JPH02185505A - Purification of modified polyolefin - Google Patents
Purification of modified polyolefinInfo
- Publication number
- JPH02185505A JPH02185505A JP447189A JP447189A JPH02185505A JP H02185505 A JPH02185505 A JP H02185505A JP 447189 A JP447189 A JP 447189A JP 447189 A JP447189 A JP 447189A JP H02185505 A JPH02185505 A JP H02185505A
- Authority
- JP
- Japan
- Prior art keywords
- maleic anhydride
- modified polyolefin
- solvent
- modified
- polyolefin
- 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
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 64
- 238000000746 purification Methods 0.000 title description 23
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 30
- 239000008188 pellet Substances 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- -1 polyethylene terephthalate Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 238000001226 reprecipitation Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（１）産業上の利用分野
本発明は、金属またはポリアミド、ポリエチレンテレフ
タレート、エチレン−酢酸ビニル共重合体ケン化物、ポ
リプロピレン、ポリスチレン等のプラスチックとの接着
性が良好な変性ポリオレフィンの精製方法に関する。本
発明の精製方法を用いたポリオレフィンは多層積層体の
優れた接着性材料となり、かつ未反応無水マレイン酸及
び反応副生物が存在しないため衛生性も優れたものであ
る。DETAILED DESCRIPTION OF THE INVENTION (1) Industrial Application Field The present invention is directed to a modified material having good adhesion to metals or plastics such as polyamide, polyethylene terephthalate, saponified ethylene-vinyl acetate copolymer, polypropylene, and polystyrene. The present invention relates to a polyolefin purification method. The polyolefin obtained using the purification method of the present invention becomes an excellent adhesive material for multilayer laminates, and also has excellent hygiene properties since unreacted maleic anhydride and reaction by-products are not present.
（２）従来の技術
無水マレイン酸グラフトポリオレフィンの製法は溶液法
、溶融法等が知られている。その内ポリオレフィン、無
水マレイン酸及びラジカル開始剤の混合物を押出機を用
いて溶融混練りしてグラフト重合する溶融法は広く工業
的に用いられている。(2) Prior Art Methods for producing maleic anhydride grafted polyolefins include a solution method and a melt method. Among them, a melt method in which a mixture of polyolefin, maleic anhydride, and a radical initiator is melt-kneaded using an extruder and graft polymerized is widely used industrially.
これらの無水マレイン酸グラフトポリオレフィン中に存
在する未反応の無水マレイン酸、反応副生物を除去する
方法としては、
■溶液グラフト重合後、重合溶液を冷却し、常温におい
てアセトンを用いて再沈澱処理を行い、さらに繰り返し
アセトンにより未反応無水マレイン酸を洗浄する方法（
特公昭５２−３２６５４号。The method for removing unreacted maleic anhydride and reaction by-products present in these maleic anhydride grafted polyolefins is as follows: - After solution graft polymerization, the polymerization solution is cooled and reprecipitation treatment is performed using acetone at room temperature. A method of repeatedly washing unreacted maleic anhydride with acetone (
Special Publication No. 52-32654.
特公昭４４−１５４２２号）、
■無水マレイン酸グラフトポリオレフィンに加圧水蒸気
を吹き付けて洗浄し、未反応無水マレイン酸を除去する
方法、
■無水マレイン酸グラフトポリオレフィンを溶解したの
ちエマルジョン状態をつくり水洗により未反応無水マレ
イン酸を除去する方法（特開昭６１−２６６４１１号）
、
■ポリオレフィンおよび未反応無水マレイン酸の良溶媒
である芳香族溶媒を使用して除去する方法（特開昭５４
．−９９１９３号）党が公知である。(Japanese Patent Publication No. 44-15422), ■ A method in which maleic anhydride-grafted polyolefin is sprayed with pressurized steam and washed to remove unreacted maleic anhydride, ■ After dissolving the maleic anhydride-grafted polyolefin, an emulsion is created and the unreacted maleic anhydride is removed by washing with water. Method for removing reacted maleic anhydride (JP-A-61-266411)
, ■ A method for removing polyolefins and unreacted maleic anhydride using an aromatic solvent that is a good solvent (Japanese Patent Application Laid-Open No. 1989-1999)
．． -99193) Party is known.
上記■、■はすべでグラフト重合時もしくは精製工程時
に溶媒に溶解させるため精製工程が高価となる欠点を有
している。■はグラフト変性樹脂の粒子径が大きい場合
は除去効率が充分でない。All of the above methods (1) and (2) have the disadvantage that the purification process is expensive because they are dissolved in a solvent during the graft polymerization or purification process. Regarding (2), if the particle size of the graft-modified resin is large, the removal efficiency is not sufficient.
