JPH0433908A - Production of block copolymer - Google Patents
Production of block copolymerInfo
- Publication number
- JPH0433908A JPH0433908A JP13846590A JP13846590A JPH0433908A JP H0433908 A JPH0433908 A JP H0433908A JP 13846590 A JP13846590 A JP 13846590A JP 13846590 A JP13846590 A JP 13846590A JP H0433908 A JPH0433908 A JP H0433908A
- Authority
- JP
- Japan
- Prior art keywords
- polymerizable unsaturated
- unsaturated monomer
- azo
- polyurethane
- block copolymer
- 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
- 229920001400 block copolymer Polymers 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
- -1 azo compound Chemical class 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 31
- 239000005056 polyisocyanate Substances 0.000 claims description 16
- 229920001228 polyisocyanate Polymers 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 18
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- COZQDNPLORIALF-UHFFFAOYSA-N 3-hydroxy-2-methylpropanenitrile Chemical compound OCC(C)C#N COZQDNPLORIALF-UHFFFAOYSA-N 0.000 abstract 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 abstract 1
- 229920003232 aliphatic polyester Polymers 0.000 abstract 1
- 239000003999 initiator Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- LGOHHOGAZVMVSL-UHFFFAOYSA-N 2-(hydroxymethyl)pentanenitrile Chemical compound CCCC(CO)C#N LGOHHOGAZVMVSL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000002794 monomerizing effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は縮合ポリマー成分とビニルポリマー成分からな
るブロック共重合体の製造方法に係わるものであり、さ
らに詳細には飽和ポリエステル、ポリエーテル、ポリア
ミドなどの活性水素含有化合物、水酸基含有アゾ化合物
、ポリイソシアネート及び重合性不飽和単量体中を反応
させて得られるアゾ基含有ポリウレタンを重合開始剤と
して連続して重合性不飽和単量体を重合させることから
得られる多種多様な製品設計が可能であるブロック共重
合体の製造方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a block copolymer consisting of a condensation polymer component and a vinyl polymer component, and more specifically relates to a method for producing a block copolymer consisting of a condensation polymer component and a vinyl polymer component, and more specifically, it relates to a method for producing a block copolymer consisting of a condensation polymer component and a vinyl polymer component. Continuously polymerize the polymerizable unsaturated monomer using an azo group-containing polyurethane obtained by reacting an active hydrogen-containing compound such as hydroxyl group-containing azo compound, polyisocyanate, and a polymerizable unsaturated monomer as a polymerization initiator. The present invention relates to a method for producing a block copolymer that enables a wide variety of product designs.
［従来の技術］
本発明のごとき、水酸基含有アゾ化合物を使用してポリ
ウレタン成分とビニルポリマー成分からなるブロック共
重合体の製法は知られている。[Prior Art] A method for producing a block copolymer comprising a polyurethane component and a vinyl polymer component using a hydroxyl group-containing azo compound as in the present invention is known.
例えばＡｎｇｅｗ、 Ｍａｃｒｏｍｏｌ、Ｃｈｅｍ。For example, Angew, Macromol, Chem.
ｖｏｌ、１ ９２−１０４ （１９６７）ではテトラヒ
ドロフラン中でポリプロピレングリコールとトリレンジ
イソシアネートを反応させ、更にアゾビスシアノペンタ
ノールを加え得られた高分子アゾ開始剤を乾燥させる。Vol. 1 92-104 (1967), polypropylene glycol and tolylene diisocyanate are reacted in tetrahydrofuran, azobiscyanopentanol is added, and the resulting polymeric azo initiator is dried.
