JPH0420020B2 - - Google Patents
Info
- Publication number
- JPH0420020B2 JPH0420020B2 JP56214076A JP21407681A JPH0420020B2 JP H0420020 B2 JPH0420020 B2 JP H0420020B2 JP 56214076 A JP56214076 A JP 56214076A JP 21407681 A JP21407681 A JP 21407681A JP H0420020 B2 JPH0420020 B2 JP H0420020B2
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- present
- odor
- catalyst
- purified
- 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.)
- Expired - Lifetime
Links
- 229920000098 polyolefin Polymers 0.000 claims description 42
- 239000003054 catalyst Substances 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000009965 odorless effect Effects 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229910016310 MxSiy Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 230000000415 inactivating effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 11
- 235000019645 odor Nutrition 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 230000001364 causal effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012629 purifying agent Substances 0.000 description 2
- -1 salt compound Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
本発明は、無臭化ポリオレフイン組成物に関
し、さらに詳しくはチーグラー法ポリオレフイン
の触媒キル剤に由来するポリオレフイン製品中の
悪臭を除去した該製品とその製造法（脱臭法）に
関する。
チーグラー法触媒によるポリオレフインの製造
法は、近年所謂高活性触媒の出願により、プロセ
ス的には著しく単純化されている。古典的プロセ
スと対比して省略され得た工程としては、たとえ
ば無定形ポリオレフイン分離工程、溶媒回収工程
（近相法の場合）、触媒除去工程などがあげられ
る。しかしながら、触媒除去工程の不要な場合で
あつても、重合直後の粗製ポリオレフイン中に含
まれる触媒残渣には、未だ活性が残存しているの
で、該ポリオレフインは次の工程に送られる前に
精製工程（触媒キル工程）にかけられなければな
らない。該精製剤（キル剤）としては、触媒と反
応してこれを不活性化できる水、アルコール類若
しくはアルキレンオキサイドが知られている。中
でも、プロセス上の取り扱い易さと不活性化効果
が適確であることから、該精製剤としてアルキレ
ンオキサイドが広く実用されていると考えられ、
しかしながら、アルキレンオキサイドを用いて精
製処理されたポリオレフイン（以下アルキレンオ
キサイド処理品）には次の欠点がある。その欠点
とは、アルキレンオキサイド処理品を用いて成形
した成型品、フイルム、繊維、其他加工製品に独
特の異臭が伴うことである。この異臭は該成型品
等の商品価値を低下させ、用途によつては使用不
可能となるおそれがある。
ただし、この事実（因果関係）は、本願出願時
においては、公然知られている事実ではなく、精
製結果としてのポリオレフインを用いた成形品の
異臭と精製剤との因果関係を本発明者等が追究し
た結果判明した事実である。他方、後に詳述する
本発明に単に外見上類似する技術として、未精製
ポリオレフイン中の微量の触媒残渣中の酸性物質
を中和する目的で例えば水酸化カルシウム若しく
は水酸化マグネシウム（特開昭49−3947号）また
はハイドロタルサイト（特開昭52−49285、特開
昭55−80447号を混合する技術が知られている。
しかしながらこれ等の技術と本発明とは、具体的
構成と効果を異にしている。
本発明者等は、この問題解決につき鋭意研究し
た。その結果後述する特定の無機複塩化合物若し
くはそれらの燬焼物（脱水品）を精製ポリオレフ
インに微量添加することによつて充分にその異臭
を除去できることを知つて本発明を完成した。以
上の記述から明らかなように本発明の目的は、精