また、グラフトされた無水マレイン酸基が開環する欠点
を有する。■は実質的にポリオレフィンを溶解させず未
反応無水マレイン酸等を除去するものの本質的にポリオ
レフィンの良溶媒であるために精製工程の温度制御が不
十分であるとポリオレフィンの溶解が生じる欠点を有す
る。It also has the disadvantage that the grafted maleic anhydride group opens the ring. (2) removes unreacted maleic anhydride without substantially dissolving the polyolefin, but since it is essentially a good solvent for polyolefin, it has the disadvantage that polyolefin may dissolve if the temperature control in the purification process is insufficient. .
（３）発明が解決しようとする課題
本発明は上記従来技術の欠点を克服し、無水マレイン酸
変性ポリオレフィン中に存在し、製品の性能を悪化させ
る未反応無水マレイン酸および反応副生成物を効率よく
また経済的に精製除去する方法を提供しようとするもの
である。(3) Problems to be Solved by the Invention The present invention overcomes the above-mentioned drawbacks of the prior art and efficiently removes unreacted maleic anhydride and reaction by-products that are present in maleic anhydride-modified polyolefins and deteriorate the performance of the product. The aim is to provide an efficient and economical method for purification and removal.
（４）課題を解決するための手段
本発明者らは鋭意研究の結果以下を骨子とする方法によ
り上記課題を解決できる事を発見し本発明に到達した。(4) Means for Solving the Problems As a result of intensive research, the present inventors discovered that the above problems could be solved by a method based on the following points, and arrived at the present invention.
すなわち、溶融状態で無水マレイン酸を用いてグラフト
変性をした変性ポリオレフィンを精製するにあたり、炭
素数が多くとも６であるカルボニル基を有する溶媒を使
用しくＴｍ ｐ −１，１Ｎｚ４） ℃ないしく０．７
ｘＴｍＰ ０．８１’Ｊ２．４）℃（ただしＴ ｍ
ｐは該ポリオレフィンの融解ピーク温度（℃）、Ｎは該
溶媒の炭素数を表す）の温度範囲で未反応無水マレイン
酸及び反応副生物を該ポリオレフィンから除去すること
を特徴とする変性ポリオレフィンの精製方法であり、と
くに精製すべき変性ポリオレフィンがペレット状である
ときに有効である変性ポリオレフィンの精製方法である
。That is, when purifying a modified polyolefin that has been graft-modified using maleic anhydride in a molten state, a solvent having a carbonyl group having at most 6 carbon atoms should be used. 7
xTmP 0.81'J2.4)℃ (However, T m
Purification of a modified polyolefin, characterized in that unreacted maleic anhydride and reaction by-products are removed from the polyolefin in a temperature range in which p represents the melting peak temperature (°C) of the polyolefin and N represents the number of carbon atoms in the solvent. This method is particularly effective when the modified polyolefin to be purified is in the form of pellets.
本発明において用いられるポリオレフィンとしては、エ
チレン、プロピレン、 １−ブテン、 ］ヘキセン、３
−メチル−１−ペンテン等のオレフィンの単独重合体ま
たはこれらのオレフィンの２種以上とのランダムないし
ブロック共重合体もしくは、これらオレフィンを主成分
とし、これと酢酸ビニル、アクリル酸、メタクリル酸、
アクリル酸エステル、メタクリル酸エステル等との共重
合体である。具体的には、高密度ポリエチレン、低密度
ポリエチレン、線状低密度ポリエチレン、ポリプロピレ
ン、エチレン−プロピレンランダム共重合体、エチレン
−酢酸ビニル共重合体、エチレン−ブテン−１共重合体
、プロピレン−ブテン−１共重合体、エチレン−アクリ
ル酸エステル共重合体、エチレン−メタクリル酸共重合
体の亜鉛塩等である。これらは、単独もしくは２種以上
混合して用いてもよい。溶融状態での無水マレイン酸を
ポリオレフィンにグラフト変性する方法は通常知られて
いる方法を用いることができる。たとえば、ポリオレフ
ィン、無水マレイン酸及びラジカル開始剤の混合物を押
出機を用いて溶融混練りしてグラフト重合する方法（特
公昭５５−１２６４５０）を利用することができる。The polyolefins used in the present invention include ethylene, propylene, 1-butene, ]hexene, 3
- A homopolymer of olefins such as methyl-1-pentene, or a random or block copolymer with two or more of these olefins, or a mixture containing these olefins as the main component and vinyl acetate, acrylic acid, methacrylic acid,
It is a copolymer with acrylic ester, methacrylic ester, etc. Specifically, high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-vinyl acetate copolymer, ethylene-butene-1 copolymer, propylene-butene-1 1 copolymer, ethylene-acrylic acid ester copolymer, zinc salt of ethylene-methacrylic acid copolymer, and the like. These may be used alone or in combination of two or more. A commonly known method can be used to graft-modify maleic anhydride in a molten state onto a polyolefin. For example, a method may be used in which a mixture of polyolefin, maleic anhydride, and a radical initiator is melt-kneaded using an extruder and graft polymerized (Japanese Patent Publication No. 126450/1983).