次いで高分子アゾ開始剤をベンゼンに溶解させ重合性不
飽和単量体を加え重合させることにより、ブロック共重
合体溶液を得ている。また、Ｊ、Ａｐｐｌ ｆｅｄ
Ｐｏｌｙｍｅｒ Ｓｃｉ、、ｖｏｌ、３１．２１７
１−２１８３ （１９８６）にはトルエン中でポリエチ
レングリコールとイソホロンジイソシアネートを反応さ
せ、ジクロルメタンに溶解させ、石油エーテルにて再沈
後乾燥させ、得られた高分子アゾ開始剤をスチレンに溶
解させ重合後ジクロルメタンに再度溶解させメタノール
に沈澱し乾燥してブロック共重合体を作製している。こ
のように公知の文献にみられる製法は溶媒中で高分子ア
ゾ開始剤を合成し沈澱液に沈澱させ、沈澱物をアゾ開始
剤が分解しないように低温で真空乾燥させて、高分子ア
ゾ開始剤を得ている。さらに得られた高分子アゾ開始剤
を溶媒中でモノマーを重合させた後沈澱液に沈澱させ乾
燥しブロック共重合体を得る方法である。Next, a block copolymer solution is obtained by dissolving a polymer azo initiator in benzene, adding a polymerizable unsaturated monomer, and polymerizing the solution. Also, J, Appl fed
Polymer Sci,, vol, 31.217
1-2183 (1986), polyethylene glycol and isophorone diisocyanate were reacted in toluene, dissolved in dichloromethane, re-precipitated in petroleum ether and dried, and the resulting polymeric azo initiator was dissolved in styrene. A block copolymer is produced by dissolving it again in dichloromethane, precipitating it in methanol, and drying it. As described above, the production method found in known literature is to synthesize a polymeric azo initiator in a solvent, precipitate it in a precipitation solution, vacuum dry the precipitate at a low temperature to prevent the azo initiator from decomposing, and synthesize a polymeric azo initiator. are receiving drugs. Furthermore, the obtained polymeric azo initiator is used to polymerize monomers in a solvent, and then precipitated in a precipitation solution and dried to obtain a block copolymer.
［発明が解決しようとする課題］
これらの方法は、高分子アゾ開始剤を乾燥しているため
所要時間が長いこと、溶媒及び沈澱液を使用しており工
業的に製造するにはこれらの溶媒を回収する必要があり
、著しく不経済である。[Problems to be Solved by the Invention] These methods require a long time because the polymeric azo initiator is dried, and they use solvents and precipitation solutions, so these solvents are not necessary for industrial production. must be recovered, which is extremely uneconomical.
［課題を解決するための手段］
かかる実情に鑑み、本発明者らは鋭意研究した結果、生
産効率の良い製造方法を見い出し本発明を完成するに至
った。[Means for Solving the Problems] In view of the above circumstances, the present inventors conducted intensive research and as a result, they discovered a manufacturing method with good production efficiency and completed the present invention.
すなわち本発明は、水酸基含有アゾ化合物、ポリイソシ
アネート、活性水素含有化合物及び重合性不飽和単量体
を反応せしめてアゾ基含有ポリウレタンを形成し、次い
で重合性不飽和単量体を重合せしめてなることを特徴と
するブロック共重合体の製造方法、更には水酸基含有ア
ゾ化合物とポリイソシアネートを溶媒中にて反応せしめ
てアゾ基含有ポリイソシアネートを合成し、次いで該ポ
リイソシアネートと重合性不飽和単量体と活性水素含有
化合物を反応せしめてアゾ基含有ポリウレタンを形成し
、次いで重合性不飽和単量体を重合することを特徴とす
るブロック共重合体の製造方法を提供するものである。That is, the present invention comprises reacting a hydroxyl group-containing azo compound, a polyisocyanate, an active hydrogen-containing compound, and a polymerizable unsaturated monomer to form an azo group-containing polyurethane, and then polymerizing the polymerizable unsaturated monomer. A method for producing a block copolymer, further comprising reacting a hydroxyl group-containing azo compound and a polyisocyanate in a solvent to synthesize an azo group-containing polyisocyanate, and then reacting the polyisocyanate with the polyisocyanate and a polymerizable unsaturated monomer. The present invention provides a method for producing a block copolymer, which comprises reacting the polyurethane with an active hydrogen-containing compound to form an azo group-containing polyurethane, and then polymerizing a polymerizable unsaturated monomer.
