JPS63130603A - Production of low-molecular weight acrylic polymer - Google Patents
Production of low-molecular weight acrylic polymerInfo
- Publication number
- JPS63130603A JPS63130603A JP27517986A JP27517986A JPS63130603A JP S63130603 A JPS63130603 A JP S63130603A JP 27517986 A JP27517986 A JP 27517986A JP 27517986 A JP27517986 A JP 27517986A JP S63130603 A JPS63130603 A JP S63130603A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- polymerization
- isobutyl ketone
- methyl isobutyl
- mixture
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920000058 polyacrylate Polymers 0.000 title claims description 4
- -1 methyl isobutyl ketone peroxide Chemical class 0.000 claims abstract description 22
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract 2
- 229920000642 polymer Polymers 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000008096 xylene Substances 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011541 reaction mixture Substances 0.000 abstract description 3
- 238000010533 azeotropic distillation Methods 0.000 abstract description 2
- 239000012044 organic layer Substances 0.000 abstract description 2
- 238000005292 vacuum distillation Methods 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 9
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、低分子量アクリル系重合体の製造において、
ラジカル重合開始剤として、メチルイソブチルケトンパ
ーオキサイドを用いることに関する。Detailed Description of the Invention (Industrial Application Field) The present invention provides a method for producing low molecular weight acrylic polymers.
The present invention relates to using methyl isobutyl ketone peroxide as a radical polymerization initiator.
（従来の技術）
近年、低分子量（共）重合体の様々の優れた性質が見直
され、多（の分野において、新たな用途開発が進んでお
り、原材料・中間体としての低分子量重合体はますます
その重要性が高まりて米ている。例えば、低分子量スチ
レン系重合体では、印刷インキ、塗料、紙処理剤、接着
剤等の分野において、その特性が見い出されて、需要が
増して来ている。塗料業界においては、環境汚染低減・
防止の観点から、塗料のハイソリッド化に注目が集まっ
ている。かかるハイソリッド化達成のためには、塗料用
共重合体を低分子量化することが必須である。(Conventional technology) In recent years, the various excellent properties of low molecular weight (co)polymers have been reconsidered, and new applications are being developed in many fields. For example, low molecular weight styrene polymers have been discovered to have such properties in the fields of printing inks, paints, paper processing agents, adhesives, etc., and demand is increasing. In the paint industry, environmental pollution reduction and
From the viewpoint of prevention, attention is being paid to the use of high-solid paints. In order to achieve such a high solid state, it is essential to lower the molecular weight of the coating copolymer.
（発明が帛決しようとする問題点）
そのため、重合体の製造時に連鎖移動剤として、たとえ
ばメルカプタン類を添加し、その量を増やして行くと、
低分子量化が達成される。(Problem to be solved by the invention) Therefore, if mercaptans, for example, are added as a chain transfer agent during the production of a polymer and the amount thereof is increased,
Lower molecular weight is achieved.
しかし、メルカプタン類自身に基づく強烈な悪用いると
か、高温度領域で重合を行うと、やはり重合体の低分子
量化は達成されるが、重合溶媒に制限があったり、特殊
な反応製電を必要とするので、工業的に充分納得のいく
簡便な低分子量重合体の製造法は未だ確立されていない
と本発明者らは、これらの問題点を解決すべく種々の有
機過酸化物をラジカル重合開始剤とし重合体が得られる
ことを見い出し、この発明に至った。However, if the mercaptans themselves are subjected to severe abuse, or if polymerization is carried out at high temperatures, a lower molecular weight of the polymer can be achieved, but there are restrictions on the polymerization solvent and special reaction production is required. Therefore, an industrially acceptable and simple method for producing low molecular weight polymers has not yet been established.In order to solve these problems, the inventors of the present invention conducted radical polymerization of various organic peroxides. It was discovered that a polymer can be obtained as an initiator, leading to the present invention.