製剤としてアルキレンオキサイドを用いた精製ポ
リオレフインであつて成形品とした際に異臭のな
い無臭化ポリオレフイン組成物ならびにその製造
法（無臭化法）を提供するにある。本発明の他の
目的は無臭化ポリオレフインを用いた無臭成形品
を提供することであり、別の目的は、ポリオレフ
インの精製工程における精製剤としてのアルキレ
ンオキサイドの適用を容易にすることである。
本発明は、
(1) オレフインをチーグラー法触媒を用いて重合
させて得た未精製ポリオレフイン中の触媒残渣
をアルキレンオキサイドを用いて不活性化して
得られた精製ポリオレフインに下記〜若し
くはこれらの燬焼生成物から選ばれた１種以上
の処理剤を0.001〜0.5重量％混合してなる無臭
化ポリオレフイン組成物である。また、本発明
の第２の発明は、
(2) オレフインをチーグラー型触媒を用いて重合
させて得た未精製ポリオレフイン中の触媒残渣
をアルキレンオキサイドを用いて不活性化して
得られたポリオレフインに下記〜若しくは
これらの燬焼生成物から選ばれた１種以上の処
理剤を0.001〜0.5重量％混合することを特徴と
する無臭化ポリオレフインの製造法である。
AlxSiy（OH）3x+4y・nH2O
Mgx（OH）22y+2x（CO3）ｙ・nH2O
MgXCay（CO3）2x+2y/2・nH2O
MxSiy（OH）2x+4y・nH2O
MgxAlySiz（Ｈ）2x+3y+4z・2H2O
MxAly（OH）2y+3y-2z（Ａ）・nH2O
ただし、ＭはMg若しくはCa、ＡはCO3、
ｘ、ｙ、ｚは正数、ｎは０若しくは正の整数。
以下本発明の構成と効果につき詳細に説明す
る。本発明にいうポリオレフインとは、実質的に
ポリオレフインの製造原料となるものをいい、た
とえば、エチレン、プロピレン、ブテン−１、４
−メチルペンテン−１、ヘキセン−１のようなモ
ノα−オレフイン、スチレン、ビニルシクロヘキ
サンのような環式ビニル化合物のほか、ブタジエ
ンのようなジオレフインも含まれる。チーグラー
型触媒とは、代表的には周期律表第〜族金属
の有機金属化合物と同じく第〜族の遷移金属
化合物（最高原子価より低い原子価を有する化合
物を含む）の組合せとして知られたもの若しくは
その改良に係るものをいう。さらにチーグラー型
触媒には、触媒性能の改良を目的として種々の第
三成分を添加し若しくは遷移金属化合物成分を担
体に担持させ、または、触媒系全体をα−オレフ
インで予備重合させることにより重合機能を増進
させたものも含む。
本発明の処理対象となる未精製ポリオレフイン
とは、前述のオレフインを前述の触媒を用いて比
較的低温（例えば０℃〜200℃）低圧（例えば常
圧ないし50Kg／cm2）で重合させ、必要ならば中和
処理および溶媒除去（懸濁重合の場合）を行つた
ものである。
本発明に使用するアルキレンオキサイドとは、
好ましくはエチレンオキサイドプロピレンオキサ
イドのような低級アルキレンオキサイドであつて
未精製ポリオレフイン中の触媒残渣と反応してこ
れを不活性化させうる薬剤である。アルキレンオ
キサイドは別種の該不活性化剤例えば水、メタノ
ール、イソプロパノールのような薬剤と組合せて
使用することもできる。不活性化処理条件（温
度、時間、圧力、薬剤と未精製ポリオレフインと
の量比）は、公知の条件の範囲内なら使用でき
る。しかしながら20℃〜200℃、１分〜４時間、
常圧〜100Kg／cm2、および0.01〜10％の範囲内が
実施しやすい。このような精製処理により精製ポ
リオレフイン中の活性塩素分は、非検出ないし
10ppm程度まで低下させることができる。
本発明に係る上述の精製ポリオレフインには、
次の〜の結晶水を有する無機複塩若しくはこ
れらの燬焼生成物の一定量を混合する。
AlxSiy（OH）3x+4y・nH2O
Mgx（OH）2y-2x（CO3）y・nH2O
MgxCay（CO3）22x+2y/2・nH2O
MxSiy（CH）2x+4y・nH2O
MgxAlySiz（OH）2x+3y+4z・nH2O
MxAly（OH）2x+3y-2z（Ａ）・nH2O
ただし、ＭはMg若しくはCa、ＡはCO3、ｘ、
ｙ、ｎは正数、ｎは０若しくは正の整数。
上述の燬焼生成物とは、これらの複塩を加熱し
て付着水若しくは結晶水を完全に若しくは部分的
に除去脱水したものをいう。上記〜の無機複
塩またはこれらの燬焼生成物（以下、本発明に係
る無機複塩等ということがある）の粒度若しくは
平均粒径は10μ以下好ましくは1μ以下0.01μ程度で
ある。0.01μ未満のものでも均一な混合が可能な
限り使用できる。平均粒径のみならず、本発明に
係る無機複塩等の粒子の比表面積は限定はされな
いが高いものが好ましい。好ましい該表面積は、
10〜300m2／ｇである。本発明に係る無機複塩等
と精製ポリオレフインとの混合割合は、後者を基
準として0.001〜0.5重量％好ましくは0.005〜0.1
重量％である。この混合割合から明らかなよう
に、本発明に係る無機複塩等の添加量は、他の添
加剤（例えば熱安定剤）に較べて実質的に非常に
少ない。したがつてかかる微量の添加により、精