［発明の構成］
本発明に用いられる水酸基含有アゾ化合物は、代表的な
例として２，２−アゾビス（２−シアツブロバノール）
、２．２−アゾビス（２−シアノペンタノール）、２．
２−アゾビス［２−メチルー−Ｎ−（２−ヒドロキシエ
チル）プロピオアミトコなどがあげられる。[Structure of the Invention] A typical example of the hydroxyl group-containing azo compound used in the present invention is 2,2-azobis(2-cyatuburobanol).
, 2.2-azobis(2-cyanopentanol), 2.
Examples include 2-azobis[2-methyl-N-(2-hydroxyethyl)propioamitoco].
ポリイソシアネートとしては、例えばジフェニルジメタ
ンジイソシアネート、トリレンジイソシアネート、キシ
レンジイソシアネート、ヘキサメチレンジイソシアネー
ト、イソホロンジイソシアネート、水添ジフェニルメタ
ンジイソシアネート、水添トリレンジイソシアネート、
およびこれらを用いて得られる両末端イソシアネートの
プレポリマーなどが用いられる。ポリイソシアネートの
使用量は、ＮＣ０１０Ｈ（モル数）の比が０．８〜１．
１となるように使用される。Examples of the polyisocyanate include diphenyl dimethane diisocyanate, tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate,
and prepolymers of isocyanate at both ends obtained using these are used. The amount of polyisocyanate used is such that the ratio of NC010H (number of moles) is 0.8 to 1.
1.
活性化水素含有化合物としては、−０Ｈ１−ＳＨ，ＮＨ
ｓ、＝ＮＨ，Ｃ５ＮＨｓ、 Ｃ（＝ＮＨ）ＯＨ，−Ｃ
（＝ＮＨ）ＮＨ，＝ＮＯＨ。Activated hydrogen-containing compounds include -0H1-SH, NH
s, =NH,C5NHs, C(=NH)OH, -C
(=NH)NH,=NOH.
−ＮＨＮＨ，、−ＣＯＮＨＮＨ，、−ＮＲＮＨ，、＝Ｎ
ＮＨ！、−ＮＨＣＯＮＨ，、−ＮＨＣ８ＮＨ２、−ＮＲ
Ｃ３ＮＨ２、−ＮＲＣＯＮＨ！、 −ＮＨＣ（＝ＮＲ）
ＮＨｓ、ｌはアルキル基）等の有機基を含む化合物のこ
とであり、好ましくは一〇Ｈ１−ＮＨ２を含むものであ
る。これらの有機基は、ポリウレタン系樹脂−分子中に
一種含まれていても良いし、二種歯まれていても良い。-NHNH,, -CONHNH,, -NRNH,, =N
NH! , -NHCONH, -NHC8NH2, -NR
C3NH2, -NRCONH! , -NHC (=NR)
It refers to a compound containing an organic group such as NHs (l is an alkyl group), and preferably one containing 10H1-NH2. One kind of these organic groups may be contained in the polyurethane resin molecule, or two kinds thereof may be contained in the polyurethane resin molecule.
重合性不飽和単量体の例としては、スチレン、α−メチ
ルスチレン、ビニルトルエンの如キ芳香族ビニル類、メ
チル（メタ）アクリレート、ブチル（メタ）アクリレー
トの如き（メタ）アクリル酸エステル類、酢酸ビニル、
プロピオン酸ビニル、安息香酸ビニルの如きビニルエス
テル類、塩化ビニル、塩化ビニリデン、フッ化ビニル、
フッ化ビニリデンの如きハロゲン化ビニル類などが用い
られる。Examples of polymerizable unsaturated monomers include styrene, α-methylstyrene, aromatic vinyls such as vinyltoluene, (meth)acrylic acid esters such as methyl (meth)acrylate and butyl (meth)acrylate, vinyl acetate,
Vinyl esters such as vinyl propionate and vinyl benzoate, vinyl chloride, vinylidene chloride, vinyl fluoride,
Vinyl halides such as vinylidene fluoride are used.