すなわち、従来から、メチルイソブチルケトンパーオキ
サイドは広く不飽和ポリエステル樹脂の硬化剤として使
われてきているが、下記する一般式で表わされる構造の
化合物を主たる成分とする混合組成物として存在してお
り、通常（３型）
（４型）
３型が４型に対して７０％以下の含有組成物が多用され
ている。本発明では、メチルイソブチルケトンパーオキ
サイド、好ましくは、３型が４型に対して７０％以上含
まれるメチルイソブチルケトンパーオキサイド組成物を
ラジカル重合開始剤として使用することにより、低分子
量アクリル系重合体を有利に製造する点に特徴がある。That is, methyl isobutyl ketone peroxide has traditionally been widely used as a curing agent for unsaturated polyester resins, but it exists as a mixed composition whose main component is a compound having the structure represented by the general formula below. , Usually (Type 3) (Type 4) Compositions containing 70% or less of type 3 relative to type 4 are often used. In the present invention, by using methyl isobutyl ketone peroxide, preferably a methyl isobutyl ketone peroxide composition containing 70% or more of type 3 to type 4, as a radical polymerization initiator, a low molecular weight acrylic polymer can be produced. It is characterized by the fact that it can be manufactured advantageously.
これら３型、４型の含有比率の異なるメチルイソブチル
ケトンパーオキサイド組成物は通常の方法にて合成でき
るが、特に３型を主たる成分とする本発明に用いる組成
物については米国特許第４０５２４６５号明細書の実施
例５および６に記載の方法に準じれば比較的簡単に合成
できる。例えば７０％の過酸化水素水３８．９ｇ（０，
８モル）を、ベンゼン３０ｍ１．’メチルインブチルケ
トン５０ｇ（０，５モル）およびｐ−トルエンスルホン
酸（２ＩＩ１ｇ当量１モルケトン）に添加し、１５分間
混合し、その後、冷却して２０℃に温度を保つ。添加終
了後約２０ｇの水を、３０℃、減圧下共沸蒸留により反
応混合物から除去する。次に４０ｍ１の水を加え、混合
物のｐＨを、２Ｎ−水酸化ナトリウムの溶液により約５
．５に調整する。キシレン３１ｇを有機層に添加し、ベ
ンゼンを減圧蒸留により除去する。These methyl isobutyl ketone peroxide compositions having different content ratios of type 3 and type 4 can be synthesized by conventional methods, but in particular, the composition used in the present invention containing type 3 as a main component is disclosed in US Pat. No. 4,052,465. It can be synthesized relatively easily by following the method described in Examples 5 and 6 of the book. For example, 38.9 g of 70% hydrogen peroxide (0,
8 mol) in 30 ml of benzene. 'Add to 50 g (0.5 mol) of methyl imbutyl ketone and p-toluenesulfonic acid (2II 1 g equivalent 1 mol ketone) and mix for 15 minutes, then cool and maintain temperature at 20<0>C. After the addition is complete, about 20 g of water are removed from the reaction mixture by azeotropic distillation at 30° C. and reduced pressure. Then 40 ml of water is added and the pH of the mixture is brought to about 5 with a solution of 2N sodium hydroxide.
．． Adjust to 5. 31 g of xylene is added to the organic layer and benzene is removed by vacuum distillation.
その結果、総活性酸素量（ＡＯ）が１３．１％のメチル
イソブチルケトンパーオキサイド溶液８０ｇを得る。こ
の溶液は、約７０％が３塑成分を含んでいる（薄′層ク
ロマトグラフィー）。As a result, 80 g of methyl isobutyl ketone peroxide solution having a total active oxygen amount (AO) of 13.1% is obtained. This solution contains approximately 70% triplastic components (thin layer chromatography).
得られた溶液は、そのままの形でも使用可能であるが、
さらに、°１５℃で水洗を伴うサルフチイト水溶液によ
る処理を行い、キシレン１９ｇで希釈した結果、ＡＯ含
有量９．５％で３塑成分を９４％含むメチルイソブチル
ケトンパーオキサイド溶液９０ｇが得らる。The resulting solution can be used as is, but
Furthermore, treatment with an aqueous sulftite solution accompanied by water washing at 15° C. and dilution with 19 g of xylene yields 90 g of a methyl isobutyl ketone peroxide solution containing 9.5% AO content and 94% 3 plastic components.