溶媒は炭素数が多くとも６であるカルボニル基を有する
溶媒を使用しく Ｔ ｍ ｐ −０，８Ｎ２．４） ℃
ないしく０．７’ｘＴｍｐ’−０．８Ｎ２．４）℃の温
度範囲で未反応無水マレイン酸及び反応副生物を゛該ポ
リオレフィンから除去する。該温度範囲を逸股すると変
性ポリオレフィン中に残存する未反応の無水マレインお
よび反応副生物の除去が効率的に進まなかったり、該ポ
リオレフィンの溶融互着が生し精製が困難になる。被除
去成分に対して本発明に使用する溶媒は良溶媒であるが
、該ポリオレフィンに対しては貧溶媒である。しかしな
がら、該溶媒の炭素数の増加につれてポリオレフィンに
対する親和性が増加するため本発明に記載した関係式を
必要とすることを見いだして本発明に到った。除去温度
が本発明に記載した温度を越えなければ溶融互着は生じ
ない。特に、好ましい温度範囲は（０，９７ｘＴｍｐ−
０，８Ｎ２．４）℃〜（０，７３ｘ Ｔｍ ｐ −０，
８Ｎ２．４） ℃である。炭素数が６を越えるとポリオ
レフィンとの親和性が高くなる結果、溶解性が高まり実
質的に精製が不可能になる。The solvent should be one that has a carbonyl group with at most 6 carbon atoms. T m p -0.8N2.4) °C
unreacted maleic anhydride and reaction by-products are removed from the polyolefin in a temperature range of 0.7'xTmp'-0.8N2.4)°C. If the temperature exceeds this range, the removal of unreacted anhydride maleic and reaction by-products remaining in the modified polyolefin may not proceed efficiently, or the polyolefin may become melted together, making purification difficult. The solvent used in the present invention is a good solvent for the component to be removed, but is a poor solvent for the polyolefin. However, as the number of carbon atoms in the solvent increases, the affinity for polyolefins increases, so the inventors have discovered that the relational expression described in the present invention is necessary, leading to the present invention. Melt bonding does not occur unless the removal temperature exceeds the temperature described in this invention. In particular, the preferred temperature range is (0,97xTmp-
0,8N2.4)℃~(0,73x Tm p -0,
8N2.4) °C. When the number of carbon atoms exceeds 6, the affinity with polyolefins increases, resulting in increased solubility and purification becomes virtually impossible.
炭素数が多くとも６であるカルボニル基を有する溶媒の
具体的な例を示せば、アセトアルデヒド、プロパナール
、アセトン、ブタナール、エチルメチルケトン、ペンタ
ナール、ジエチルケトン、メチルプロピルケトン、酢酸
メチル、・酢酸エチル、ジメチルホルムアルデヒド、ジ
メチルアセトアルデヒド等をあげることができる。臭い
の点では、好ましくは、ジメチルホルムアミド、ジメチ
ルアセトアルデヒドである。臭気上の問題は存在するが
、精製プロセスを完備すれば、エタナール、プロパナー
ル、ブタナールが好まれる。また、経済性の点ではアセ
トン、エチルメチルケトンを好ましいものとしてあげる
ことができる。該カルボニル基を有する溶媒は無水マレ
イン酸を用いてグラフト変性をした変性ポリオレフィン
１００重量部に対して１００ないし３０００重量部を使
用する。Specific examples of solvents having a carbonyl group having at most 6 carbon atoms include acetaldehyde, propanal, acetone, butanal, ethyl methyl ketone, pentanal, diethyl ketone, methyl propyl ketone, methyl acetate, and ethyl acetate. , dimethyl formaldehyde, dimethyl acetaldehyde, etc. In terms of odor, dimethylformamide and dimethylacetaldehyde are preferred. Although odor problems exist, ethanal, propanal, and butanal are preferred if the purification process is complete. Moreover, from the point of view of economy, acetone and ethyl methyl ketone are preferable. The carbonyl group-containing solvent is used in an amount of 100 to 3,000 parts by weight per 100 parts by weight of the modified polyolefin graft-modified using maleic anhydride.
