な
るからである。即ち、反応器外部のオイルジャケットと反応器内部の冷却コイル
を有するタイプの反応器では反応温度の制御が容易でないことが分る。As shown in Tables 1 and 2, the molecular weight distribution of the styrene / acrylic water-soluble resin controlled at the same reaction temperature by a normal reactor is based on the styrene / acrylic water soluble resin obtained by the reactor according to the present invention. Wider than the molecular weight distribution of the conductive resin. This is because even if the average reaction temperature is the same, the reaction temperature is partially different due to the temperature deviation inside the reactor. That is, it can be seen that control of the reaction temperature is not easy in a reactor having an oil jacket outside the reactor and a cooling coil inside the reactor.
【００３５】 実施例６〜９ 揮発分除去装置である脱揮装置の運転条件の影響を調べるために、前記実施例４
と同一の条件下で脱揮装置の運転条件を変化させながら、スチレン／アクリル系
水溶性樹脂を製造した。これに対する結果を次の表３に示す。Embodiments 6 to 9 In order to investigate the influence of the operating conditions of the devolatilizer, which is a devolatilizer, the embodiment 4 was used.
A styrene / acrylic water-soluble resin was produced under the same conditions as above and while changing the operating conditions of the devolatilizer. The results are shown in Table 3 below.
【００３６】[0036]
【表３】 [Table 3]
【００３７】 比較例４〜５ 脱揮装置の運転条件に対する影響を更に詳しく調べるために、実施例４と同一の
条件下で運転条件を変化させながら、スチレン／アクリル系水溶性樹脂を製造し
た。これに対する結果を次の表４に示す。Comparative Examples 4 to 5 In order to investigate the influence on the operating conditions of the devolatilizer in more detail, a styrene / acrylic water-soluble resin was produced while changing the operating conditions under the same conditions as in Example 4. The results are shown in Table 4 below.
【００３８】[0038]
【表４】 [Table 4]
【００３９】 前記表４から分るように、脱揮装置の温度が低く且つ圧力が高い場合には揮発
分含量が高く、脱揮装置の温度が高く且つ圧力が低い場合には揮発分含量は低い
が、分子量分布が広くなり酸価が多少低下する。As can be seen from Table 4, when the temperature of the devolatilizer is low and the pressure is high, the volatile content is high. When the temperature of the devolatilizer is high and the pressure is low, the volatile content is high. Although low, the molecular weight distribution is broad and the acid value is slightly reduced.
【００４０】 実施例１０〜１３ 使用した混合溶媒の影響を調べるために、前記実施例４と同一の条件下で、混合
溶媒の使用量（ジプロピレングリコールメチルエーテルと水との混合液）及び混
合溶媒の組成を変化させ、スチレン／アクリル系水溶性樹脂を製造した。Examples 10 to 13 In order to examine the influence of the mixed solvent used, the amount of the mixed solvent used (mixed liquid of dipropylene glycol methyl ether and water) and the mixing under the same conditions as in Example 4 above The composition of the solvent was changed to produce a styrene / acrylic water-soluble resin.
【００４１】 比較例６ 前記実施例１０において溶媒としてジプロピレングリコールメチルエーテルのみ
を使用したことを除いては同様に実施した。これに対する結果を次の表５に示す
。表５において、比較例６は単独溶媒の使用量である。Comparative Example 6 The same procedure was performed as in Example 10 except that only dipropylene glycol methyl ether was used as a solvent. The results are shown in Table 5 below. In Table 5, Comparative Example 6 is the amount of a single solvent used.
【００４２】[0042]
【表５】 [Table 5]
【００４３】 実施例１４〜１７ 使用したスチレン系モノマー含量の影響を調べるために、前記実施例４と同一の
条件下でスチレンとα-メチルスチレンモノマーの使用量を変化させ、スチレン
／アクリル系水溶性樹脂を製造した。これに対する結果を次の表６に示す。Examples 14 to 17 In order to examine the effect of the content of the styrene monomer used, the amounts of styrene and α-methylstyrene monomer were changed under the same conditions as in Example 4 to obtain a styrene / acrylic aqueous solution. A reactive resin was manufactured. The results are shown in Table 6 below.