製ポリオレフイン中の異臭（註、成形品の段階で
顕著にあらわれる）を充分防止できることは驚く
べきことである。添加量はこのように微量である
が、均一な混合さえ可能ならば、本発明に係る無
機塩等の精製ポリオレフイン等への混合方法は、
格別限定されない。
先づ、混合時期としては、他の添加剤に先立つ
て精製ポリオレフインに混合してもよく、該他の
添加剤と同時に若しくは、他の添加剤をすべて添
加した後すなわち精製ポリオレフインをペレツト
化する際の可塑化工程において添加混合すること
もできる。また添加量が微量であるためあらかじ
め少量の精製ポリオレフイン粉末と均一に混合し
たものを精製ポリオレフインに混合することが望
ましい。混合装置、混合条件は限定されないが、
たとえば、高速撹拌式混合器（商品名ヘンシエル
ミキサー）を用い、室温ないし50℃、１分ないし
30分混合する。他の混合装置例えば、リボンブレ
ンダー若しくはＶ型ブレンダーも用いることがで
きる。
本発明の無臭化ポリオレフイン組成物はこれを
成型品、フイルムおよび繊維その他の成形品に加
工してもアルキレンオキサイドに由来する独特の
悪臭が殆んど若しくは全くなく、したがつてこれ
らの成形品の異臭にもとづく用途的制限（例えば
食品容器への使用不能）をなくし若しくは商品価
値の低下を防止できる。
以下実施例、比較例をもつて本発明を説明す
る。なお、実施例および比較例に示す諸数値は下
記の方法で測定した。
MFR；ASTM−D1738
ポリオレフイン中の灰分；けい光Ｘ線分析法に
より、Al、TiおよびClを測定した。XRFClで
示した。
活性クロル；試料量のポリオレフインを300℃
に加熱し、発生するガス中の塩化
水素の量を測定し、ポリオレフイ
ン当りの発生量で示した。
YI（イエローネス・インデツクス）：色差計
（スガ試験機(株)製）を用いて測定した。
成型品の臭い：成型機から取り出された直後の試
験片について官能検査
により、つぎの５段階で数値表示した。
１；臭いが非常に強い ２；臭いがかなりある
３；臭いがある ４；わずかに臭いがあ
る
５；臭いが全くない
また、実施例および比較例に使用した添加剤（化
合物若しくはそれらの燬焼物）についても次のよ
うに数値記号で示した。
The present invention relates to an odor-free polyolefin composition, and more particularly to a polyolefin product that removes bad odors derived from a catalyst-killing agent for Ziegler process polyolefins, and a method for producing the same (deodorizing method). The process for producing polyolefins using Ziegler method catalysts has been significantly simplified in recent years due to the application of so-called highly active catalysts. Steps that can be omitted in comparison with classical processes include, for example, an amorphous polyolefin separation step, a solvent recovery step (in the case of a near-phase method), a catalyst removal step, and the like. However, even if the catalyst removal step is not necessary, the catalyst residue contained in the crude polyolefin immediately after polymerization still has some activity, so the polyolefin is subjected to the purification step before being sent to the next step. (catalyst kill step). Water, alcohols, or alkylene oxides that can react with the catalyst to inactivate it are known as the purifying agent (killing agent). Among them, alkylene oxide is thought to be widely used as a purification agent because of its ease of handling in the process and its appropriate inactivation effect.