本発明の製造方法は、アゾ基含有ポリウレタンといった
高分子量アゾ開始剤を合成する工程及び該ポリウレタン
と重合性不飽和単量体との重合工程の二工程からなるも
のである。高分子■アゾ開始剤（アゾ基含有ポリウレタ
ン）を合成する方法としては、 （１）重合性不飽和単
量体中で水酸基含有アゾ化合物、活性化水素含有化合物
、ポリイソシアネートを反応させて、アゾ基含有ポリウ
レタンの重合性不飽和単量体溶液を得る方法。（２）ア
ゾ化合物を溶解しうる溶媒、例えばＮ−メチルピロリド
ン、アセトン、ジメチルホルムアミドの如き溶媒中で水
酸基含有アゾ化合物（開始剤）とポリイソシアネートを
反応させ、次いで重合性不飽和単量体と活性水素含有化
合物を添加し反応せしめてアゾ基含有ポリウレタンの重
合性不飽和単量体溶媒溶液を得る方法などがある。 （
１）の方法は、最も理想的であるが、水酸基含有アゾ化
合物は、重合性不飽和単量体に溶解しにくいため高分子
量のアゾ基含有ポリウレタンが得られない。The production method of the present invention consists of two steps: a step of synthesizing a high molecular weight azo initiator such as an azo group-containing polyurethane, and a step of polymerizing the polyurethane with a polymerizable unsaturated monomer. The method for synthesizing a polymer ■azo initiator (azo group-containing polyurethane) is as follows: (1) Reacting a hydroxyl group-containing azo compound, an activated hydrogen-containing compound, and a polyisocyanate in a polymerizable unsaturated monomer, A method for obtaining a polymerizable unsaturated monomer solution of group-containing polyurethane. (2) A hydroxyl group-containing azo compound (initiator) is reacted with a polyisocyanate in a solvent capable of dissolving the azo compound, such as N-methylpyrrolidone, acetone, or dimethylformamide, and then a polymerizable unsaturated monomer is reacted with the polyisocyanate. There is a method in which an active hydrogen-containing compound is added and reacted to obtain a solution of an azo group-containing polyurethane in a polymerizable unsaturated monomer solvent. (
Method 1) is the most ideal, but since the hydroxyl group-containing azo compound is difficult to dissolve in the polymerizable unsaturated monomer, a high molecular weight azo group-containing polyurethane cannot be obtained.
（２）の方法は、少量の溶媒を逸するけれども高分子量
のアゾ基含有ポリウレタンが得られ、好ましい方法であ
る。Method (2) is a preferred method because it yields a high molecular weight azo group-containing polyurethane, although a small amount of solvent is lost.
反応は、ウレタン化反応中にアゾ基の分解を抑える必要
があるので、好ましくは１０℃以上でアゾ化合物の１０
時間半減期温度より１０°Ｃ低い温度以下の温度範囲で
行われる。Since it is necessary to suppress the decomposition of the azo group during the urethanization reaction, the reaction is preferably carried out at a temperature of 10°C or higher.
The temperature range is 10°C lower than the time half-life temperature.
高分子量アゾ基含有ポリウレタンにおける水酸基含有ア
ゾ化合物の量は、１〜１０重量％であり、好ましくは２
〜５重量％である。１重量％以下ではビニルモノマー野
重合を完了させることができず、また１０重量％以上で
はブロック共重合体野ポリウレタン部分の分子量が小さ
いものとなるので好ましくない。The amount of the hydroxyl group-containing azo compound in the high molecular weight azo group-containing polyurethane is 1 to 10% by weight, preferably 2% by weight.
~5% by weight. If it is less than 1% by weight, the vinyl monomer polymerization cannot be completed, and if it is more than 10% by weight, the molecular weight of the polyurethane portion of the block copolymer will be undesirably small.
本発明で得られるブロック共重合体は、重合性不飽和単
量体の重合体成分とポリウレタン成分とからなり、その
構成比率（重量比）は、好ましくは０．１７０．９〜０
．９１０． ｌの範囲からなる、特に好ましくは、０．
３７０．７〜０．７７０．３の範囲内である。The block copolymer obtained in the present invention consists of a polymer component of a polymerizable unsaturated monomer and a polyurethane component, and the composition ratio (weight ratio) thereof is preferably 0.170.9 to 0.
