JPS63117028A - Production of block copolymer - Google Patents
Production of block copolymerInfo
- Publication number
- JPS63117028A JPS63117028A JP61263261A JP26326186A JPS63117028A JP S63117028 A JPS63117028 A JP S63117028A JP 61263261 A JP61263261 A JP 61263261A JP 26326186 A JP26326186 A JP 26326186A JP S63117028 A JPS63117028 A JP S63117028A
- Authority
- JP
- Japan
- Prior art keywords
- block copolymer
- liquid rubber
- polyester
- compound
- polybutadiene
- 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 36
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 229920001971 elastomer Polymers 0.000 claims abstract description 34
- 239000005060 rubber Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000728 polyester Polymers 0.000 claims description 30
- 239000005062 Polybutadiene Substances 0.000 claims description 9
- 229920002857 polybutadiene Polymers 0.000 claims description 9
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 21
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000465 moulding Methods 0.000 abstract description 8
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 abstract description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 13
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 229920006337 unsaturated polyester resin Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 241001234572 Polycera Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 238000011191 terminal modification Methods 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- VMSLCPKYRPDHLN-UHFFFAOYSA-N (R)-Humulone Chemical compound CC(C)CC(=O)C1=C(O)C(CC=C(C)C)=C(O)C(O)(CC=C(C)C)C1=O VMSLCPKYRPDHLN-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920006305 unsaturated polyester Polymers 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はブロック共重合体の製造方法に関し、特に液状
ゴム系化合物部分とポリエステル部分とをセグメントと
して有するブロック共重合体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a block copolymer, and particularly to a method for producing a block copolymer having a liquid rubber compound portion and a polyester portion as segments.
液状ゴム系化合物の代表的なものとして、ポリブタジェ
ン、ポリイソプレン、ポリクロロプレンのようなジエン
系ホモポリマーの他に、これらに部分的にビニル系化合
物が含まれるポリマーが知られている。かかる液状ゴム
系化合物は、その加工品がゴム状弾性物質として広く利
用されているが、多くの熱硬化性樹脂や熱可塑性樹脂に
添加され、衝撃強度の向上、可撓性の付与、成形収縮や
成形クラックの防止、接着性情の向上、耐水性の向上等
、種々の目的を持って、他のポリマーの改質剤としても
利用されている。In addition to diene homopolymers such as polybutadiene, polyisoprene, and polychloroprene, polymers partially containing vinyl compounds are known as typical liquid rubber compounds. Processed products of such liquid rubber compounds are widely used as rubber-like elastic substances, and they are added to many thermosetting resins and thermoplastic resins to improve impact strength, add flexibility, and improve molding shrinkage. It is also used as a modifier for other polymers for various purposes, such as preventing mold cracks, improving adhesive properties, and improving water resistance.
一方、ポリエステル系ポリマーとして、脂肪族二塩基酸
、芳香層二塩基酸、脂環族二塩基酸又はこれらのエステ
ル形成性誘導体と脂肪族二価アルコールとの重縮合反応
によって得られる熱可塑性ポリエステルが知られており
、なかでもテレフタル酸を主とする芳香族ジカルボン酸
とエチレングリコールやブチレングリコールとから得ら
れるポリエステル類は、その優れた特性から、合成繊維
、合成樹脂成形品、フィルム、シート、コーティング材
料として広く利用されている。また、二塩基酸としてα
、β−不飽和ジカルボン酸を含む不飽和ポリエステルも
工業材料に広く利用されている。On the other hand, as polyester polymers, thermoplastic polyesters obtained by a polycondensation reaction of aliphatic dibasic acids, aromatic layer dibasic acids, alicyclic dibasic acids, or ester-forming derivatives thereof and aliphatic dihydric alcohols are used. Among them, polyesters obtained from aromatic dicarboxylic acids, mainly terephthalic acid, and ethylene glycol or butylene glycol are used as synthetic fibers, synthetic resin molded products, films, sheets, and coatings due to their excellent properties. Widely used as a material. Also, as a dibasic acid, α
, unsaturated polyesters containing β-unsaturated dicarboxylic acids are also widely used in industrial materials.
このように、液状ゴム系化合物とポリエステル系ポリマ
ーは、それぞれ固有の特性に応じて広く工業的に利用さ
れているが、双方の間には前記したような物性乃至特性
上の大きな相違がある。双方の特性を併せ有するポリマ
ーの工業的利用価値は計り知れないものがあり、その出
現が強く要請されているのであるが、現段階ではそのよ
うなポリマーは余り知られていない。As described above, liquid rubber compounds and polyester polymers are widely used industrially depending on their unique characteristics, but there are large differences in physical properties and characteristics between the two as described above. The industrial utility value of a polymer that has both of these properties is immeasurable, and its appearance is strongly desired, but at present, such a polymer is not well known.