そして合成条件を選んでやれば、３型のみから成るメチ
ルインブチルケトンパーオキサイドの合成も可能である
。If the synthesis conditions are selected, it is also possible to synthesize methyl in butyl ketone peroxide consisting of only type 3.
本１発明に使用できる単量体はビニル型であり主に塗料
用重合体を生成しうるものであればよく、通常はアクリ
ル系単量体である。たとえば（メタ）アクリル酸アルキ
ルエステルであり、具体的には、メタクリル酸メチル、
メタクリル障エチル、メタクリル酸ブチル、メタクリル
酸イソブチル、アクリル酸メチル、アクリル酸エチル、
アクリル酸ブチル、アクリル酸イソブチル、アクリル酸
２−エチルヘキシル、メタクリル酸２−エチルヘキシル
テアル。The monomers that can be used in the present invention are vinyl type monomers that can mainly produce coating polymers, and are usually acrylic monomers. For example, (meth)acrylic acid alkyl esters, specifically methyl methacrylate,
Ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, methyl acrylate, ethyl acrylate,
Butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexylteal methacrylate.
また、水酸基含有単量体も使用でき、たとえば、アクリ
ル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキ
シエチルであり、カルボキシル基含有単量体も使用でき
、アクリル酸、メタクリル酸が例示できる。Furthermore, hydroxyl group-containing monomers can also be used, such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, and carboxyl group-containing monomers can also be used, examples of which include acrylic acid and methacrylic acid.
さらには、仁れらアクリル系単量体と共重合可能な単量
体も同時に使用することは差しつかえなく、たとえば、
スチレンを代表とするスチレン系単量体が例としてあげ
られる。Furthermore, monomers copolymerizable with Nire et al.'s acrylic monomer may also be used at the same time; for example,
An example is a styrenic monomer represented by styrene.
これらの単量体は重合体の最終用途に応じてその組み合
わせや混合比率はおのずと変わり５ることはもちろんで
ある。そしてここに列記した範囲に限定されるものでは
ない。Of course, the combination and mixing ratio of these monomers will vary depending on the final use of the polymer. And it is not limited to the range listed here.
本発明の低分子量重合体の製造忙用いることのできる重
合開始剤としての有機過酸化物は、メチルイソブチルケ
トンパーオキサイドである。An organic peroxide as a polymerization initiator that can be used in the production of the low molecular weight polymer of the present invention is methyl isobutyl ketone peroxide.
好ましくは、３型含有高が７０％以上の組成物である。Preferably, the composition has a type 3 content of 70% or more.
通常安全化のためにフタル酸エステル類で希釈されるが
、その希釈剤として、トルエン、キシレン等の芳香族炭
化水素溶媒、又は脂肪族炭化水素溶媒であってもさしつ
かえなく、生成する重合体の最終用途上問題とならなけ
れば、特に限定されるものではない。It is usually diluted with phthalate esters for safety, but aromatic hydrocarbon solvents such as toluene, xylene, or aliphatic hydrocarbon solvents can also be used as the diluent. There is no particular limitation as long as it does not pose a problem in terms of end use.
重合開始剤としてのメチルイソブチルケトンである。好
ましくは、１重量％から８重量％である。０．５重量％
以下では重合収車があまり上がらず、分子量もあまり低
下しない。また１０重量％以上では、急激な重合による
発熱にともない尊台制御困難となることもある。Methyl isobutyl ketone is used as a polymerization initiator. Preferably it is 1% to 8% by weight. 0.5% by weight
Below this, the polymerization yield does not increase much and the molecular weight does not decrease much either. Moreover, if it exceeds 10% by weight, it may become difficult to control the weight due to heat generation due to rapid polymerization.
効果的な重合温度は９０℃以上１６０℃以下である。こ
の温度域からはずれると所望する低分子量化が効果的に
得にくくなる。Effective polymerization temperature is 90°C or higher and 160°C or lower. If the temperature is outside this range, it becomes difficult to effectively achieve the desired low molecular weight.