．． 910. 1, particularly preferably in the range 0.1.
It is within the range of 370.7 to 0.770.3.
そのまま加熱によってアゾ化合物を分解せしめてラジカ
ルを発生させ重合性不飽和単量体を重合させる方法であ
る。This is a method in which the azo compound is directly decomposed by heating to generate radicals to polymerize the polymerizable unsaturated monomer.
重合性不飽和単量体を重合させる方法は、塊状重合法、
溶液重合法、懸濁重合法のいずれでも良く、常法により
行う。Methods for polymerizing the polymerizable unsaturated monomer include bulk polymerization method,
Either a solution polymerization method or a suspension polymerization method may be used, and a conventional method is used.
本発明の方法によるとブロック共重合体製造時に１つの
釜を使用するだけでよく、さらに高分子アゾ開始剤を乾
燥する必要がないため乾燥工程、溶媒回収工稈が省ける
。さらに高分子アゾ開始剤のアゾ活性量が高いため、ブ
ロック化率の高いブロック共重合体が得られる。According to the method of the present invention, only one kettle needs to be used during the production of the block copolymer, and furthermore, there is no need to dry the polymeric azo initiator, so the drying process and solvent recovery process can be omitted. Furthermore, since the polymeric azo initiator has a high azo activity, a block copolymer with a high blocking rate can be obtained.
本発明により製造されるブロック共重合体は、ポリマー
ブレンド、ポリマーアロイなどの相溶化剤、耐衝撃性、
防湿性、耐水性、耐候性などを付与するポリマー改質剤
、およびブロック共重合体自身による成形品、フィルム
、シート、接着剤、塗料などに使用される。The block copolymer produced according to the present invention has a compatibilizing agent, impact resistance,
It is used as a polymer modifier that imparts moisture resistance, water resistance, weather resistance, etc., and in molded products, films, sheets, adhesives, paints, etc. made of the block copolymer itself.
次に、本発明の詳細な説明する。文中「部」及び「％」
は特に断りのない限り重量基準である。Next, the present invention will be explained in detail. "Part" and "%" in the text
are based on weight unless otherwise specified.
実施例１
２リツトルの四ツロフラスコに２，２−−アゾビス（２
−シアツブロバノール）２４．６ｇ。Example 1 2,2-Azobis(2
-cyatuburobanol) 24.6 g.
Ｎ−メチルピロリドン１００ ｇ、 ブチレングリコ
ールとアジピン酸からなる分子量２０００の飽和ポリエ
ステルポリオール７５０ ｇ、オクチル酸スズ９４ｍｇ
、 スチレン７５０ｇを入れ、３５℃にて均一溶液とし
た。次いで、２５°Ｃに冷却し、ヘキサメチレンジイソ
シアネートを８９．７ｇ入れ窒素雰囲気下で、２５°Ｃ
にて撹拌しながら、３０時間反応させたところ、系のイ
ンシアネート含量は、１，０％以下となった。反応終了
後、ｎ−ブタノール３０ｇを加え、撹拌し、高分子アゾ
開始剤スチレン溶液を得た。このアゾ開始剤２００ｇに
ジメチルホルムアミド２００ｇを加え、９０’Ｃで３時
間、さらに１００℃で５時間、スチレンを重合させた。100 g of N-methylpyrrolidone, 750 g of a saturated polyester polyol with a molecular weight of 2000 consisting of butylene glycol and adipic acid, and 94 mg of tin octylate.
, 750 g of styrene was added to form a homogeneous solution at 35°C. Next, it was cooled to 25°C, and 89.7g of hexamethylene diisocyanate was added thereto at 25°C under a nitrogen atmosphere.
When the mixture was reacted for 30 hours with stirring, the incyanate content of the system was 1.0% or less. After the reaction was completed, 30 g of n-butanol was added and stirred to obtain a polymer azo initiator styrene solution. 200 g of dimethylformamide was added to 200 g of this azo initiator, and styrene was polymerized at 90'C for 3 hours and then at 100C for 5 hours.