〈従来の技術、その問題点〉
そこで従来は例えば、ポリエチレンテレフタレートやポ
リブチレンテレフタレート等の熱可塑性芳香族ポリエス
テル系樹脂に対し、これらは熱安定性、耐光性、成形性
、機械的物性が優れているため、前記したような工業材
料として広く利用されているが、更に靭性を付与して耐
衝撃強度等を向上させるために、各種ゴム系物質等が添
加混合されている。しかし、この種の従来法では、ポリ
エステル系樹脂とゴム系物質とが双方の物性で大きく異
なるため、均−且つ安定にゴム系物質をポリエステルマ
トリックス中に分散させることが困難であり、その目的
のために施す機械的な操作や方法も極めて煩雑であって
、ゴム分散相とポリエステルマトリックス相との界面接
着強度、が低いために界面剥離を起こす等、数多くの問
題点があり、所望の物性改良に至っていない。<Conventional technology and its problems> Conventionally, for example, thermoplastic aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate have excellent thermal stability, light resistance, moldability, and mechanical properties. Because of this, it is widely used as an industrial material as described above, but various rubber-based substances are added and mixed in order to further impart toughness and improve impact resistance and strength. However, in this type of conventional method, it is difficult to uniformly and stably disperse the rubber material in the polyester matrix because the physical properties of the polyester resin and the rubber material are significantly different. The mechanical operations and methods used for this purpose are extremely complicated, and there are many problems such as interfacial delamination due to low interfacial adhesion strength between the rubber dispersed phase and the polyester matrix phase, making it difficult to achieve the desired physical property improvement. has not yet been reached.
また従来同様に、熱硬化性不飽和ポリエステル樹脂にお
いても、硬化時の体積収縮を低減し、成形物の外観や寸
法精度更には耐衝撃性等を向上させるために、各種ゴム
系物質や熱可塑性樹脂がいわゆる低収縮化剤の意味を含
めて添加混合されている。しかし、この種の従来法でも
、上記のような低収縮化剤は一般に、不飽和ポリエステ
ル樹脂に対して分散性及び相溶性が不良であるため、不
飽和ポリエステル樹脂に充填剤、増粘剤、繊維補強剤等
を配合した樹脂組成物から上記低収縮化剤が貯蔵中に又
は硬化成形工程中で分離し、その硬化成形物の表面外観
が著しく不良になってしまうというような多くの問題点
がある。As in the past, thermosetting unsaturated polyester resins also use various rubber-based substances and thermoplastics to reduce volume shrinkage during curing and improve the appearance, dimensional accuracy, and impact resistance of molded products. A resin is added and mixed as a so-called low shrinkage agent. However, even with this type of conventional method, the above-mentioned low-shrinkage agents generally have poor dispersibility and compatibility with unsaturated polyester resins, so fillers, thickeners, There are many problems such as the above-mentioned shrinkage reducing agent separating from a resin composition containing a fiber reinforcing agent etc. during storage or during the curing molding process, resulting in a significantly poor surface appearance of the cured molded product. There is.
そこで従来、相溶性を改善した前記のような低収縮化剤
としてスチレン系ポリマーのブロック共重合体が提案さ
れている（特開昭５３−７４５９２、特開昭８Ｏ−９９
１５８）、Ｌかし、この従来提案は、相溶性はある程度
改善されているものの、木質的に靭性の乏しいスチレン
系ポリマーを用いるものであるため、低収縮性並びにと
りわけ耐衝撃性等が著しく劣るという問題点がある。Therefore, block copolymers of styrenic polymers have been proposed as the above-mentioned low shrinkage agents with improved compatibility (JP-A-53-74592, JP-A-8O-99).
158), L. Although this conventional proposal has improved compatibility to some extent, it uses a styrene-based polymer that has poor woody toughness, so it is significantly inferior in low shrinkage and especially impact resistance. There is a problem.
〈発明が解決しようとする問題点、その解決手段〉
本発明は、以上の如き従来の問題点を解決し、前述した
実際の強い要請に応える、新規で且つ安定した品質の共
重合体を工業上有利に製造する方法を提供するものであ
る。<Problems to be Solved by the Invention and Means for Solving the Problems> The present invention solves the conventional problems as described above and industrially produces a new and stable quality copolymer that meets the strong actual demands mentioned above. The present invention provides an advantageous manufacturing method.
しかして本発明者等は、上記観点で鋭意研究した結果、
液状ゴム系化合物及びポリエステル系ポリマーの双方の
特性を併せ有し或いはまた双方に親和性を有するポリマ
ーとして、その分子内に双方をセグメントの形態で有す
る共重合体が有効であり、該共重合体を製造するには例
えば、液状ゴム系化合物に二塩基酸及び脂肪族二価アル
コールをｆｆ（ｍ合させる方法や、液状ゴム系化合物と
ポリエステル系ポリマーとを直接に又は架橋剤を用いて
結合させる方法等も考えられたが、この種の方法では構
造不明の副生物ができてしまい、かかる方法を工業上実
施するには難点があるのに対し、分子内に水酸基を有す
る液状ゴム系化合物を出発物質とし、触媒存在下に、（
−脂肪族ラクトンを逐次開ｙＪ重合させて、液状ゴム系
化合物にポリエステル鎖を導入することにより、正しく
、安定した品質の目的とする共重合体が工業上も有利に
得られることを見出したのである。However, as a result of intensive research from the above viewpoint, the present inventors found that
A copolymer having both in the form of a segment in its molecule is effective as a polymer that has both the characteristics of a liquid rubber compound and a polyester polymer, or has an affinity for both. For example, a method of combining a dibasic acid and an aliphatic dihydric alcohol with a liquid rubber compound, or a method of bonding a liquid rubber compound and a polyester polymer directly or using a crosslinking agent. Although other methods have been considered, this type of method produces by-products with unknown structures, and there are difficulties in implementing such methods industrially. As a starting material, in the presence of a catalyst, (
- It has been discovered that the desired copolymer of correct and stable quality can be obtained industrially advantageously by sequentially carrying out open-yJ polymerization of aliphatic lactones and introducing polyester chains into a liquid rubber compound. be.