重合溶媒としては、トルエン、キシレン等はもちろんの
こと、生成する重合体の最終用途上問題とならなければ
特に制限されるものではないＯ
本発明の実施にお〜・ては、あらかじめ単量体にメチル
インブチルケトンパーオキサイドを添加しておき、これ
らを適肖な溶媒中で重合させることができる。さらには
、重合温度まで予熱しておいた溶媒中に単量体とメチル
イソブチルケトンパーオキサイドの混合物を連ｉ的にｉ
下する方式も取ることができ、重合処決についての特別
の制限はない。Examples of the polymerization solvent include toluene, xylene, etc., and there are no particular restrictions as long as it does not pose a problem in the final use of the resulting polymer. Methyl inbutyl ketone peroxide can be added to the solution, and these can be polymerized in a suitable solvent. Furthermore, a mixture of monomers and methyl isobutyl ketone peroxide is sequentially added to a solvent preheated to the polymerization temperature.
There are no particular restrictions on the polymerization treatment.
言うまでもなく、重合体の分子量は、メチルイソブチル
ケトンパーオキサイドの添加量、重合温度、単量体と溶
媒の仕込比高等により制御されることはもちろんである
。なお、重合形態については、溶液重合に留まらず、塊
状重合。Needless to say, the molecular weight of the polymer is controlled by the amount of methyl isobutyl ketone peroxide added, the polymerization temperature, and the charging ratio of monomer and solvent. The polymerization form is not limited to solution polymerization, but also bulk polymerization.
懸濁重合さらには乳化重合にも応用でき、限定されるも
のではない。It can be applied to suspension polymerization and even emulsion polymerization, and is not limited thereto.
（実施例）
以下実施例により本発明の詳細な説明するが実施例のみ
の範囲に限定されるものではないことはもちろんである
。(Examples) The present invention will be described in detail below with reference to Examples, but it goes without saying that the scope is not limited to the Examples only.
酸メチルあるいは必要に応じて共重合可能な単量体を、
ここではスチレ／を、溶媒およびメチルイソブチルケト
ンパーオキサイドと共に合計１０ｍ１になるようにパイ
レックス製の封管に仕込み、ドライアイス／メタノール
系浴中冷却下に脱気／チッソガス置換操作を数回行った
後、減圧下に溶封した。油浴中、所定温度・時間・反応
させた後、開封して、内容物を取り出し°、分析中測定
試料とした。なお、メチルイソブチルケトンパーオキサ
イドの添加量は、重量％であり、対単量体量で表わした
。また単量体、溶媒の仕込量は、重量部で表わした。methyl acid or a copolymerizable monomer as necessary,
Here, styrene was placed in a Pyrex sealed tube together with the solvent and methyl isobutyl ketone peroxide to a total volume of 10 ml, and after being cooled in a dry ice/methanol bath, deaeration/nitrogen gas replacement was performed several times. , and melt-sealed under reduced pressure. After reacting in an oil bath at a predetermined temperature and time, the package was opened and the contents were taken out to be used as a measurement sample during analysis. Note that the amount of methyl isobutyl ketone peroxide added is expressed in weight %, based on the amount of monomer. Further, the amounts of monomers and solvents were expressed in parts by weight.
重合一体の取高（％）は、ＧＬＣによる残留単量体の測
定値から計算して求めた。また、数平均分子量値（Ｍｎ
）はポリスチレンを標準とするＧＰＣ測定から求めたも
のである。The yield (%) of the polymerized product was calculated from the measured value of the residual monomer by GLC. In addition, the number average molecular weight value (Mn
) was determined from GPC measurement using polystyrene as a standard.
表ＩＫ実施例１〜５および比較例１〜８の重合条件、仕
込比そしてそのときのそれぞれの重合結果をまとめた。Table IK The polymerization conditions, charging ratios, and respective polymerization results of Examples 1 to 5 and Comparative Examples 1 to 8 are summarized.
これらの結果より、メチルイソブチルケトンパーオキサ
イドを用いると分子［１万以下の低分子量重合体が容易
如得られることがわかる。These results show that when methyl isobutyl ketone peroxide is used, a low molecular weight polymer having a molecular weight of 10,000 or less can be easily obtained.