得られたスラリーを水洗乾燥し、１９４ｇのポリウレタ
ン−ポリスチレンブロック共重合体を得た。さらに下記
の方法でブロック化率を求めたところ、９３％であった
。The obtained slurry was washed with water and dried to obtain 194 g of polyurethane-polystyrene block copolymer. Furthermore, when the blocking rate was determined using the method described below, it was found to be 93%.
くブロック化率の測定方法〉
フロック共重合体２０ｇをテトラヒドロフラン８０ｃｃ
に溶解させた溶液を メタノール６００ＣＣとアセトン
３００ｃｃの混合液中に沈澱し、濾別する。ろ液を蒸発
乾固してその重量を測定したものをＡとする。またろ過
残物を乾燥し 再度テトラヒドロフラン８０ｃｃに溶解
させ アセトン８００ｃｃとメタノール１００ｃｃの混
合液中に沈澱しろ別する。ろ液を蒸発乾固してその重量
を測定したものをＢとする。また、ろ過残物を乾燥し重
量を測定したものをＣとする。下記（Ｉ）式よりブロッ
ク化率を求めた。なお、赤外吸収スペクトルによりＡは
ブチレングリコールとアジピン酸からなるポリウレタン
であり、またＣはポリスチレンであることを確認した。Measuring method of blocking rate> 20g of floc copolymer was added to 80cc of tetrahydrofuran.
The solution was precipitated in a mixed solution of 600 cc of methanol and 300 cc of acetone, and filtered. The filtrate was evaporated to dryness and its weight was measured and designated as A. The filtered residue was dried, dissolved again in 80 cc of tetrahydrofuran, precipitated in a mixed solution of 800 cc of acetone and 100 cc of methanol, and filtered. The filtrate was evaporated to dryness and its weight was measured and designated as B. Further, the filtered residue was dried and its weight was measured and designated as C. The blocking rate was determined from the following formula (I). In addition, it was confirmed by infrared absorption spectrum that A was polyurethane consisting of butylene glycol and adipic acid, and C was polystyrene.
（Ｉ）式
１リツトルの四ツロフラスコに ２，２−−アゾビス（
２−シアツブロバノール）１４．７ｇ。(I) Formula 2,2-Azobis(
2-cyatuburobanol) 14.7 g.
メチルエチルケトン４９．０ｇを入れ溶解させ、オクチ
ル酸スズ４．６ｍｇを添加した。窒素雰囲気下でトリレ
ンジイソシア＊−ト３６．５４ｇを滴下し、撹拌しなが
ら２０℃で８時間反応させた。49.0 g of methyl ethyl ketone was added and dissolved, and 4.6 mg of tin octylate was added. 36.54 g of tolylene diisocyanate was added dropwise under a nitrogen atmosphere, and the mixture was reacted at 20° C. for 8 hours with stirring.
次いでε−カプロラクトンからなる分子量２０００のポ
リエステルポリオール３００ｇ、スチレン３５０ｇを入
れ、２０°Ｃで２４時間反応させたところ系のイソシア
ネート含量は ０． ５％以下となった。反応終了後、
ｎ−ブタノール３０ｇを加え、撹拌し、高分子アゾ開始
剤スチレン溶液を得た。Next, 300 g of a polyester polyol consisting of ε-caprolactone with a molecular weight of 2000 and 350 g of styrene were added and reacted at 20°C for 24 hours, and the isocyanate content of the system was 0. It became less than 5%. After the reaction is complete,
30 g of n-butanol was added and stirred to obtain a polymer azo initiator styrene solution.
この溶液にメチルエチルケトン６００ｇを加え冷却管ヲ
つけた２リツトルのフラスコで、８０°Ｃで８時間スチ
レンを重合させた。これを６０℃で真空乾燥させ６６８
ｇのポリウレタン−ポリスチレンフロック共重合体を得
た。さらに実施例１と同様にしてブロック化率を測定し
たところ８８％であった。600 g of methyl ethyl ketone was added to this solution, and styrene was polymerized at 80° C. for 8 hours in a 2 liter flask equipped with a condenser. This was vacuum dried at 60°C and 668
A polyurethane-polystyrene flock copolymer of g was obtained. Furthermore, when the blocking rate was measured in the same manner as in Example 1, it was 88%.