したがって本発明は、
分子内に１個又は２個以上の水酸基を有する液状ゴム系
化合物に（−脂肪族ラクトンを触媒存在下に反応させる
ことを特徴とする液状ゴム系−ポリエステル系ブロック
共重合体の製造方法に係る。Therefore, the present invention provides a liquid rubber-polyester block copolymer characterized by reacting a liquid rubber compound having one or two or more hydroxyl groups in the molecule with an aliphatic lactone in the presence of a catalyst. It pertains to the manufacturing method.
本発明は、分子内に水酸基を１個又は２個以上有する液
状ゴム系化合物を出発物質とし、触媒存在化に、ε−脂
肪族ラクトンを逐次開環重合させ、液状ゴム系化合物の
水酸基を介してポリエステル鎖を形成することにより、
工業上有利に安定してブロック共重合体を得るものであ
るが、液状ゴム系化合物に存在する水酸基は、該化合物
の鎖中であっても又は末端であってもよく、鎖に直接連
結されていても又は任意の原子団を介して間接連結され
ていてもよい、またセグメントを構成する液状ゴム系化
合物は、ラジカル重合、イオン重合、リビング重合等に
よって得られるもの或いはそれらを部分的に又は完全に
氷菓添加したものであって、その重合方法の相違による
立体異性や構造異性を問題とするものではない。In the present invention, a liquid rubber compound having one or more hydroxyl groups in the molecule is used as a starting material, and ε-aliphatic lactone is sequentially subjected to ring-opening polymerization to form a catalyst. By forming polyester chains,
Although it is industrially advantageous to stably obtain a block copolymer, the hydroxyl group present in the liquid rubber compound may be in the chain or at the end of the compound, or may be directly connected to the chain. The liquid rubber compounds constituting the segments may be obtained by radical polymerization, ionic polymerization, living polymerization, etc., or they may be partially or indirectly connected through arbitrary atomic groups. Since it is completely added to ice cream, there are no problems with stereoisomerism or structural isomerism due to differences in the polymerization method.
液状ゴム系化合物を構成することとなる単量体ジエン化
合物は、ブタジェン、イソプレン、クロロブレン、１，
３−ペンタジェン等であるが、本発明で有利に使用でき
る液状ゴム系化合物を例示すると、α、ω−１．２−ポ
リブタジェングリコール（Ｎｆｓｓｏ ＰＢ−Ｇシリ
ーズ）、水素添加α、ω−１．２−ポリブタジェングリ
コール（Ｎｉｓｓｏ ＰＢ−ＧＩシリーズ、以上２点
は日本曹達社製）、末端水酸基変性１．４−ポリブタジ
ｘン（Ｐｏ ｌ ｙ−ｂｄ Ｒ−４５Ｍ又はＲ−４５
ＨＴ、出光石油化学社製又はアーコケミカル社製）等が
挙げられる。上記のような、水酸基が直接炭化水素鎖に
付いた液状ゴム系化合物以外のものでは、カルボキシ変
性液状ゴム系化合物のカルボキシル基にフルキレンオキ
サイドを付加させてヒドロキシアルキルエステル化した
もの、エポキシ変性液状ゴム系化合物のエポキシ基に水
又はアルコール又は１価の有ａ酸を反応させてエポキシ
基を開環させたもの等も供試できる。The monomeric diene compounds that will constitute the liquid rubber compound include butadiene, isoprene, chlorobrene, 1,
Examples of liquid rubber compounds that can be advantageously used in the present invention include α,ω-1,2-polybutadiene glycol (Nfsso PB-G series), hydrogenated α,ω-1, etc. .2-polybutadiene glycol (Nisso PB-GI series, the above two items are manufactured by Nippon Soda Co., Ltd.), terminal hydroxyl group-modified 1,4-polybutadiene glycol (Poly-bd R-45M or R-45)
HT, manufactured by Idemitsu Petrochemical Co., Ltd. or Arco Chemical Co., Ltd.), and the like. In addition to the above-mentioned liquid rubber compounds in which a hydroxyl group is directly attached to a hydrocarbon chain, there are compounds obtained by adding fullkylene oxide to the carboxyl group of a carboxy-modified liquid rubber compound to form a hydroxyalkyl ester, and epoxy-modified liquid rubber compounds. Rubber-based compounds whose epoxy groups are reacted with water, alcohol, or monovalent alpha acid to open the epoxy groups can also be used.
また前記反応において、ε−脂肪族ラクトンとしては、
（−カプロラクトンが代表例として挙げられる。In the above reaction, the ε-aliphatic lactone is
(-Caprolactone is a typical example.