充分に該変性ポリオレフィンが浸せきする事が必要であ
り、更に該変性ポリオレフィン中に未反応無水マレイン
酸および反応副生物を溶解した溶媒を含むため、実質的
にその残存量が影響を及ぼさないためには、１０００な
いし２０００重量部を使用する事が望ましい。もしくは
、上記精製を２度以上行なうことは精製された変性ポリ
オレフィン中に含浸された溶媒に溶解して残存する未反
応無水マレイン酸および反応副生物の量を低減すること
に非常に有効である。この場合は、上記の好ましい範囲
よりはるかに少ない溶媒量で精製が可能である。精製工
程では該溶媒と該変性ポリオレフィンの接触及び精製が
有効に行なわれるために攪拌等を行なうことが好ましい
。またその精製時間は３０分間ないし３時間程度行なえ
ばよい。続いて公知の渡過、遠心分離等の方法で固液分
離を行い、減圧もしくは加熱乾燥を行うことにより精製
を完了する事ができる。It is necessary to sufficiently soak the modified polyolefin, and furthermore, since the modified polyolefin contains a solvent in which unreacted maleic anhydride and reaction by-products are dissolved, the remaining amount does not substantially affect the process. It is desirable to use 1000 to 2000 parts by weight. Alternatively, performing the above purification twice or more is very effective in reducing the amount of unreacted maleic anhydride and reaction by-products that remain dissolved in the solvent impregnated into the purified modified polyolefin. In this case, purification is possible with a much smaller amount of solvent than the above-mentioned preferred range. In the purification step, it is preferable to carry out stirring or the like in order to effectively bring the solvent into contact with the modified polyolefin and purify it. Further, the purification time may be about 30 minutes to 3 hours. Subsequently, solid-liquid separation is performed by a known method such as traversal separation or centrifugation, and purification can be completed by performing reduced pressure or heat drying.
精製すべき変性ポリオレフィンの形状は特に限定するも
のではなく、粉末状、フレーク状、ペレット状の原料を
扱うことができる。しかし、本発明の方法はペレット状
の原料を取り扱うのに最も適している。本発明の溶媒お
よび温度条件を適切に選択する事により、従来の方法で
は精製が不完全にしか行えなかったペレット状原料を用
いても有効な精製が可能になる。従って、固液分離、搬
送、乾燥等の工程が簡略化され従って精製を経済的に行
う事ができる。The shape of the modified polyolefin to be purified is not particularly limited, and raw materials in the form of powder, flakes, and pellets can be used. However, the method of the present invention is most suitable for handling pelleted raw materials. By appropriately selecting the solvent and temperature conditions of the present invention, effective purification can be achieved even using pelleted raw materials, which could only be purified incompletely by conventional methods. Therefore, steps such as solid-liquid separation, transportation, and drying are simplified, and purification can therefore be carried out economically.
さらに該変性ポリオレフィンの乾燥の前の段階において
、必要とされる樹脂の安定剤をアセトン等の溶媒に溶解
させて該変性ポリオレフィンに添加し乾燥することがで
きる。この方法によれば乾燥工程における樹脂の劣化を
防ぐことが可能となり該変性ポリオレフィンの色相等に
対して非常に好ましい結果を与える。Furthermore, in a step before drying the modified polyolefin, a necessary resin stabilizer can be dissolved in a solvent such as acetone, added to the modified polyolefin, and dried. According to this method, it is possible to prevent deterioration of the resin during the drying process, and very favorable results can be obtained in terms of the hue, etc. of the modified polyolefin.