However, polyolefins purified using alkylene oxide (hereinafter referred to as alkylene oxide treated products) have the following drawbacks. The disadvantage is that molded products, films, fibers, and other processed products made using alkylene oxide-treated products have a unique odor. This off-odor may reduce the commercial value of the molded product, making it unusable for some purposes. However, this fact (causal relationship) is not a publicly known fact at the time of filing this application, and the inventors and others are aware of the causal relationship between the purification agent and the off-odor of molded products using polyolefin as a result of purification. This is a fact that was discovered as a result of investigation. On the other hand, as a technique that is simply similar in appearance to the present invention which will be described in detail later, for example, calcium hydroxide or magnesium hydroxide (JP-A-49-1999) is used for the purpose of neutralizing acidic substances in trace amounts of catalyst residue in unpurified polyolefin 3947) or hydrotalcite (JP-A-52-49285, JP-A-55-80447) is known.
However, these techniques and the present invention differ in specific configurations and effects. The inventors of the present invention have conducted extensive research into solving this problem. As a result, the present invention was completed with the knowledge that by adding a small amount of a specific inorganic double salt compound or a dehydrated product thereof to purified polyolefin, the off-odor thereof can be sufficiently removed. As is clear from the above description, the object of the present invention is to provide a deodorized polyolefin composition which is a purified polyolefin using alkylene oxide as a purifying agent and which has no off-odor when molded, and a method for producing the same (deodorization method). is to provide. Another object of the present invention is to provide an odorless molded article using an odorless polyolefin, and another object is to facilitate the application of alkylene oxide as a refining agent in the polyolefin purification process. The present invention provides: (1) A refined polyolefin obtained by inactivating a catalyst residue in an unpurified polyolefin obtained by polymerizing an olefin using a Ziegler method catalyst using an alkylene oxide, and a purified polyolefin obtained by This is an odorless polyolefin composition prepared by mixing 0.001 to 0.5% by weight of one or more processing agents selected from the products. In addition, the second invention of the present invention provides that (2) the catalyst residue in unpurified polyolefin obtained by polymerizing olefin using a Ziegler type catalyst is inactivated using alkylene oxide, This is a method for producing an odorless polyolefin, which is characterized by mixing 0.001 to 0.5% by weight of one or more processing agents selected from the following. AlxSiy(OH) 3x+4y・nH 2 O Mgx(OH) 22y+2x (CO 3 )y・nH 2 O MgXCay(CO 3 ) 2x+2y/2・nH 2 O MxSiy(OH) 2x+4y・nH 2 O MgxAlySiz(H) 2x+3y+4z・2H 2 O MxAly(OH) 2y+3y-2z (A)・nH 2 O However, M is Mg or Ca, A is CO 3 ,
x, y, z are positive numbers, and n is 0 or a positive integer. The structure and effects of the present invention will be explained in detail below. The polyolefin referred to in the present invention refers to a substance that is essentially a raw material for producing polyolefin, such as ethylene, propylene, butene-1, 4-butene, etc.
-In addition to mono-alpha-olefins such as methylpentene-1 and hexene-1, cyclic vinyl compounds such as styrene and vinylcyclohexane, diolefins such as butadiene are also included. Ziegler-type catalysts are typically known as a combination of organometallic compounds of metals in Groups ~ of the periodic table and transition metal compounds of Groups ~ (including compounds with valences lower than the highest valence). A product or an improvement thereof. Furthermore, Ziegler-type catalysts can be modified to have a polymerization function by adding various third components or supporting transition metal compound components on a carrier for the purpose of improving catalyst performance, or by prepolymerizing the entire catalyst system with α-olefin. Including those that have been enhanced. The unpurified polyolefin to be treated in the present invention is obtained by polymerizing the above-mentioned olefin using the above-mentioned catalyst at a relatively low temperature (e.g. 0°C to 200°C) and low pressure (e.g. normal pressure to 50 kg/cm 2 ). In this case, neutralization treatment and solvent removal (in the case of suspension polymerization) are performed. The alkylene oxide used in the present invention is