そして、ε−脂肪族ラクトンを液状ゴム系化合物の官能
基として存在する水酸基に対し逐次開環重合させるのに
用いられる触媒としては、「講座重合反応部７巻開環重
合（ＩＩ）Ｊ（化学同人発行、１０８頁）に記載されて
いるような、アニオン重合触媒、配位アニオン重合触媒
、カチオン重合触媒等が利用できる。特に、テトラブチ
ルチタネート、テトラプロピルチタネート、テトラエチ
ルチタネート等のチタン系触媒や、ジブチル錫オキシド
、オクチル酸錫、塩化第−錫等の錫系触媒が有利である
。Catalysts used for sequential ring-opening polymerization of ε-aliphatic lactones to hydroxyl groups present as functional groups in liquid rubber compounds are listed in "Course Polymerization Reaction Section Vol. 7 Ring-Opening Polymerization (II) J (Chemistry Anionic polymerization catalysts, coordination anionic polymerization catalysts, cationic polymerization catalysts, etc., such as those described in Dojin Publishing, p. , dibutyltin oxide, tin octylate, tin-based catalysts are preferred.
いうまでもなく、以上例示したいずれについても、本発
明がそれらに限定されるというものではない。Needless to say, the present invention is not limited to any of the examples given above.
かくして得られる本発明のブロック共重合体中のポリエ
ステル鎖の末端基は１通常、水酸基となるが、該末端基
と反応性のある物質を反応させ、エーテル結合やエステ
ル結合等の連結基を介して各種の反応性基１例えばビニ
ル基、エポキシ基、イソシアネート基等を付加し、末端
変性を行なうことができ、また末端の水酸基に対し、ジ
カルボン酸、二価以上の多塩基酸又はそれらの酸無水物
を反応させて末端カルボキシル変性をすることもできる
。更に末端基としての水酸基又はカルボキシル基を、エ
ーテル結合、エステル結合又はアミド結合等を介して封
鎖し、非反応性の末端変性を行なうこともでき、末端の
カルボキシル基の反応性を不活性化する目的で、該カル
ボキシル基をアルカリ金属塩やアルカリ土類金属塩等の
塩に変性することもできる。The terminal group of the polyester chain in the block copolymer of the present invention thus obtained is usually a hydroxyl group, but by reacting the terminal group with a reactive substance, it is possible to form a hydroxyl group through a linking group such as an ether bond or an ester bond. Terminal modification can be carried out by adding various reactive groups 1, such as vinyl groups, epoxy groups, isocyanate groups, etc., and the terminal hydroxyl group can be modified with dicarboxylic acids, divalent or higher polybasic acids, or their acids. Terminal carboxyl modification can also be carried out by reacting with an anhydride. Furthermore, a hydroxyl group or a carboxyl group as a terminal group can be blocked via an ether bond, an ester bond, an amide bond, etc. to perform non-reactive terminal modification, thereby inactivating the reactivity of the terminal carboxyl group. For this purpose, the carboxyl group can also be modified into a salt such as an alkali metal salt or an alkaline earth metal salt.
本発明のブロック共重合体の物性を支配する重要な技術
的要因の一つは、該ブロック共重合体中の液状ゴム系化
合物セグメントの分子量に対するポリエステル系ポリマ
ーセグメントの分子量の比率である。これは１本発明の
ブロック共重合体が固有することとなるゴム系物質及び
ポリエステル系ポリマーに対する両親媒特性を左右する
最も重要な技術的事項の一つでもある。液状ゴム系化合
物セグメント部分の分子量に対してポリエステル系ポリ
マーセグメント部分の分子量の比率が相対的に低い場合
、そのブロック共重合体はポリエステル系ポリマーに対
する親和性が相対的に小さく、該比率を上げることによ
ってポリエステル系ポリマーに対する親和性を相対的に
大きくすることができる。本発明のブロック共重合体が
両親媒特性を示す範囲は、該ブロック共重合体に占める
液状ゴム系化合物セグメント部分の割合が９５〜５重量
％の場合である。いずれにしても、上記のような見地か
ら、本発明のブロック共重合体は、そのポリエステル系
ポリマーセグメントを構成するポリエステル鎖の鎖長を
所望通りに選択することができるのである。One of the important technical factors governing the physical properties of the block copolymer of the present invention is the ratio of the molecular weight of the polyester polymer segment to the molecular weight of the liquid rubber compound segment in the block copolymer. This is one of the most important technical matters that influences the amphiphilic properties of the block copolymer of the present invention for rubber materials and polyester polymers. If the ratio of the molecular weight of the polyester polymer segment to the molecular weight of the liquid rubber compound segment is relatively low, the block copolymer has a relatively low affinity for the polyester polymer, and the ratio should be increased. This allows the affinity for polyester polymers to be relatively increased. The range in which the block copolymer of the present invention exhibits amphiphilic properties is when the proportion of the liquid rubber compound segment portion in the block copolymer is 95 to 5% by weight. In any case, from the above viewpoint, in the block copolymer of the present invention, the chain length of the polyester chain constituting the polyester polymer segment can be selected as desired.
本発明のブロック共重合体の物性を支配する重要な技術
的要因の他の一つは、該ブロック共重合体中の液状ゴム
系化合物セグメント及びポリエステル系ポリマーセグメ
ントを構成する各ポリマーの構造及び組成である。ブロ
ック共重合体の物性はこれを構成する個々のセグメント
の物性によって必然大きく影響され、個々のセグメント
の物性は該セグメントを構成することとなる七ツマ−の
特性によって支配される。それ故、各セグメントの物性
、例えば融点、軟化点、ガラス転位点等のポリマー固有
の物性、ひいては本発明のブロック共重合体の物性は、
各セグメントのポリマー重合に使用する七ツマ−の種類
やそれ以外に含まれることがある他の化合物によって適
宜に変えるとかできるのである。Another important technical factor governing the physical properties of the block copolymer of the present invention is the structure and composition of each polymer constituting the liquid rubber compound segment and polyester polymer segment in the block copolymer. It is. The physical properties of a block copolymer are inevitably greatly influenced by the physical properties of the individual segments that make up the block copolymer, and the physical properties of the individual segments are controlled by the properties of the heptamers that make up the segment. Therefore, the physical properties of each segment, such as melting point, softening point, glass transition point, etc., and the physical properties of the block copolymer of the present invention are as follows:
It can be changed as appropriate depending on the type of heptamer used in the polymerization of each segment and other compounds that may be included.