このようにして、得られた変性ポリオレフィンの有する
無水マレイン酸に由来する基は０．０１〜１５重量％、
好ましくはＯ，１〜１０重量％である。、この変性ポリ
オレフィンはそれ自身単独でもしくは未変性のポリオレ
フィンで希釈して使用される。また、ゴム、ポリアミド
、エチレン−酢酸ビニル共重合体のケン化物等の他の熱
可塑性樹脂とブレンドして接着剤樹脂、コーティング用
樹脂、無機微細粉末や顔料の分散剤、ポリマーアロイの
界面補強材として利用し得る。In this way, the group derived from maleic anhydride that the obtained modified polyolefin has is 0.01 to 15% by weight,
Preferably it is O, 1 to 10% by weight. This modified polyolefin can be used alone or diluted with an unmodified polyolefin. It can also be blended with other thermoplastic resins such as rubber, polyamide, and saponified products of ethylene-vinyl acetate copolymer to produce adhesive resins, coating resins, dispersants for inorganic fine powders and pigments, and interface reinforcing materials for polymer alloys. It can be used as
（５）実施例 以下実施例により本発明をさらに具体的に説明する。(5) Examples The present invention will be explained in more detail below using Examples.
（変性ポリオレフィンの製造）
ポリプロピレン粉末（ＭＦＲ：、０．８）１００重量部
に過酸化ベンゾイル１． ０重量部、無水マレイン酸１
．５重量部を添加後ヘンシェルミキサーにて混合し、４
（Ｌｍｍφ、Ｌ／Ｄ２８のベント付き押出機にて２２０
℃で押出し、水冷後ペレット化した。ここで得た、変性
ポリプロピレンを沸騰キシレンに溶解した後、アセトン
を使用して再沈した。充分アセトンにて洗浄した後、６
０℃で減圧乾燥１２時間を行い、赤外吸収スペクトル分
析法でポリプロピレンにグラフトされた無水マレイン酸
に基づく基を定量した結果０．６７重量％を得た。キシ
レン溶解前の無水マレイン酸にＪ、Ｇづく基は１．２６
重量％であった。Ｔｍは１５９゜Ｃであった。 （Ａ）
以下、類似の条件にて第１表に示すポリオレフィン変性
物を得た。(Manufacture of modified polyolefin) 100 parts by weight of polypropylene powder (MFR: 0.8) was mixed with 1.0 parts by weight of benzoyl peroxide. 0 parts by weight, 1 part maleic anhydride
．． After adding 5 parts by weight, mix in a Henschel mixer,
(Lmmφ, L/D28 with vented extruder
It was extruded at ℃ and pelletized after cooling with water. The modified polypropylene obtained here was dissolved in boiling xylene, and then reprecipitated using acetone. After thoroughly washing with acetone,
Drying was carried out under reduced pressure at 0° C. for 12 hours, and the amount of maleic anhydride-based groups grafted onto polypropylene was determined to be 0.67% by weight using infrared absorption spectroscopy. The J and G groups on maleic anhydride before dissolving in xylene are 1.26
% by weight. Tm was 159°C. (A) Modified polyolefins shown in Table 1 were obtained under similar conditions.
（変性ポリオレフィンの精製）
実施例１
攪拌機付き２０１耐圧容器に変性ポリオレフィンＡのペ
レット５ｋｇとエチルメチルケトン１０ｋｇを入れ、１
２０℃にて１時間攪拌したのち、室温まで冷却し、エチ
ルメチルケトン溶媒を底から抜きだした。該エチルメチ
ルケトン溶媒は赤褐色に着色していた。再び、新しいエ
チルメチルケトンを７ｋｇ追加し、１２０℃で１時間攪
拌した後、室温にまで冷却し、エルメチルケトン溶媒を
１】−
底から抜きだした。該エチルメチルケトン溶媒はかすか
に赤褐色に着色していた。更に、新しいエチルメチルケ
トンを７ｋｇ追加し、１２０℃で１時間攪拌した後、室
温にまで冷却し、エチルメチルケトン溶媒を底から抜き
だした。そののち、イルガノックス１０７６ （チバガ
イギー社製）を２０ｇを含むアセトン３００ ｍ ｌを
添加し、５０℃にて４８時間減圧乾燥をし白色度の高い
ペレットが得られた。上記処理後に得られた、変性ポリ
オレフィン（ａ）中には無水マレイン酸に基づく基は０
．６７重量％であり、先に示した、キシレン再沈の結果
とよく一致した。本実験に使用した温度は本発明に示し
た式から計算される値、１３７℃と８９℃の範囲内であ
る。(Purification of modified polyolefin) Example 1 5 kg of modified polyolefin A pellets and 10 kg of ethyl methyl ketone were placed in a 201 pressure-resistant container equipped with a stirrer, and 1
After stirring at 20° C. for 1 hour, the mixture was cooled to room temperature, and the ethyl methyl ketone solvent was drawn out from the bottom. The ethyl methyl ketone solvent was colored reddish brown. Again, 7 kg of fresh ethyl methyl ketone was added, and the mixture was stirred at 120°C for 1 hour, then cooled to room temperature, and 1]- of the ethyl methyl ketone solvent was drawn out from the bottom. The ethyl methyl ketone solvent was slightly reddish brown in color. Furthermore, 7 kg of fresh ethyl methyl ketone was added, and after stirring at 120° C. for 1 hour, the mixture was cooled to room temperature, and the ethyl methyl ketone solvent was drawn out from the bottom. Thereafter, 300 ml of acetone containing 20 g of Irganox 1076 (manufactured by Ciba Geigy) was added, and the mixture was dried under reduced pressure at 50° C. for 48 hours to obtain pellets with high whiteness. There are no groups based on maleic anhydride in the modified polyolefin (a) obtained after the above treatment.