Preferably, the agent is a lower alkylene oxide such as ethylene oxide or propylene oxide, which is capable of reacting with the catalyst residue in the crude polyolefin to inactivate it. Alkylene oxides can also be used in combination with other deactivating agents such as water, methanol, isopropanol, and the like. The inactivation treatment conditions (temperature, time, pressure, ratio of amount of drug to unpurified polyolefin) can be used as long as they are within the range of known conditions. However, at 20°C to 200°C for 1 minute to 4 hours,
Normal pressure to 100 Kg/cm 2 and a range of 0.01 to 10% are easy to implement. Through this purification process, the active chlorine content in purified polyolefin is either undetectable or
It can be reduced to about 10ppm. The above-mentioned purified polyolefin according to the present invention includes:
Mix a certain amount of the following inorganic double salts with water of crystallization or their calcined products. AlxSiy(OH) 3x+4y・nH 2 O Mgx(OH) 2y-2x (CO 3 ) y・nH 2 O MgxCay(CO 3 ) 22x+2y/2・nH 2 O MxSiy(CH) 2x+4y・nH 2 O MgxAlySiz(OH) 2x+3y+4z・nH 2 O MxAly(OH) 2x+3y-2z (A)・nH 2 O However, M is Mg or Ca, A is CO 3 , x,
y and n are positive numbers, and n is 0 or a positive integer. The above-mentioned kettled products refer to those obtained by heating these double salts to completely or partially remove attached water or water of crystallization and dehydrate them. The particle size or average particle diameter of the above-mentioned inorganic double salts or their calcined products (hereinafter sometimes referred to as the inorganic double salts according to the present invention, etc.) is about 10 μm or less, preferably 1 μm or less and about 0.01 μm. Even particles with a particle diameter of less than 0.01μ can be used as long as uniform mixing is possible. Not only the average particle diameter but also the specific surface area of the particles of the inorganic double salt according to the present invention are not limited, but a high one is preferable. The preferred surface area is
It is 10 to 300 m 2 /g. The mixing ratio of the inorganic double salt etc. and the purified polyolefin according to the present invention is 0.001 to 0.5% by weight based on the latter, preferably 0.005 to 0.1% by weight.
Weight%. As is clear from this mixing ratio, the amount of the inorganic double salt and the like according to the present invention added is substantially very small compared to other additives (eg, heat stabilizers). Therefore, it is surprising that the addition of such a small amount can sufficiently prevent off-odor (note: this noticeably appears in the molded product stage) in purified polyolefin. Although the amount added is small in this way, as long as uniform mixing is possible, the method of mixing the inorganic salt etc. into purified polyolefin etc. according to the present invention is as follows.
Not particularly limited. First, as for the timing of mixing, it may be mixed into the purified polyolefin before other additives, at the same time as the other additives, or after all other additives have been added, that is, when the purified polyolefin is pelletized. They can also be added and mixed in the plasticizing step. Further, since the amount added is very small, it is desirable to uniformly mix it with a small amount of purified polyolefin powder in advance and mix it with the purified polyolefin. Mixing equipment and mixing conditions are not limited, but
For example, use a high-speed stirring mixer (trade name: Henschel mixer) at room temperature to 50°C for 1 minute to 50°C.
Mix for 30 minutes. Other mixing devices may also be used, such as a ribbon blender or a V-blender. Even when the odorless polyolefin composition of the present invention is processed into molded products, films, fibers, and other molded products, there is little or no characteristic odor derived from alkylene oxide, and therefore, these molded products are It is possible to eliminate usage restrictions based on off-flavors (for example, the inability to use them in food containers) or to prevent a decrease in commercial value. The present invention will be explained below with reference to Examples and Comparative Examples. In addition, the numerical values shown in Examples and Comparative Examples were measured by the following method. MFR; ASTM-D1738 Ash content in polyolefin; Al, Ti, and Cl were measured by fluorescent X-ray analysis. Shown as XRFCl. Active Chlorine; sample amount of polyolefin at 300℃
The amount of hydrogen chloride in the gas generated was measured and expressed as the amount generated per polyolefin. YI (yellowness index): Measured using a color difference meter (manufactured by Suga Test Instruments Co., Ltd.). Molded product odor: A sensory test was conducted on the test piece immediately after it was taken out of the molding machine, and the odor was rated on the following five scales. 1: Very strong odor 2: Very strong odor 3: Odor 4: Slight odor 5: No odor ) are also shown using numerical symbols as shown below.