【００４４】[0044]
【表６】 [Table 6]
【００４５】 実施例１８〜２０ 使用したアクリル系モノマー含量の影響を調べるために、前記実施例４と同一の
条件下でアクリル酸とメチルアクリラートの使用量を変化させ、スチレン／アク
リル系水溶性樹脂を製造した。これに対する結果を次の表７に示す。Examples 18 to 20 In order to investigate the influence of the content of the acrylic monomer used, the amounts of acrylic acid and methyl acrylate were changed under the same conditions as in Example 4 to obtain a water-soluble styrene / acrylic solution. A resin was manufactured. The results are shown in Table 7 below.
【００４６】[0046]
【表７】 [Table 7]
【００４７】 比較例７ 米国特許第４，４１４，３７０号に提示された方法によって、反応器ジャケット
に熱媒油を流し、反応器の内部に冷却コイルを設けて温度を制御し得る連続攪拌
型反応器に、次の表８に記載の量だけスチレン系モノマー（スチレン及びα-メ
チルスチレン）とアクリル系モノマー（アクリル酸）を入れ、反応溶媒としては
ジエチレングリコールモノエチルエーテルを使用し、次の表８に記載の温度でス
チレン／アクリル系水溶性樹脂を製造した。これに対する結果を次の表８に示す
。Comparative Example 7 According to the method disclosed in US Pat. No. 4,414,370, a continuous stirring type in which a heating medium oil is supplied to a reactor jacket and a cooling coil is provided inside the reactor to control the temperature. The styrene monomer (styrene and α-methylstyrene) and the acrylic monomer (acrylic acid) were charged into the reactor in the amounts shown in Table 8 below, and diethylene glycol monoethyl ether was used as a reaction solvent. A styrene / acrylic water-soluble resin was produced at the temperature described in No. 8. The results are shown in Table 8 below.
【００４８】[0048]
【表８】 [Table 8]
【００４９】 実施例２１〜２２ 使用したα-メチルスチレンオリゴマーの影響を調べるために、前記実施例４と
同一の条件下でα-メチルスチレンオリゴマーの使用量を変化させ、スチレン／
アクリル系水溶性樹脂を製造した。これに対する結果を次の表９に示す。Examples 21 to 22 In order to examine the influence of the α-methylstyrene oligomer used, the amount of the α-methylstyrene oligomer was changed under the same conditions as in Example 4 above.
Acrylic water-soluble resin was manufactured. The results are shown in Table 9 below.
【００５０】[0050]
【表９】 [Table 9]
【００５１】 産業上の利用可能性 以上説明したように、スチレン／アクリル系水溶性樹脂を製造する連続バルク
重合工程において、ジプロピレングリコールメチルエーテルと水との混合物を溶
媒とし、従来の技術とは異なる方式の反応温度の制御方式、フォーリングストラ
ンド型脱揮装置の形態及び運転方法によって製造された本発明のスチレン／アク
リル系水溶性樹脂は、従来の方法で製造された樹脂より低温においても低い分子
量、狭い分子量分布、高い酸価及び低い揮発分含量を有するので、産業上非常に
有用である。Industrial Applicability As described above, in the continuous bulk polymerization step for producing a styrene / acrylic water-soluble resin, a mixture of dipropylene glycol methyl ether and water is used as a solvent, The styrene / acrylic water-soluble resin of the present invention produced by a different method of controlling the reaction temperature, the form of the falling strand type devolatilizer, and the operating method is lower than the resin produced by the conventional method even at a lower temperature. It has a high molecular weight, a narrow molecular weight distribution, a high acid number and a low volatile content, which is very useful in industry.