実施例６゜
攪拌機、温度計、還流冷却器、Ｎ２ガス導入管および滴
下ロートを備えたセパラブル丸底フラスコにキシレン７
０部を仕込み、Ｎ２ガスを導入しつつ１３０℃に昇温し
た後、メタクリル酸メチル１２０部とメチルイソブチル
ケトンパーオキサイド８部の混合物を滴下ロートより３
時間かけて滴下した。滴下終了後１時間そのまま、１３
０℃で保温後、メチルイソブチルケトンパーオキサイド
２部とキシレン１０部の混合物を再び１時間かけて滴下
した。滴下終了後１３０℃°で５時間熟成し、その後冷
却して樹脂溶液を得た。Example 6゜Xylene 7 was placed in a separable round bottom flask equipped with a stirrer, thermometer, reflux condenser, N2 gas inlet tube and dropping funnel.
After charging 0 parts and raising the temperature to 130°C while introducing N2 gas, 3 parts of a mixture of 120 parts of methyl methacrylate and 8 parts of methyl isobutyl ketone peroxide was added through the dropping funnel.
It dripped over time. Leave it as it is for 1 hour after the completion of dripping, 13
After keeping the temperature at 0° C., a mixture of 2 parts of methyl isobutyl ketone peroxide and 10 parts of xylene was again added dropwise over 1 hour. After completion of the dropwise addition, the mixture was aged at 130°C for 5 hours, and then cooled to obtain a resin solution.
得られた樹脂の数平均分子量は３０００．また重合収率
は９７．３％であった。得られた樹脂溶液はほぼ透明無
色であった。The number average molecular weight of the obtained resin was 3000. Moreover, the polymerization yield was 97.3%. The resulting resin solution was almost transparent and colorless.
実施例７゜
パイレックス製重合封管に、メタクリル酸メチル５ｇと
メチルイソブチルケトンパーオキサイド０．３５ｇの混
合物を仕込み、前述の実施例１〜５と同様に、脱気した
後、溶封した。Example 7 A mixture of 5 g of methyl methacrylate and 0.35 g of methyl isobutyl ketone peroxide was charged into a polymer sealed tube made of Pyrex, and the tube was degassed and then melt-sealed in the same manner as in Examples 1 to 5 above.
１０５℃の油浴中、１０時間反応させた。得られた重合
体の数平均分子量は７０００、重合収出は９８．８％で
あった。The reaction was carried out for 10 hours in an oil bath at 105°C. The number average molecular weight of the obtained polymer was 7000, and the polymerization yield was 98.8%.
比較例９゜ 実施例７と同一条件下で塊状重合を行った。Comparative example 9° Bulk polymerization was carried out under the same conditions as in Example 7.
ただし、重合開始剤として、ＴＢＰＢを用いた。However, TBPB was used as a polymerization initiator.
得られた重合体の数平均分子量は１２０００、重合収出
は９７．５％であった。The number average molecular weight of the obtained polymer was 12,000, and the polymerization yield was 97.5%.
実施例８゜
パイレックス製重合用封管に、アクリル酸２−エチルヘ
キシル５ｇ１キシレン５ｇ、おヨヒメチルインプチルケ
トンバーオキサイド０．５ｇを仕込み、前述の実施例１
〜５と同様に、脱気後溶封した。１３０℃の油浴中、１
０時間反応させた。分析の結果得られた重合体の数平均
分子量は３０００、重合収率は９８．１％であった。Example 8 A Pyrex sealed tube for polymerization was charged with 5 g of 2-ethylhexyl acrylate, 5 g of xylene, and 0.5 g of methyl imptyl ketone peroxide.
In the same manner as in ~5, it was melt-sealed after degassing. In an oil bath at 130°C, 1
The reaction was allowed to proceed for 0 hours. The number average molecular weight of the polymer obtained as a result of analysis was 3000, and the polymerization yield was 98.1%.
比較例１０６
実施例８と同一条件下で重合を行った。ただし、重合開
始剤としてＴＢＰＢを用いた。得られた重合体の数平均
分子域は９０００、重合収車は９．５．９％であった。Comparative Example 106 Polymerization was carried out under the same conditions as in Example 8. However, TBPB was used as a polymerization initiator. The number average molecular area of the obtained polymer was 9000, and the polymerization fraction was 9.5.9%.