【表】【table】
Claims (1)
させて得た未精製ポリオレフイン中の触媒残渣を
アルキレンオキサイドを用いて不活性化して得ら
れた精製ポリオレフインに下記〜若しくはこ
れらのか焼生成物から選ばれた１種以上の処理剤
を0.001〜0.5重量％混合してなる無臭化ポリオレ
フイン組成物。 AlxSiy（OH）3x+4y・nH2O Mgx（OH）2y-2x（CO3）y・nH2O MgxCay（CO3）2x+2y/2・nH2O MxSiy（OH）2x+4y・nH2O MgxAlySiz（OH）2x+3y+4z・nH2O MxAly（OH）2x+3y-2z（Ａ）・nH2O ただし、ＭはMg若しくはCa、ＡはCO3、ｘ、
ｙ、ｚは整数、ｎは０若しくは正の整数。[Scope of Claims] 1. A purified polyolefin obtained by inactivating a catalyst residue in an unpurified polyolefin obtained by polymerizing an olefin using a Ziegler type catalyst using an alkylene oxide, and a calcined product of the following or these. An odorless polyolefin composition comprising 0.001 to 0.5% by weight of one or more processing agents selected from the following. AlxSiy(OH) 3x+4y・nH 2 O Mgx(OH) 2y-2x (CO 3 ) y・nH 2 O MgxCay(CO 3 ) 2x+2y/2・nH 2 O MxSiy(OH) 2x+4y・nH 2 O MgxAlySiz(OH) 2x+3y+4z・nH 2 O MxAly(OH) 2x+3y-2z (A)・nH 2 O However, M is Mg or Ca, A is CO 3 , x,
y and z are integers, and n is 0 or a positive integer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56214076A JPS58111807A (en) | 1981-12-24 | 1981-12-24 | Odorless polyolefin and its production |
| DE19823247842 DE3247842A1 (en) | 1981-12-24 | 1982-12-23 | Deodorised polyolefins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56214076A JPS58111807A (en) | 1981-12-24 | 1981-12-24 | Odorless polyolefin and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58111807A JPS58111807A (en) | 1983-07-04 |
| JPH0420020B2 true JPH0420020B2 (en) | 1992-03-31 |
Family
ID=16649845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56214076A Granted JPS58111807A (en) | 1981-12-24 | 1981-12-24 | Odorless polyolefin and its production |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS58111807A (en) |
| DE (1) | DE3247842A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60195141A (en) * | 1984-03-16 | 1985-10-03 | Mitsubishi Petrochem Co Ltd | Crystalline propylene polymer composition |
| JP3526062B2 (en) * | 1992-12-24 | 2004-05-10 | 旭電化工業株式会社 | Synthetic resin composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4912892A (en) * | 1972-05-15 | 1974-02-04 | ||
| DE2224558B2 (en) * | 1972-05-19 | 1979-02-22 | Basf Ag, 6700 Ludwigshafen | Process for reducing the halogen content from catalyst constituents in small-particle polyolefins |
| JPS50151243A (en) * | 1974-05-29 | 1975-12-04 | ||
| JPS5263246A (en) * | 1975-11-19 | 1977-05-25 | Matsushita Electric Ind Co Ltd | Thermoplastic resin compositions |
| DE2826623A1 (en) * | 1978-06-19 | 1980-01-03 | Basf Ag | METHOD FOR REDUCING THE HALOGEN CONTENT OF SMALL PARTICLES BY MEANS OF HALOGEN CATALYSTS OF POLYOLEFINS PRODUCED |
| JPS5580447A (en) * | 1978-12-14 | 1980-06-17 | Kyowa Chem Ind Co Ltd | Prevention of rust, deterioration or coloring of polyolefin and composition |
| JPS5672034A (en) * | 1979-11-20 | 1981-06-16 | Tokuyama Soda Co Ltd | Polyolefin composition |
-
1981
- 1981-12-24 JP JP56214076A patent/JPS58111807A/en active Granted
-
1982
- 1982-12-23 DE DE19823247842 patent/DE3247842A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3247842A1 (en) | 1983-07-14 |
| JPS58111807A (en) | 1983-07-04 |
| DE3247842C2 (en) | 1990-05-17 |
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