．． It was 67% by weight, which was in good agreement with the xylene reprecipitation results shown above. The temperature used in this experiment was within the range of 137°C and 89°C, which is the value calculated from the formula shown in the present invention.
実施例２〜４
変性ポリオレフィンＢおよびアセ、トンを使用し１２５
℃にて行なった以外は実施例１と同様にして行なった。Examples 2-4 Using modified polyolefin B and acetate 125
The same procedure as in Example 1 was carried out except that the temperature was 0.degree.
上記処理後に得られた、変性ポリオレフィン（ｂ）中に
は無水マレイン酸に基づく基は０．８１重量％であり、
先に示した、キシレン再沈の結果とよく一致した。本実
験に使用した温度は本発明に示した式から計算される値
、１３７℃と９２℃の範囲内である。 （実施例２）変
性ポリオレフィンＣおよびアセトンを使用し１１５℃に
て行なった以外は実施例１と同様にし・て行なった。上
記処理後に得られた、変性ポリオレフィン（Ｃ）中には
無水マレイン酸に基づく基は０．３４重量％であり、先
に示した、キシレン再沈の結果とよく一致した。本実験
に使用した温度は本発明に示した式から計算される（ｌ
ｌｔ、１２１℃と８１℃の範囲内である。 （実施例３
）変性ポリオレフィンＤおよびエチルメチルケトンを使
用し７５℃にて行なった以外は実施例１と同様にして行
なった。上記処理後に得られた、変性ポリオレフィン（
ｄ）中には無水マレイン酸に基づく基は０．３３重量％
であり、先に示した、キシレン再沈の結果とよく一致し
た。本実験に使用した温度は本発明に示した式から計算
される値、８１℃と５０℃の範囲内である。 （実施例
４）実施例５
イルガノックス１０７６ （チバガイギー製）を２０ｇ
含むアセトン３００ ｍ ｌを添加しなかった以外は実
施例１と同様に行った。上記処理後に得られた変性ポリ
オレフィン（ｆ）中には無水マレイン酸に基づく基は０
゜６７重量％であり、さきに示したキシレン再沈澱の結
果とよく一致した。The modified polyolefin (b) obtained after the above treatment contains 0.81% by weight of groups based on maleic anhydride,
This was in good agreement with the xylene reprecipitation results shown above. The temperature used in this experiment was within the range of 137°C and 92°C, which is the value calculated from the formula shown in the present invention. (Example 2) The same procedure as in Example 1 was carried out except that modified polyolefin C and acetone were used and the temperature was 115°C. The modified polyolefin (C) obtained after the above treatment contained 0.34% by weight of groups based on maleic anhydride, which was in good agreement with the xylene reprecipitation results shown above. The temperature used in this experiment is calculated from the formula shown in the present invention (l
lt, within the range of 121°C and 81°C. (Example 3
) The same procedure as in Example 1 was carried out except that modified polyolefin D and ethyl methyl ketone were used and the temperature was 75°C. The modified polyolefin obtained after the above treatment (
d) contains 0.33% by weight of groups based on maleic anhydride.
This was in good agreement with the xylene reprecipitation results shown above. The temperature used in this experiment was within the range of 81°C and 50°C, which is the value calculated from the formula shown in the present invention. (Example 4) Example 5 20g of Irganox 1076 (manufactured by Ciba Geigy)
The same procedure as in Example 1 was conducted except that 300 ml of acetone was not added. There are no groups based on maleic anhydride in the modified polyolefin (f) obtained after the above treatment.
It was 67% by weight, which was in good agreement with the xylene reprecipitation results shown earlier.