【図１】 本発明の連続バルク重合工程を示す概略図である。FIG. 1 is a schematic diagram showing a continuous bulk polymerization step of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 オ、ソクヒョン 大韓民国、デジョン−シ、ユウソン−ク、 シンソン−ドン、デリム アパート 110 −705 (72)発明者 ウオン、ホ−ヨン 大韓民国、デジョン−シ、ユウソン−ク、 シンソン−ドン、デリム アパート 110 −605 Ｆターム(参考） 4J011 AA04 AA05 AA07 AB02 AB05 BA01 DA04 DB26 DB28 FA02 FB05 HA08 HB02 HB12 PA65 PB23 PB40 PC02 PC08 PC13 PC15 4J026 AA17 BA05 BA25 BB03 DB02 DB05 DB08 DB32 DB38 4J100 AB02P AB03R AJ02Q CA04 CA05 DA38 FA18 FA19 FA28 FA47 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Oh, Seokhyeon Republic of Korea, Daejeon-si, Yusong-ku, Shinsung-dong, Daelim Apartment 110-705 Yousung-ku, Shinsung-dong, Daelim Apartment 110-605 F-term (reference) 4J011 AA04 AA05 AA07 AB02 AB05 BA01 DA04 DB26 DB28 FA02 FB05 HA08 HB02 HB12 PA65 PB23 PB40 PC02 PC08 PC13 PC15 4J026 AA17 BA05 DB05 DB05 DB02 DB05 4J100 AB02P AB03R AJ02Q CA04 CA05 DA38 FA18 FA19 FA28 FA47
Claims (9)
ロピレングリコールメチルエーテルと水との混合溶媒存在下で、スチレン系モノ
マーとアクリル系モノマーを１５０〜２２０℃の反応温度で重合した後、前記重
合物からフォーリングストランド型の脱揮装置で揮発分を除去することを特徴と
する連続バルク重合によるスチレン／アクリル系水溶性樹脂の製造方法。1. A method for producing a styrene / acrylic water-soluble resin, wherein a styrene monomer and an acrylic monomer are polymerized at a reaction temperature of 150 to 220 ° C. in the presence of a mixed solvent of dipropylene glycol methyl ether and water. A method for producing a styrene / acrylic water-soluble resin by continuous bulk polymerization, wherein volatile matter is removed from the polymer by a falling strand type devolatilizer.
〜１５重量部であることを特徴とする請求項１記載の連続バルク重合によるスチ
レン／アクリル系水溶性樹脂の製造方法。2. The amount of the mixed solvent used is 5 to 100 parts by weight of the monomer.
The method for producing a styrene / acrylic water-soluble resin by continuous bulk polymerization according to claim 1, wherein the amount is from 15 to 15 parts by weight.
を特徴とする請求項１記載の連続バルク重合によるスチレン／アクリル系水溶性
樹脂の製造方法。3. The method for producing a water-soluble styrene / acrylic resin by continuous bulk polymerization according to claim 1, wherein the content of water in the mixed solvent is 20 to 45% by weight.
を６０〜８０：２０〜４０の重量比で混合した混合物であることを特徴とする請
求項１記載のスチレン／アクリル系水溶性樹脂の製造方法。4. The styrene / acrylic water-soluble resin according to claim 1, wherein the monomer is a mixture of a styrene monomer and an acrylic monomer mixed at a weight ratio of 60 to 80:20 to 40. Manufacturing method.
とα-メチルスチレンモノマーを５０〜９０：１０〜５０の重量比で混合した混
合物であることを特徴とする請求項１又は４記載のスチレン／アクリル系水溶性
樹脂の製造方法。5. The styrene monomer according to claim 1, wherein the styrene monomer is styrene alone or a mixture of styrene and α-methylstyrene monomer in a weight ratio of 50 to 90:10 to 50. A method for producing a styrene / acrylic water-soluble resin.
酸とアルキルアクリラートモノマーとの混合物であり、前記アルキルアクリラー
トモノマーの含量は２０重量％以下であることを特徴とする請求項１又は４記載
のスチレン／アクリル系水溶性樹脂の製造方法。6. The method of claim 1, wherein the acrylic monomer is acrylic acid alone or a mixture of acrylic acid and an alkyl acrylate monomer, and the content of the alkyl acrylate monomer is 20% by weight or less. Or the method for producing a styrene / acrylic water-soluble resin according to 4.
び−５００〜−７５０ｍｍＨｇの圧力条件で運転されることを特徴とする請求項
１記載のスチレン／アクリル系水溶性樹脂の製造方法。7. The styrene / acrylic water-soluble resin according to claim 1, wherein the devolatilizer is operated at a temperature of 180 to 210 ° C. and a pressure of −500 to −750 mmHg. Production method.
コイルとを用いて温度を制御するタイプの反応器で行われることを特徴とする請
求項１記載のスチレン／アクリル系水溶性樹脂の製造方法。8. The styrene / acrylic water-soluble resin according to claim 1, wherein the reaction is performed in a reactor of a type that controls the temperature using an oil jacket and a cooling coil inside the oil jacket. Production method.
のα-メチルスチレンオリゴマーを更に含むことを特徴とする請求項１記載のス
チレン／アクリル系水溶性樹脂の製造方法。9. The method for producing a water-soluble styrene / acrylic resin according to claim 1, wherein the method further comprises 2 to 6 parts by weight of an α-methylstyrene oligomer based on 100 parts by weight of the monomer. .