以下、本発明をより具体的にするため、実施例及び評価
例を挙げるが、本発明はこれらの実施例に限定されるも
のではない、これらの例示を含めて、以上説明した本発
明に基く枝質思想内の変更や修正は本発明に包含される
ものである。Examples and evaluation examples will be given below to make the present invention more specific, but the present invention is not limited to these examples. Changes and modifications within the underlying concept are included in the present invention.
〈実施例等〉
・実施例１
水素添加α、ω−１．２−ポリブタジェングリコール（
Ｎｉｓｓｏ ＰＢ−ＧＩｌｏｏＯ，平均分子１１４０
０、日本曹達社製）７００ｇ （０。<Examples, etc.> ・Example 1 Hydrogenated α, ω-1.2-polybutadiene glycol (
Nisso PB-GIlooO, average molecule 1140
0, manufactured by Nippon Soda Co., Ltd.) 700g (0.
５モル）、触媒としてテトラブチルチタネート。5 mol), tetrabutyl titanate as catalyst.
・７ｇ、及びε−カプロラクトン３００ｇ（２゜６３モ
ル）を反応缶に仕込み、窒素ガス雰囲気下、１５０℃で
３時間反応させ、淡黄色透明粘液状の生成物９９７ｇを
得た。・7 g and 300 g (2°63 mol) of ε-caprolactone were placed in a reaction vessel and reacted at 150° C. for 3 hours in a nitrogen gas atmosphere to obtain 997 g of a pale yellow transparent viscous product.
ここで得られた水添ポリブタジェン−ポリエステルブロ
ック共重合体の分子量は２０００ （計算値、以下分子
量は計算値）、ポリカプロラクトンからなるポリエステ
ルセグメントの比率は３０゜０１敬％（以下％は重量％
）、酸価０．３、水酸基価５４．６であった。The molecular weight of the hydrogenated polybutadiene-polyester block copolymer obtained here is 2000 (calculated value, hereinafter the molecular weight is a calculated value), and the ratio of polyester segments consisting of polycaprolactone is 30°01% (hereinafter % is weight %).
), acid value 0.3, and hydroxyl value 54.6.
・実施例２
実施例１で得られたブロック共重合体８００ｇ（０，４
モル）及び無水コハク酸８０ｇ（０，８モル）をフラス
コに仕込み、１２０〜１２５℃の温度下、窒素気流中に
て、２時間反応させた。内容物を５０℃に冷却後、スチ
レンモノマー２２０ｇを加えて、ブロック共重合体８０
ｆｉｌ１％を含むスチレン溶液を調整した。・Example 2 800 g of the block copolymer obtained in Example 1 (0,4
mol) and 80 g (0.8 mol) of succinic anhydride were charged into a flask and reacted for 2 hours in a nitrogen stream at a temperature of 120 to 125°C. After cooling the contents to 50°C, 220g of styrene monomer was added, and 80g of block copolymer was added.
A styrene solution containing 1% fil was prepared.
このブロック共重合体を含むスチレン溶液の酸価５０．
２、水酸基価１．２であり、ポリエステル鎖の末端がカ
ルボキシル変性された水添ポリブタジェン−ポリエステ
ルブロック共重合体が得られた。The acid value of the styrene solution containing this block copolymer is 50.
2. A hydrogenated polybutadiene-polyester block copolymer having a hydroxyl value of 1.2 and having carboxyl-modified ends of the polyester chain was obtained.
・実施例３
α、ω−１．２−ポリブタジェンジヵルポン酸（Ｎｉｓ
ｓｏ ＰＢ−Ｃ１００Ｏ５平均分子呈１５２０、日本
曹達社製）７６０ｇ （０，５モル）及び塩化リチウム
１．５ｇをオートクレーブに仕込み、窒素ガスで反応系
内を置換後、攪拌しながら１３０℃まで加熱した０次い
で、エチレンオキサイド４８ 、４ｇ （１、１モル）
を３０分間かけて１３５〜１４５℃の温度下で圧入した
。この温度で２時間熟成を行ない、反応を完結させ、α
。・Example 3 α, ω-1,2-polybutadiene dicarboxylic acid (Nis
So PB-C100O5 average molecular weight 1520, manufactured by Nippon Soda Co., Ltd.) 760 g (0.5 mol) and 1.5 g of lithium chloride were placed in an autoclave, and after purging the reaction system with nitrogen gas, it was heated to 130 ° C. with stirring. 0 then ethylene oxide 48,4g (1,1 mol)
was press-fitted over a period of 30 minutes at a temperature of 135 to 145°C. Aging is performed at this temperature for 2 hours to complete the reaction, and α
.