なお本実験に使用した精製温度は本発明に示した式から
計算される値、１３７−８９’ Ｃの範囲内である。The purification temperature used in this experiment was within the range of 137-89'C, which is the value calculated from the formula shown in the present invention.
比較例１，２
精製温度を７０℃にした以外は実施例１と同様にして行
なった。上記処理後に得られた、変性ポリオレフィン（
ｅ）中には無水マレイン酸に基づく基は１．１０重量％
であり、先に示した、キシレン再沈の結果と比較して殆
ど精製がされていないことを認めた。 （比較例１）
精製温度を１００℃にした以外は実施例４と同様にして
行なったところ、変性ポリオレフィンは完全に溶融互着
し攪拌軸に塊として付着し、ペレットとして取り扱うこ
とは全くできなかった。 （比較例２）
（接着性の評価）
本実験で得られた変性ポリオレフィンおよび実施例、比
較例で得られたポリオレフィンを、同し種類の樹脂によ
り、変性ポリオレフィン量が２０重量％にまで希釈した
。更に、使用した樹脂は出来上りの変性ポリオレフィン
組成物のＭＦＲがＴダイス成形性を発現するように同じ
種類の樹脂のＭＦＲを選択した。接着性能をエチレンと
ビニルアルコール共重合体（エチレン含有量： ３２モ
ル％）とを４０ ｍ ｍ、４５ ｍ ｍの二種二層共押
出し成形機を用いてダイス温度２２０℃、通水状態のチ
ルロールを使用して二種二層フィルムをつくり１８０度
剥離試験を剥離速度２００ ｍ ｍ ７分にて評価した
。その結果を第２表に示す。明らかに、精製が充分され
た系の接着性は優れている。Comparative Examples 1 and 2 The same procedure as in Example 1 was carried out except that the purification temperature was 70°C. The modified polyolefin obtained after the above treatment (
e) contains 1.10% by weight of groups based on maleic anhydride.
It was recognized that there was almost no purification compared to the results of xylene reprecipitation shown above. (Comparative Example 1) The process was carried out in the same manner as in Example 4 except that the purification temperature was 100°C. The modified polyolefin was completely melted and adhered to the stirring shaft as a lump, and could not be handled as pellets at all. Ta. (Comparative Example 2) (Evaluation of Adhesion) The modified polyolefin obtained in this experiment and the polyolefin obtained in Examples and Comparative Examples were diluted with the same type of resin until the amount of modified polyolefin was 20% by weight. . Furthermore, the MFR of the same type of resin was selected so that the MFR of the finished modified polyolefin composition would exhibit T-die moldability. Adhesive performance was evaluated using a two-layer coextrusion molding machine of 40 mm and 45 mm using ethylene and vinyl alcohol copolymer (ethylene content: 32 mol%) at a die temperature of 220°C and a chill roll with water flowing through it. Two types of two-layer films were made using the following, and a 180 degree peel test was performed at a peel rate of 200 mm and 7 minutes. The results are shown in Table 2. Clearly, the adhesion of well-purified systems is superior.
さらに実施例１と実施例５とを比較すると抗酸化剤を加
えた実施例１の方が接着性に優れまた色相も良好であっ
た。Furthermore, when comparing Example 1 and Example 5, Example 1 containing an antioxidant had better adhesive properties and a better hue.
（以下余白）
（６）効果
本発明の方法により精製した変性ポリオレフィンは良好
な接着性能を示すため各種の多層フィルムの層間接着層
として有用に使用できるばがってなく、未反応の無水マ
レイン酸および反応副生成物が少ないため衛生性も優れ
たものであり、食品用途にも好適に使用することが出来
る。(Left below) (6) Effect The modified polyolefin purified by the method of the present invention exhibits good adhesive performance and can be usefully used as an interlayer adhesive layer of various multilayer films. Moreover, since there are few reaction by-products, the hygienic property is also excellent, and it can be suitably used for food applications.
また一方において経済的な変性ポリオレフィンの生成方
法を提供するものである。On the other hand, it provides an economical method for producing modified polyolefins.