比較例１
実ｍ例１の２，２−−アゾビス（２−シアツブロバノー
ル）の代わりにアゾビスイソブチルニトリルを用いて同
様に合成したところ、１８９．５ｇのポリマーを得た。Comparative Example 1 Synthesis was carried out in the same manner as in Example 1 using azobisisobutylnitrile instead of 2,2-azobis(2-cyatuburobanol), and 189.5 g of polymer was obtained.
実施例１と同様にして フロック化率を測定したところ
２．５％でありポリウレタンとポリスチレンのブレン
ド物であった。When the flocculation rate was measured in the same manner as in Example 1, it was 2.5%, indicating that it was a blend of polyurethane and polystyrene.
［発明の効果］
実施例で示した如く、本発明によるブロック共重合体の
製造方法は、高分子アゾ開始剤とブロック共重合体の合
成を１つの釜で行うことができ、さらに高分子アゾ開始
剤を乾燥する必要がないため、乾燥工程、溶媒回収工程
が省は合成の所要時間が短い。しかも得られる共重合体
のブロック化率は高い。一方、比較例で示したように、
水酸基を持たないアゾ化合物で重合させたものはブロッ
ク共重合体にならない。[Effects of the Invention] As shown in the examples, the method for producing a block copolymer according to the present invention allows synthesis of a polymeric azo initiator and a block copolymer in one pot, and furthermore, Since there is no need to dry the initiator, the drying step and solvent recovery step are eliminated, and the synthesis time is shortened. Moreover, the blocking rate of the obtained copolymer is high. On the other hand, as shown in the comparative example,
Polymerization with an azo compound that does not have a hydroxyl group does not result in a block copolymer.
Claims (1)
水素含有化合物及び重合性不飽和単量体を反応せしめて
アゾ基含有ポリウレタンを形成し、次いで重合性不飽和
単量体を重合せしめてなることを特徴とするブロック共
重合体の製造方法。 ２、水酸基含有アゾ化合物とポリイソシアネートを溶媒
中にて反応せしめてアゾ基含有ポリイソシアネートを合
成し、次いで該ポリイソシアネートと重合性不飽和単量
体と活性水素含有化合物を反応せしめてアゾ基含有ポリ
ウレタンを形成し、次いで重合性不飽和単量体を重合す
ることを特徴とする請求項１の製造方法。[Claims] 1. A hydroxyl group-containing azo compound, a polyisocyanate, an active hydrogen-containing compound, and a polymerizable unsaturated monomer are reacted to form an azo group-containing polyurethane, and then the polymerizable unsaturated monomer is polymerized. A method for producing a block copolymer, characterized in that: 2. Synthesize an azo group-containing polyisocyanate by reacting a hydroxyl group-containing azo compound and a polyisocyanate in a solvent, and then reacting the polyisocyanate with a polymerizable unsaturated monomer and an active hydrogen-containing compound to synthesize an azo group-containing polyisocyanate. 2. The method of claim 1, wherein the polyurethane is formed and then the polymerizable unsaturated monomer is polymerized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13846590A JPH0433908A (en) | 1990-05-30 | 1990-05-30 | Production of block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13846590A JPH0433908A (en) | 1990-05-30 | 1990-05-30 | Production of block copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0433908A true JPH0433908A (en) | 1992-02-05 |
Family
ID=15222673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13846590A Pending JPH0433908A (en) | 1990-05-30 | 1990-05-30 | Production of block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0433908A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5536173A (en) * | 1993-07-22 | 1996-07-16 | Sumitomo Wiring Systems, Ltd. | Charge connector for electric vehicles |
-
1990
- 1990-05-30 JP JP13846590A patent/JPH0433908A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5536173A (en) * | 1993-07-22 | 1996-07-16 | Sumitomo Wiring Systems, Ltd. | Charge connector for electric vehicles |
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