ω−１，２−ポリブタジェンジカルポン酸ジヒドロキシ
エチルエステル８０５ｇを得た。そして、触媒としてテ
トラブチルチタネート０．５ｇ、及びε−カプロラクト
ン７９８ｇＣ７モル）を仕込み、１４５〜１５０℃の温
度下、窒素気流中にて４時間反応させ、淡黄色透明粘液
状の生成物１６００ｇを得た。805 g of ω-1,2-polybutadiene dicarboxylic acid dihydroxyethyl ester was obtained. Then, 0.5 g of tetrabutyl titanate and 798 g (C7 mol) of ε-caprolactone were added as catalysts, and the reaction was carried out for 4 hours in a nitrogen stream at a temperature of 145 to 150°C to obtain 1600 g of a pale yellow transparent viscous product. Ta.
ここで得られたポリブタジェンーポリエステルブロック
共重合体は１分子ｆｉ３２０４、ポリエステルセグメン
ト部の比率５２．６％、酸価１．２、同水酸基価３４．
７であった。The polybutadiene-polyester block copolymer obtained here had a molecular fi of 3204, a polyester segment ratio of 52.6%, an acid value of 1.2, and a hydroxyl value of 34.
It was 7.
・比較例１
α、ω−１．２−ポリブタジェンジカルボン酸（実施例
３に記載のもの）７６０ｇ （０，５モル）、ポリカプ
ロラクトン（Ｐｌａｃｃｅｌ ２０５、平均分子量５
５０、水酸基価２３０〜２４０、酸価ｌ以下、ダイセル
社製）５５０ｇ （１モル）、キシレン５００１及び触
媒としてパラトルエンスルホン酸６．５ｇをフラスコに
仕込み１、キシレン環流下にエステル化反応を行なった
。３時間反応させた時点での留出水は７１（理論留出水
１８１）であり、更に１時間反応を続けたところ、反応
による留出水の増加は殆ど認められず、反応内容物が暗
褐色に若色していた。この時点で反応を停止し、パラト
ルエンスルホン酸を炭酸ナトリウム溶液で中和した後、
減圧下にキシレンを留去して生成物を得た。Comparative Example 1 α,ω-1.2-polybutadiene dicarboxylic acid (described in Example 3) 760 g (0.5 mol), polycaprolactone (Placcel 205, average molecular weight 5
50, hydroxyl value 230-240, acid value 1 or less, manufactured by Daicel) 550 g (1 mol), xylene 5001, and 6.5 g of para-toluenesulfonic acid as a catalyst were placed in a flask 1, and an esterification reaction was carried out under xylene reflux. Ta. The amount of distilled water after 3 hours of reaction was 71 (theoretical distilled water: 181), and when the reaction was continued for another 1 hour, almost no increase in distilled water due to the reaction was observed, and the reaction contents became dark. It was brown and young. After stopping the reaction at this point and neutralizing the para-toluenesulfonic acid with sodium carbonate solution,
Xylene was distilled off under reduced pressure to obtain a product.
ここで得られた生成物は著しく懸濁しており。The product obtained here is highly suspended.
静置１時間後には、二層に成層分離し、上層部は未反応
のα、ω−１，２−ポリブタジエンジカルポン酸を主成
分とする混合物が約４２０ｇを占めた。残りの下層部を
ポリブタジェン変性ポリエステルとして後述の評価に供
した。After one hour of standing, the mixture was separated into two layers, and the upper layer contained about 420 g of a mixture containing unreacted α,ω-1,2-polybutadiene dicarboxylic acid as a main component. The remaining lower layer portion was used as a polybutadiene-modified polyester and was subjected to the evaluation described below.
・評価例１
実施例１、同２、同３で得られた３ｇのブロック共重合
体の３３％スチレン溶液を調整し、各溶液について、以
下の熱硬化性不飽和ポリエステル樹脂との相溶性乃至分
散性を試験した。用いた熱硬化性不飽和ポリエステル樹
脂はユビカ７５０７（日本ユピカ社製）、ポリセラ）９
１２０、ポリセット９ＬＯ７、ポリセット２２１２、ポ
リセット６２００ （以上４点は日立化成社製）の５種
である。ポリセット９１０７と組合わせた場合について
結果を第１表に示すが、本発明のブロック共重合体の場
合、他の組合わせはいずれも、増粘剤なしでも、相分離
は認められなかった。尚、比較のため、他のポリジエン
誘導体等について同様の試験を行ない、結果を第１表に
併記した。・Evaluation Example 1 A 33% styrene solution of 3 g of the block copolymer obtained in Examples 1, 2, and 3 was prepared, and each solution was evaluated for compatibility with the following thermosetting unsaturated polyester resin. Dispersibility was tested. The thermosetting unsaturated polyester resin used was Yubica 7507 (manufactured by Nippon Upica Co., Ltd., Polycera) 9
There are five types: Polyset 120, Polyset 9LO7, Polyset 2212, and Polyset 6200 (the above four items are manufactured by Hitachi Chemical). The results are shown in Table 1 for the combination with Polyset 9107, but in the case of the block copolymer of the present invention, no phase separation was observed in any of the other combinations even without a thickener. For comparison, similar tests were conducted on other polydiene derivatives, and the results are also listed in Table 1.