Claims (2)
をした変性ポリオレフィンを精製するにあたり、炭素数
が多くとも６であるカルボニル基を有する溶媒を使用し
（Ｔｍｐ−１．１Ｎ＾２＾．＾４）℃ないし（０．７ｘ
Ｔｍｐ−０．８Ｎ＾２＾．＾４）℃（ただしＴｍｐは該
ポリオレフィンの融解ピーク温度（℃）、Ｎは該溶媒の
炭素数を表す）の温度範囲で未反応無水マレイン酸及び
反応副生物を該ポリオレフィンから除去することを特徴
とする変性ポリオレフィンの精製方法。(1) When purifying a modified polyolefin that has been graft-modified using maleic anhydride in a molten state, a solvent having a carbonyl group having at most 6 carbon atoms is used (Tmp-1.1N^2^.^ 4)℃ to (0.7x
Tmp-0.8N^2^. ^4) It is characterized by removing unreacted maleic anhydride and reaction by-products from the polyolefin in a temperature range of ℃ (where Tmp is the melting peak temperature of the polyolefin (℃) and N is the number of carbon atoms in the solvent). A method for purifying a modified polyolefin.
る請求項（１）記載の変性ポリオレフィンの精製方法。(2) The method for purifying a modified polyolefin according to claim (1), wherein the modified polyolefin to be purified is in the form of pellets.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP447189A JPH02185505A (en) | 1989-01-11 | 1989-01-11 | Purification of modified polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP447189A JPH02185505A (en) | 1989-01-11 | 1989-01-11 | Purification of modified polyolefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02185505A true JPH02185505A (en) | 1990-07-19 |
Family
ID=11585039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP447189A Pending JPH02185505A (en) | 1989-01-11 | 1989-01-11 | Purification of modified polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02185505A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002167484A (en) * | 2000-12-04 | 2002-06-11 | Japan Polychem Corp | Polypropylene based resin composition and production method therefor |
| WO2005113611A1 (en) | 2004-05-14 | 2005-12-01 | Lyondell Chemical Technology, L.P. | Extraction of impurities from grafted polyolefins |
| JPWO2005113667A1 (en) * | 2004-05-24 | 2008-03-27 | 株式会社プライムポリマー | Fiber reinforced resin composition and molded article thereof |
| US7550065B2 (en) | 2005-04-21 | 2009-06-23 | Lyondell Chemical Technology, L.P. | Method for recovering solvents |
| JPWO2008059938A1 (en) * | 2006-11-17 | 2010-03-04 | 三井化学株式会社 | Method for producing syndiotactic propylene polymer |
| US8709586B2 (en) * | 2004-10-22 | 2014-04-29 | Prime Polymer Co., Ltd. | Modified polyolefin resin for glass fiber treatment, surface-treated glass fiber, and fiber-reinforced polyolefin resin |
| JP2016056318A (en) * | 2014-09-11 | 2016-04-21 | 三井化学株式会社 | Production method and purification method of modified polyolefin particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4996095A (en) * | 1972-12-18 | 1974-09-11 | ||
| JPS6390511A (en) * | 1986-10-06 | 1988-04-21 | Mitsui Petrochem Ind Ltd | Modified polypropylene |
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1989
- 1989-01-11 JP JP447189A patent/JPH02185505A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4996095A (en) * | 1972-12-18 | 1974-09-11 | ||
| JPS6390511A (en) * | 1986-10-06 | 1988-04-21 | Mitsui Petrochem Ind Ltd | Modified polypropylene |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002167484A (en) * | 2000-12-04 | 2002-06-11 | Japan Polychem Corp | Polypropylene based resin composition and production method therefor |
| WO2005113611A1 (en) | 2004-05-14 | 2005-12-01 | Lyondell Chemical Technology, L.P. | Extraction of impurities from grafted polyolefins |
| US7060787B2 (en) | 2004-05-14 | 2006-06-13 | Lyondell Chemical Technology, L.P. | Extraction of impurities from grafted polyolefins |
| JPWO2005113667A1 (en) * | 2004-05-24 | 2008-03-27 | 株式会社プライムポリマー | Fiber reinforced resin composition and molded article thereof |
| US8709586B2 (en) * | 2004-10-22 | 2014-04-29 | Prime Polymer Co., Ltd. | Modified polyolefin resin for glass fiber treatment, surface-treated glass fiber, and fiber-reinforced polyolefin resin |
| US7550065B2 (en) | 2005-04-21 | 2009-06-23 | Lyondell Chemical Technology, L.P. | Method for recovering solvents |
| JPWO2008059938A1 (en) * | 2006-11-17 | 2010-03-04 | 三井化学株式会社 | Method for producing syndiotactic propylene polymer |
| JP2016056318A (en) * | 2014-09-11 | 2016-04-21 | 三井化学株式会社 | Production method and purification method of modified polyolefin particles |
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