（発明の効果）
実施例として説明したように、本発明に用いる重合開始
剤としての、メチルイソブチルケトンパーオキサイドは
、重合方法に特別の工夫の必要なく、容易に高収鹿で低
分子量重合体を与えることがわかる。従って、工業的利
用価値は極めて大きいと言える。(Effects of the Invention) As explained in the examples, methyl isobutyl ketone peroxide as a polymerization initiator used in the present invention can be easily formed into a high-yielding, low-molecular-weight polymer without the need for any special innovation in the polymerization method. It can be seen that it gives Therefore, it can be said that the industrial value is extremely large.
Claims (1)
して、メチルイソブチルケトンパーオキサイドを用いる
ことを特徴とする低分子量アクリル系重合体の製造方法
。A method for producing a low molecular weight acrylic polymer, which comprises using methyl isobutyl ketone peroxide as a polymerization initiator in polymerizing an acrylic monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27517986A JPS63130603A (en) | 1986-11-20 | 1986-11-20 | Production of low-molecular weight acrylic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27517986A JPS63130603A (en) | 1986-11-20 | 1986-11-20 | Production of low-molecular weight acrylic polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63130603A true JPS63130603A (en) | 1988-06-02 |
Family
ID=17551772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27517986A Pending JPS63130603A (en) | 1986-11-20 | 1986-11-20 | Production of low-molecular weight acrylic polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63130603A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0637595A1 (en) * | 1993-02-18 | 1995-02-08 | Nippon Shokubai Co., Ltd. | Process for producing polymer |
-
1986
- 1986-11-20 JP JP27517986A patent/JPS63130603A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0637595A1 (en) * | 1993-02-18 | 1995-02-08 | Nippon Shokubai Co., Ltd. | Process for producing polymer |
| EP0637595A4 (en) * | 1993-02-18 | 1995-08-02 | Nippon Catalytic Chem Ind | Process for producing polymer. |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100577697C (en) | Method for producing an (meth)acrylate syrup | |
| US6150468A (en) | Water soluble amphiphilic heteratom star polymers and their use as emulsion stabilizers in emulsion polymerization | |
| JPH02281013A (en) | Diketone compound copolymer | |
| CN103282340A (en) | Substituted 3-xopentanoates and their uses in coating compositions | |
| JP2008522002A (en) | Branched polymer | |
| JP2847242B2 (en) | Method for producing carboxyl group-containing macromonomer | |
| JP7486721B2 (en) | Cyclocarbonate group-containing (meth)acrylate monomers and polymers | |
| JPS63130603A (en) | Production of low-molecular weight acrylic polymer | |
| JPH0119402B2 (en) | ||
| US4600755A (en) | Free radical initiated polymerization of polymerizable ethylenically unsaturated monomer component in the presence of hydrogen peroxide | |
| JPH0354226A (en) | Curable composition and production thereof | |
| JPH0532733A (en) | Production of varnish for paint | |
| HUE029754T2 (en) | Additive, composition comprising it and use thereof | |
| WO2001096411A1 (en) | Water soluble ampiphilic heteratom star polymers and their use as emulsion stabilizers in emulsion polymerization | |
| JP2019023319A (en) | Block polymer and method for producing the same | |
| JPH02193958A (en) | Methacrylic acid ester and production thereof | |
| TWI838455B (en) | (Meth)acrylate monomers and polymers containing cyclic carbonate groups | |
| JPH06199938A (en) | Production of glutarimide copolymer and its intermediate compound | |
| JPH11140127A (en) | Preparation of acrylic polymer having functional group at both ends | |
| JP4001108B2 (en) | Method for producing cured product and coating film | |
| JP4123603B2 (en) | NOVEL COPOLYMER AND METHOD FOR PRODUCING THE SAME | |
| JP3059261B2 (en) | Method for producing a novel polymer containing a lactone adduct having an epoxy group as a main component | |
| JPS61231005A (en) | Radical polymerization initiator | |
| JPH04328112A (en) | Production of varnish for paint | |
| JPH0770242A (en) | Vinyl copolymer containing allyl group at side chain and its production |