第１表
注）ＰＢＧ：α、ω−１．２−ポリブタジェングリコー
ル（Ｎｉｓｓｏ ＰＨ−ＧｌｏｏＯｌ日本曹達社製）
ＳＢＳ ：スチレンーブタジェンースチレンブロック共
重合体（カリフレックスＴＲｌＩＯ２、シェル化学社製
）
ＰＥＳ：比較例１で得たもの
ＳＥＳ：ポリエステルを末端変性したものにスチレンモ
／−Ｆ −ヲ懸濁重合したスチレン系ポリマーのブロッ
ク共重合体（特開昭６０−９９１５８の実施例１で提案
のもの）水添ＬＧＰ：水素添加α、ω−１，２−ポリブ
タジェングリコール（実施例１に記載のもの）
評価：Ｏ＝安定な分散状態で分離が認められない
Δ＝わずかに分離が認められる
×＝分離層が明らかに認められる
評価方法（相溶性乃至分散性試験）：熱硬化性不飽和ポ
リエステル樹脂（固形分６０％のスチレン溶液）８０部
と、第１表記載の添加剤（添加剤３３％のスチレン溶液
）４０部をビーカーにとり、プロペラ攪拌機にて５分間
均一に混合攪拌し、ＩＯＬ）ｍｌメスシリンダーに移し
て室温静置した。Table 1 Note) PBG: α, ω-1.2-polybutadiene glycol (Nisso PH-GlooOl manufactured by Nippon Soda Co., Ltd.) SBS: Styrene-butadiene-styrene block copolymer (Califlex TRlIO2, manufactured by Shell Chemical Co., Ltd.) ) PES: Obtained in Comparative Example 1 SES: Block copolymer of styrenic polymer obtained by suspension polymerizing styrene mo/-F- into terminally modified polyester (proposed in Example 1 of JP-A No. 60-99158) Hydrogenated LGP: Hydrogenated α,ω-1,2-polybutadiene glycol (as described in Example 1) Evaluation: O = stable dispersion with no separation Δ = slight separation Recognized × = Separated layer is clearly recognized Evaluation method (compatibility or dispersibility test): 80 parts of thermosetting unsaturated polyester resin (styrene solution with solid content of 60%) and the additives listed in Table 1 ( 40 parts of a 33% styrene solution (additive 33%) was placed in a beaker, mixed and stirred uniformly for 5 minutes using a propeller stirrer, and then transferred to an IOL (ml) graduated cylinder and allowed to stand at room temperature.
・評価例２
実施例２のブロック共重合体についてその３３％スチレ
ン溶液４０部に対し、ユビカ７５０７を６０部、ターシ
ャリ−ブチルパーベンゾエート１．５部及びステアリン
酸亜鉛３．０部の液をバンバリーミキサ−中に用意し、
それに２００部の炭酸カルシウム粉末を加え、よく均一
にした後、ｌ／２インチ長のガラス繊維６０部を添加し
て、１分後にバンバリーミキサ−を停止し、プレミック
スを作った。これを型温１４５℃で成形したところ、均
一な表面光沢を呈する成形物が得られ、その成形収縮率
は０．００３％であった。 これに対し、ブロック共重
合体に代えて水素添加α、ω−１，２−ポリブタジェン
グリコール（実施例１に記載のもの）を用いること以外
は全て同一条件で作られたプレミックスの場合、その成
形物の表面は光沢斑が著しく、見るに耐えないものであ
った。-Evaluation Example 2 Regarding the block copolymer of Example 2, a solution of 60 parts of Yuvika 7507, 1.5 parts of tertiary-butyl perbenzoate, and 3.0 parts of zinc stearate was added to 40 parts of the 33% styrene solution. Prepare in a mixer,
After adding 200 parts of calcium carbonate powder and making it well homogeneous, 60 parts of 1/2 inch long glass fibers were added and after 1 minute the Banbury mixer was stopped to make a premix. When this was molded at a mold temperature of 145° C., a molded product with uniform surface gloss was obtained, and its molding shrinkage rate was 0.003%. In contrast, in the case of a premix made under all the same conditions except that hydrogenated α,ω-1,2-polybutadiene glycol (as described in Example 1) was used instead of the block copolymer. The surface of the molded product had significant glossy spots and was unwatchable.
・評価例３
実施例２で得られたブロック共重合体の３３％スチレン
溶液を調整し、この溶液４０部に、ポリセラ）９１２０
を６０部、ステアリン酸亜鉛３部、ターシャリ−ブチル
パーベンゾエート１ 、５ｆｉｆ！、炭酸カルシウム粉
末１４０部及びバラベンゾキノン０．３部を均一混合し
、次いで醸化マグネシウム２部を加え、直ちに１インチ
長のガラス繊維１０％を含むＳＭＣ用組成物を作った。-Evaluation Example 3 A 33% styrene solution of the block copolymer obtained in Example 2 was prepared, and 40 parts of this solution was added with Polycera) 9120.
60 parts of zinc stearate, 1 part of tertiary-butyl perbenzoate, 5fif! , 140 parts of calcium carbonate powder and 0.3 parts of rose benzoquinone were uniformly mixed, and then 2 parts of fermented magnesium was added to immediately prepare a composition for SMC containing 10% of 1 inch long glass fiber.
これを型温１４０℃で成形したところ、成形物の表面に
わずかな曇りはあるが、光沢具合は均一であり、成形収
縮率は０．０４％であった。When this was molded at a mold temperature of 140° C., the surface of the molded product was slightly cloudy, but the gloss was uniform and the molding shrinkage rate was 0.04%.