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019980056434A KR100301126B1 (en) | 1998-12-19 | 1998-12-19 | Method for producing styrene / acrylic water-soluble resin by continuous bulk polymerization |
| KR1998/056434 | 1998-12-19 | ||
| PCT/KR1999/000103 WO2000037506A1 (en) | 1998-12-19 | 1999-03-04 | Process for preparing water-soluble styrene/acrylic resins by continuous bulk polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002533480A true JP2002533480A (en) | 2002-10-08 |
| JP3570624B2 JP3570624B2 (en) | 2004-09-29 |
Family
ID=19563948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000589575A Expired - Lifetime JP3570624B2 (en) | 1998-12-19 | 1999-03-04 | Method for producing styrene / acrylic water-soluble resin by continuous bulk polymerization |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP3570624B2 (en) |
| KR (1) | KR100301126B1 (en) |
| CN (1) | CN1146579C (en) |
| HK (1) | HK1043800B (en) |
| ID (1) | ID29615A (en) |
| WO (1) | WO2000037506A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009231270A (en) * | 2008-02-29 | 2009-10-08 | Commissariat A L'energie Atomique | Manufacturing method of ion conductive polymer film for fuel cell |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100560622C (en) * | 2008-02-27 | 2009-11-18 | 广东天龙油墨集团股份有限公司 | The continuous processing mass polymerization prepares the water miscible acrylic resin of polymolecularity and preparation method and the application in printing ink thereof |
| JP5947297B2 (en) * | 2010-08-05 | 2016-07-06 | ハンワ ケミカル コーポレイション | Highly efficient heat-dissipating paint composition using carbon material |
| KR101495211B1 (en) | 2013-01-08 | 2015-02-24 | 한화케미칼 주식회사 | Resin for blister package and preparation method thereof |
| KR102687446B1 (en) * | 2020-08-31 | 2024-07-23 | 한화솔루션 주식회사 | Method for preparing styrene maleic anhydride resin through continuous polymerization and styrene maleic anhydride resin preprared thereby |
| KR102732121B1 (en) * | 2020-08-31 | 2024-11-19 | 한화솔루션 주식회사 | Method for preparing high solid acrylic polyol resin through continuous polymerization and acrylic polyol resin preprared thereby |
| CN113384489B (en) * | 2021-06-16 | 2022-06-17 | 宇虹颜料股份有限公司 | Processing method of water-based nail polish preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4451612A (en) * | 1980-09-22 | 1984-05-29 | Mobil Oil Corporation | Continuous process for the preparation of rubber modified polymers |
| EP0068024B2 (en) * | 1981-01-09 | 1996-02-07 | S.C. Johnson & Son, Inc. | Process for continuous bulk copolymerization of vinyl monomers |
| US4414370A (en) * | 1981-01-09 | 1983-11-08 | S. C. Johnson & Son, Inc. | Process for continuous bulk copolymerization of vinyl monomers |
| JPS6058773B2 (en) * | 1981-06-30 | 1985-12-21 | 日立金属株式会社 | Ni-Cr-W alloy with improved high temperature fatigue strength and its manufacturing method |
| US4937298A (en) * | 1988-03-17 | 1990-06-26 | Dainippon Ink And Chemicals, Inc. | Process for producing styrene/(meth)acrylic acid copolymer |
| DE19524181A1 (en) * | 1995-07-03 | 1997-01-09 | Basf Ag | Process and device for the continuous production of polymers |
-
1998
- 1998-12-19 KR KR1019980056434A patent/KR100301126B1/en not_active IP Right Cessation
-
1999
- 1999-03-04 WO PCT/KR1999/000103 patent/WO2000037506A1/en active Search and Examination
- 1999-03-04 CN CNB998147737A patent/CN1146579C/en not_active Expired - Lifetime
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009231270A (en) * | 2008-02-29 | 2009-10-08 | Commissariat A L'energie Atomique | Manufacturing method of ion conductive polymer film for fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1043800A1 (en) | 2002-09-27 |
| HK1043800B (en) | 2005-02-18 |
| KR20000040715A (en) | 2000-07-05 |
| CN1331704A (en) | 2002-01-16 |
| ID29615A (en) | 2001-09-06 |
| KR100301126B1 (en) | 2001-09-06 |
| CN1146579C (en) | 2004-04-21 |
| WO2000037506A1 (en) | 2000-06-29 |
| JP3570624B2 (en) | 2004-09-29 |
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