これに対し、ブロック共重合体に代えて水素添加α、ω
−１．２−ポリブタジェングリコール（実施例１に記載
のもの）を用いること以外は全て同一条件で作られたＳ
ＭＣ用組成物の場合、その成形物の表面は光沢斑が著し
く、流れ模様も認められ、成形収縮率は−０，２５％で
あった。また、この場合は酸化マグネシウム添加前のド
ープの安定性も悪く、明らかに相分離し、この面からも
工業的操作の至難が明白であった。On the other hand, instead of using block copolymers, hydrogenated α, ω
-1.S made under all the same conditions except using 2-polybutadiene glycol (as described in Example 1)
In the case of the MC composition, the surface of the molded product had significant gloss spots and flow patterns, and the molding shrinkage rate was -0.25%. In addition, in this case, the stability of the dope before addition of magnesium oxide was poor, and phase separation clearly occurred, which also made it clear that industrial operation was extremely difficult.
尚、各側において１部及び％はいずれも重量表示である
。In addition, both 1 part and % on each side are expressed by weight.
〈発明の効果〉
各実施例及び評価例からも明らかなように、以上説明し
た本発明には、充分な相溶乃至分散安定性を持ち、成形
作業性がよく、その成形物に表面特性や低収縮性等の面
で優れた物性改良を施すブロック共重合体を工業上有利
に製造することができる効果がある。<Effects of the Invention> As is clear from the examples and evaluation examples, the present invention described above has sufficient compatibility and dispersion stability, good molding workability, and the molded product has good surface properties and This has the effect of making it possible to industrially advantageously produce a block copolymer with excellent physical property improvements such as low shrinkage.
Claims (1)
ム系化合物にε−脂肪族ラクトンを触媒存在下に反応さ
せることを特徴とする液状ゴム系−ポリエステル系ブロ
ック共重合体の製造方法。 ２、液状ゴム系化合物がポリブタジエン系化合物若しく
は部分的に又は完全に水素添加がされたポリブタジエン
系化合物である特許請求の範囲第１項記載のブロック共
重合体の製造方法。 ３、液状ゴム系化合物がポリイソプレン系化合物若しく
は部分的に又は完全に水素添加がされたポリイソプレン
系化合物である特許請求の範囲第１項記載のブロック共
重合体の製造方法。 ４、ε−脂肪族ラクトンがε−カプロラクトンである特
許請求の範囲第１項〜第３項のいずれか一つの項記載の
ブロック共重合体の製造方法。[Claims] 1. A liquid rubber-polyester block characterized by reacting a liquid rubber compound having one or more hydroxyl groups in the molecule with an ε-aliphatic lactone in the presence of a catalyst. Method for producing copolymer. 2. The method for producing a block copolymer according to claim 1, wherein the liquid rubber compound is a polybutadiene compound or a partially or completely hydrogenated polybutadiene compound. 3. The method for producing a block copolymer according to claim 1, wherein the liquid rubber compound is a polyisoprene compound or a partially or completely hydrogenated polyisoprene compound. 4. The method for producing a block copolymer according to any one of claims 1 to 3, wherein the ε-aliphatic lactone is ε-caprolactone.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61263261A JPS63117028A (en) | 1986-11-05 | 1986-11-05 | Production of block copolymer |
| KR1019870004928A KR900000163B1 (en) | 1986-11-05 | 1987-05-19 | Preparation of block copolymer |
| AU73229/87A AU7322987A (en) | 1986-11-05 | 1987-05-20 | Liquid rubber - polyester block copolymer |
| CA000540915A CA1320606C (en) | 1986-11-05 | 1987-06-30 | Method of producing block copolymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61263261A JPS63117028A (en) | 1986-11-05 | 1986-11-05 | Production of block copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63117028A true JPS63117028A (en) | 1988-05-21 |
Family
ID=17387008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61263261A Pending JPS63117028A (en) | 1986-11-05 | 1986-11-05 | Production of block copolymer |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS63117028A (en) |
| KR (1) | KR900000163B1 (en) |
| AU (1) | AU7322987A (en) |
| CA (1) | CA1320606C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019534368A (en) * | 2016-11-22 | 2019-11-28 | スリーエム イノベイティブ プロパティズ カンパニー | Pentablock copolymer |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU638908B2 (en) * | 1986-02-21 | 1993-07-08 | Takemoto Yushi Kabushiki Kaisha | Additives for synthetic resins |
| CN105637011B (en) | 2013-10-24 | 2019-08-06 | 日本曹达株式会社 | Glycol composition |
-
1986
- 1986-11-05 JP JP61263261A patent/JPS63117028A/en active Pending
-
1987
- 1987-05-19 KR KR1019870004928A patent/KR900000163B1/en not_active IP Right Cessation
- 1987-05-20 AU AU73229/87A patent/AU7322987A/en not_active Abandoned
- 1987-06-30 CA CA000540915A patent/CA1320606C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019534368A (en) * | 2016-11-22 | 2019-11-28 | スリーエム イノベイティブ プロパティズ カンパニー | Pentablock copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| KR900000163B1 (en) | 1990-01-23 |
| KR880006281A (en) | 1988-07-22 |
| CA1320606C (en) | 1993-07-20 |
| AU7322987A (en) | 1988-05-12 |
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